WO2023032803A1

WO2023032803A1 - Resin composition, cured product, organic el display device, and method for producing cured product

Info

Publication number: WO2023032803A1
Application number: PCT/JP2022/032018
Authority: WO
Inventors: 北村友弘; 山根麻央
Original assignee: 東レ株式会社
Priority date: 2021-08-30
Filing date: 2022-08-25
Publication date: 2023-03-09
Also published as: CN117858921A; KR20240051923A; TW202323342A

Abstract

The present invention addresses the problem of providing a resin composition which has excellent long-term reliability, does not cause luminous brightness or pixel shrinkage, and does not cause a reduced pixel luminous area ratio even over a long period of time. This resin composition comprises: an alkali-soluble resin (a) containing at least one selected from the group consisting of polyimides, polybenzoxazoles, polyamideimides, precursors of any of these, and copolymers thereof; and a novolac phenolic resin (b), wherein the content of the novolac phenolic resin having a molecular weight of 1,000 or less in the novolac phenolic resin (b) is 0.1-20 wt% in the novolac phenolic resin (b).

Description

Resin composition, cured product, organic EL display device and method for producing cured product

The present invention relates to a resin composition, a cured product, an organic EL display device, and a method for manufacturing an organic EL display device. Specifically, insulating films for organic electroluminescence (hereinafter referred to as EL) elements, flattening films for driving thin film transistor (hereinafter referred to as TFT) substrates of display devices using organic EL elements, wiring protection insulation for circuit substrates The present invention relates to a resin composition suitable for applications such as films, on-chip microlenses for solid-state imaging devices, and flattening films for various displays and solid-state imaging devices.

Many products using organic electroluminescence (hereinafter referred to as "organic EL") display devices have been developed for display devices with thin displays, such as smartphones, tablet PCs, and televisions. In general, an organic EL display device has a drive circuit, a planarizing layer, a first electrode, an insulating layer, a light-emitting layer and a second electrode on a substrate, and a voltage is applied between the first electrode and the second electrode facing each other. can be applied to emit light. Among these, resin compositions that can be patterned by ultraviolet irradiation are generally used as the material for the flattening layer and the material for the insulating layer. Among them, a resin composition using a polyimide-based resin is preferably used in that it can provide a highly reliable organic EL display device because the resin composition has high heat resistance and the gas component generated from the cured product is small. ing.

Resin compositions using polyimide-based resins that have been proposed so far include photosensitive resin compositions obtained by mixing a polyimide precursor with a photosensitive diazoquinone compound and a phenol novolac resin (see, for example, Patent Document 1), A positive photosensitive resin composition containing a resin having a phenolic hydroxyl group in a polyimide precursor or the like, a quinonediazide compound and a solvent (see, for example, Patent Document 2). However, the materials proposed in the above patent documents have a problem that the long-term reliability of the organic EL display device is low. Organic light-emitting materials are generally vulnerable to gas components and moisture, and exposure to these causes a decrease in emission luminance and pixel shrinkage. Here, the term "pixel shrinkage" refers to a phenomenon in which the luminance of light emitted from the edge of a pixel decreases or the pixel does not light up. In order to improve the long-term reliability of such display device elements, it is necessary to improve the durability of the organic light-emitting material itself, as well as to improve the peripheral properties such as a flattening layer covering the drive circuit and an insulating layer formed on the first electrode. It is essential to improve the water absorption and outgassing properties of the material. A positive photosensitive resin composition that does not cause a decrease in emission luminance or pixel shrinkage and has excellent long-term reliability has been proposed (see, for example, Patent Document 3). However, such a positive photosensitive resin composition has a problem that the retention rate of emission luminance is insufficient in terms of long-term reliability, and the emission area ratio of pixels decreases over a long period of time.

JP-A-7-248626 JP 2013-205553 A WO2017/159476

However, the materials proposed in the above-mentioned patent documents are preferable in terms of patterning processability by ultraviolet irradiation of the material for the flattening layer and the material for the insulating layer, but from the viewpoint of long-term reliability, sufficient performance It is difficult to say that it has SUMMARY OF THE INVENTION In view of the above problems, the object of the present invention is to provide a resin composition with excellent long-term reliability that does not cause a decrease in emission luminance or pixel shrinkage and does not reduce the pixel emission area ratio even over a long period of time. .

In order to solve the above problems, the resin composition of the present invention has the following constitution. i.e.
(1) Alkali-soluble resin (a) and novolac-type phenolic resin (b ), wherein the content of the novolac-type phenolic resin having a molecular weight of 1,000 or less in the novolac-type phenolic resin (b) is 0.1 to 20 in the novolac-type phenolic resin (b). Resin composition in weight percent.
(2) The weight-average molecular weight (Mw) of the novolak-type phenolic resin (b) is 3,000 or more and 15,000 or less, and the dispersion ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) ( The resin composition according to (1) above, wherein Mw)/(Mn) is from 1.1 to 3.5.
(3) The resin composition according to (1) or (2) above, wherein the novolak-type phenolic resin (b) contains an m-cresol novolac resin.
(4) The resin composition according to any one of (1) to (3), wherein the novolak-type phenolic resin (b) is 17 to 50 parts by weight per 100 parts by weight of the alkali-soluble resin (a).
(5) The resin composition according to any one of (1) to (4) above, further comprising a photosensitive compound (c).
(6) A cured product obtained by curing the resin composition according to any one of (1) to (5) above.
(7) An organic EL display device having a drive circuit, a planarizing layer, a first electrode, an insulating layer, a light-emitting layer and a second electrode on a substrate, wherein the planarizing layer and/or the insulating layer are (6) ).
(8) A step of applying the resin composition according to any one of (1) to (5) on a substrate to form a resin film, a step of exposing the resin film, and a step of developing the exposed resin film. and a method for producing a cured product, comprising the step of heat-treating the developed resin film.

The resin composition and cured product of the present invention do not cause a decrease in emission luminance or pixel shrinkage, and have excellent long-term reliability. By using this resin composition, an organic EL display device with excellent long-term reliability can be provided.

1 is a cross-sectional view of an example of an organic EL display device; FIG. It is a schematic diagram of the manufacturing procedure of the organic EL display device in the example.

An embodiment of the present invention will be described in detail.

The resin composition of the present invention contains at least one selected from the group consisting of polyimide, polybenzoxazole, polyamideimide, precursors of any of these and copolymers thereof, and an alkali-soluble resin (a) and a novolac type phenolic resin (b), wherein the content of the novolac-type phenolic resin having a molecular weight of 1,000 or less in the novolac-type phenolic resin (b) is 0.1 to 20% by weight.

In the present invention, the weight average molecular weight means the polystyrene-equivalent weight-average molecular weight measured by GPC (gel permeation chromatography), and the number-average molecular weight measured by GPC (gel permeation chromatography) means the polystyrene-equivalent number average molecular weight. . Here, the weight-average molecular weight or number-average molecular weight of the novolak-type phenolic resin (b) is the average molecular weight as a value representative of the entire novolac-type phenolic resin (b). This is the case of describing some molecules having that molecular weight in the novolac-type phenolic resin (b). In this case, the "molecular weight" is also the polystyrene-equivalent molecular weight measured by GPC (gel permeation chromatography).

<Alkali-soluble resin (a)>
The resin composition of the present invention comprises an alkali-soluble resin (a) (hereinafter referred to as , sometimes simply referred to as “alkali-soluble resin (a)”).

By including the alkali-soluble resin (a) in the resin composition of the present invention, it is possible to obtain a resin composition that has pattern workability and excellent heat resistance. In the present invention, the term “alkali-soluble” means that a solution obtained by dissolving a resin in γ-butyrolactone is coated on a silicon wafer and prebaked at 120° C. for 4 minutes to form a prebaked film having a film thickness of 10 μm±0.5 μm. After immersing the pre-baked film in a 2.38% by weight tetramethylammonium hydroxide aqueous solution (hereinafter sometimes referred to as an alkaline developer) at 23 ± 1 ° C. for 1 minute, the film thickness reduction when rinsing with pure water It means that the desired dissolution rate is 50 nm/min or more.

The alkali-soluble resin (a) used in the present invention preferably has an acidic group in the structural unit of the resin and/or at the end of its main chain in order to impart alkali solubility. Examples of acidic groups include carboxy groups, phenolic hydroxyl groups, and sulfonic acid groups. Also, the alkali-soluble resin (a) preferably contains a fluorine atom. This is because the presence of fluorine atoms makes the surface of the pre-baked film formed water-repellent, so that it is possible to prevent the alkali developer from permeating from the surface.

The alkali-soluble resin (a) used in the present invention more preferably contains a polyimide, a polyimide precursor, a polybenzoxazole precursor or a copolymer thereof, and from the viewpoint of further improving sensitivity, a polyimide precursor or More preferably, it contains a polybenzoxazole precursor. Here, the polyimide precursor refers to a resin that is converted to polyimide by heat treatment or chemical treatment, and examples thereof include polyamic acid and polyamic acid ester. A polybenzoxazole precursor refers to a resin that is converted to polybenzoxazole by heat treatment or chemical treatment, and includes, for example, polyhydroxyamide.

The polyimide described above preferably has a structural unit represented by the following general formula (1), and the polyimide precursor and the polybenzoxazole precursor preferably have a structural unit represented by the following general formula (2). In such a case, two or more of these may be contained, or a resin obtained by copolymerizing a structural unit represented by general formula (1) and a structural unit represented by general formula (2) may be used.

In general formula (1), R ¹¹ represents a 4- to 10-valent organic group having 5 to 40 carbon atoms, and R ¹² represents a di- to 8-valent organic group having 5 to 40 carbon atoms. R ¹³ and R ¹⁴ each independently represent a carboxy group, a sulfonic acid group or a hydroxyl group. p and q represent integers from 0 to 6, p+q>0.

In general formula (2), R ¹⁵ and R ¹⁶ represent a divalent to octavalent organic group having 5 to 40 carbon atoms. R ¹⁷ and R ¹⁸ each independently represent a phenolic hydroxyl group, a sulfonic acid group or COOR ¹⁹ , and may be a single group or a mixture of different groups. R ¹⁹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. r and s represent integers from 0 to 6; However, r+s>0.

The polyimide, polyimide precursor, polybenzoxazole precursor or copolymer thereof preferably has 5 to 100,000 structural units represented by general formula (1) or general formula (2). Moreover, in addition to the structural unit represented by general formula (1) or general formula (2), it may have other structural units. In this case, the polyimide, polyimide precursor, polybenzoxazole precursor or copolymer thereof contains structural units represented by general formula (1) or general formula (2) in an amount of 50 mol% or more of all structural units. It is preferable to have

In general formula (1) above, R ¹¹ -(R ¹³ ) _p represents an acid dianhydride residue. R ¹¹ is a tetravalent to decavalent organic group, preferably an organic group having 5 to 40 carbon atoms containing an aromatic ring or a cycloaliphatic group.

Specific examples of acid dianhydride residues include pyromellitic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′- biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3 ,3′-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride anhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9 ,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride, 2,3, 6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis ( 3,4-dicarboxyphenyl)hexafluoropropane, and aromatic tetracarboxylic dianhydrides such as acid dianhydrides having the structures shown in the following general formulas (3) and (4) Residues derived from, residues derived from aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride, cyclic aliphatic such as 1,2,3,4-cyclopentanetetracarboxylic dianhydride Examples include residues derived from aliphatic tetracarboxylic dianhydride containing groups. Polyimides, polyimide precursors, polybenzoxazole precursors, or copolymers thereof may have two or more thereof.

^R20 represents an oxygen atom, C( _CF3 ) ₂ or C( _CH3 ) ₂ . ^R21 and ^R22 represent a hydrogen atom or a hydroxyl group.

In general formula (2) above, R ¹⁶ -(R ¹⁸ ) _s represents an acid residue. R ¹⁶ is a divalent to octavalent organic group having 5 to 40 carbon atoms, preferably an organic group having 5 to 40 carbon atoms containing an aromatic ring or a cycloaliphatic group.

Acid residues include residues derived from dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyletherdicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyldicarboxylic acid, benzophenonedicarboxylic acid, triphenyldicarboxylic acid, trimellit residues derived from tricarboxylic acids such as acid, trimesic acid, diphenylethertricarboxylic acid, biphenyltricarboxylic acid, pyromellitic acid, 3,3′,4,4′-biphenyltetracarboxylic acid, 2,3,3′,4′ -biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 2,2',3,3'-benzophenonetetracarboxylic acid , 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 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-di carboxyphenyl)ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9, Residues derived from 10-perylenetetracarboxylic acid and aromatic tetracarboxylic acids having the structures shown in the following general formulas (5) and (6), and residues of aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and residues derived from tetracarboxylic acids such as residues derived from aliphatic tetracarboxylic acids containing cycloaliphatic groups such as 1,2,3,4-cyclopentanetetracarboxylic acid. Polyimides, polyimide precursors, polybenzoxazole precursors, or copolymers thereof may have two or more thereof.

Among these, in tricarboxylic acids and tetracarboxylic acids, one or two carboxy groups correspond to R ¹⁸ in general formula (2). More preferably, 1 to 4 hydrogen atoms bonded to carbon atoms in the dicarboxylic acids, tricarboxylic acids, and tetracarboxylic acids exemplified above are substituted with R ¹⁸ in the general formula (2), preferably hydroxyl groups.

R ¹² -(R ¹⁴ ) _q in the general formula (1) and R ¹⁵ -(R ¹⁷ ) _r in the general formula (2) represent diamine residues. R ¹² and R ¹⁵ are divalent to octavalent organic groups having 5 to 40 carbon atoms, and organic groups having 5 to 40 carbon atoms containing an aromatic ring or a cycloaliphatic group are preferred.

Diamine residues include 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy) Benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether , 1,4-bis(4-aminophenoxy)benzene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-diethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl -4,4'-diaminobiphenyl, 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, 2 ,2'-bis(trifluoromethyl)-5,5'-dihydroxybenzidine, residues derived from aromatic diamines such as compounds in which at least part of the hydrogen atoms of these aromatic rings are substituted with alkyl groups or halogen atoms. groups, residues derived from aliphatic diamines containing cycloaliphatic groups such as cyclohexyldiamine and methylenebiscyclohexylamine, residues derived from diamines having structures shown in the following general formulas (7) to (12), etc. mentioned. Polyimides, polyimide precursors, polybenzoxazole precursors, or copolymers thereof may have two or more thereof.

^R20 represents an oxygen atom, C( _CF3 ) ₂ or C( _CH3 ) ₂ . R ²¹ to R ²⁴ each independently represent a hydrogen atom or a hydroxyl group.

In addition, by blocking the terminal of these resins with a monoamine, acid anhydride, acid chloride, monocarboxylic acid, or active ester compound having an acidic group, a resin having an acidic group at the main chain terminal can be obtained. .

Preferred examples of monoamines having an acidic group include 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy -4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene , 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4 -aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothio Phenol, 3-aminothiophenol, 4-aminothiophenol and the like can be mentioned. You may use 2 or more types of these.

Preferable examples of acid anhydrides include phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, and 3-hydroxyphthalic anhydride. You may use 2 or more types of these.

Preferred examples of monocarboxylic acids include 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1 -hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene and the like. You may use 2 or more types of these.

Preferred examples of acid chlorides include monoacid chloride compounds in which the carboxy group of the monocarboxylic acid is acid chloride, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6- Examples include monoacid chloride compounds in which only one carboxy group of dicarboxylic acids such as dicarboxynaphthalene, 1,7-dicarboxynaphthalene, and 2,6-dicarboxynaphthalene is acid chlorided. You may use 2 or more types of these.

Preferred examples of active ester compounds include reaction products of the monoacid chloride compounds with N-hydroxybenzotriazole and N-hydroxy-5-norbornene-2,3-dicarboximide. You may use 2 or more types of these.

The terminal blocking agent introduced into the alkali-soluble resin (a) can be easily detected by the following method. For example, a resin into which a terminal blocking agent has been introduced is dissolved in an acidic solution, decomposed into an amine component and an acid component, which are the structural units of the resin, and subjected to gas chromatography (GC) or NMR measurement to determine the terminal The encapsulant can be easily detected. It is also possible to detect the resin into which the terminal blocking agent has been introduced by pyrolysis gas chromatography (PGC), infrared spectrum, and ¹³ C-NMR spectrum measurement.

The alkali-soluble resin (a) used in the present invention is synthesized by a known method.

Methods for producing polyamic acid or polyamic acid ester, which are polyimide precursors, include, for example, a method of reacting a tetracarboxylic dianhydride and a diamine compound at a low temperature, and a method of obtaining a diester with a tetracarboxylic dianhydride and an alcohol. , then a method of reacting with an amine in the presence of a condensing agent, a method of obtaining a diester with a tetracarboxylic dianhydride and an alcohol, followed by acid chloride of the remaining dicarboxylic acid and reaction with an amine, and the like. .

A method for producing polyhydroxyamide, which is a polybenzoxazole precursor, includes, for example, a method of condensing a bisaminophenol compound and a dicarboxylic acid. Specifically, for example, a method of reacting a dehydration condensing agent such as dicyclohexylcarbodiimide (DCC) with an acid and then adding a bisaminophenol compound thereto, a method of adding a tertiary amine such as pyridine to a solution of a bisaminophenol compound and dicarboxylic acid. A method of dropping a solution of acid dichloride and the like can be mentioned.

Examples of methods for producing polyimide include dehydration and ring closure of the polyamic acid or polyamic acid ester obtained by the above method. Methods for dehydration and ring closure include chemical treatment with an acid or base, heat treatment, and the like.

Examples of methods for producing polybenzoxazole include a method of dehydrating and ring-closing the polyhydroxyamide obtained by the above method. Methods for dehydration and ring closure include chemical treatment with an acid or base, heat treatment, and the like.

Polyamideimide precursors include tricarboxylic acids, corresponding tricarboxylic acid anhydrides, and polymers of tricarboxylic acid anhydride halides and diamine compounds, preferably polymers of trimellitic anhydride chloride and aromatic diamine compounds. Examples of the method for producing a polyamideimide precursor include a method of reacting a tricarboxylic acid, a corresponding tricarboxylic acid anhydride, a tricarboxylic acid anhydride halide, etc. with a diamine compound at a low temperature.

Examples of methods for producing polyamideimide include a method of reacting trimellitic anhydride and an aromatic diisocyanate, and a method of dehydrating and ring-closing the polyamideimide precursor obtained by the above method. Methods for dehydration and ring closure include chemical treatment with an acid or base, heat treatment, and the like.

<Novolak-type phenolic resin (b)>
The resin composition of the present invention contains a novolak-type phenolic resin (b). The novolak-type phenolic resin (b) can be obtained by a known method of heterogeneously reacting phenols and aldehydes in the presence of an acid catalyst.

The novolac-type phenolic resin (b) used in the present invention preferably contains an m-cresol novolak resin from the viewpoint of solubility in an alkaline developer. The novolac-type phenolic resin (b) is generally produced using phenols as raw materials, and m-cresol novolac resins are resins having a structure obtained by using m-cresol in phenols. When a novolac-type phenolic resin containing m-cresol novolac resin is used as the novolac-type phenolic resin, the weight average molecular weight (Mw) is preferably 3,000 or more and 15,000 or less, preferably 7000 or more and 13,000 or less. is more preferable. Furthermore, since it exhibits moderate solubility in an alkaline developer, good sensitivity can be obtained.

Preferable examples of other phenols used as raw materials for the novolac-type phenolic resin (b) used in the present invention include phenol, o-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol and the like can be mentioned.

Preferable examples of aldehydes used as raw materials for the novolak-type phenolic resin (b) used in the present invention include formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, salicylaldehyde, and the like. . Among these, formalin is particularly preferred. Two or more of these aldehydes may be combined.

The blending molar ratio (F/P) of the phenols (P) and the aldehydes (F) when producing the novolak-type phenolic resin (b) used in the present invention is preferably 0.33 to 1.20, It is more preferably 0.50 to 1.00. When the compounding ratio is within the above preferable range, the yield is good, and on the other hand, it is possible to prevent the dispersion ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polystyrene equivalent weight average molecular weight from becoming large.

The condensation reaction of phenols and aldehydes is usually carried out using an acid catalyst. Examples of acid catalysts that can be used include inorganic or organic acids such as phosphoric acid, oxalic acid, formic acid, acetic acid, p-toluenesulfonic acid, hydrochloric acid and sulfuric acid. Of these, phosphoric acid is particularly preferred. Specifically, in order to form a site for a phase separation reaction between phenols and aldehydes, for example, an aqueous solution of polyphosphoric acid such as metaphosphoric acid, pyrophosphoric acid, orthophosphoric acid, triphosphoric acid, and tetraphosphoric acid can be used. Since it plays a role of forming a field for a phase separation reaction with phenols in the presence thereof, aqueous solutions such as 75% by weight phosphoric acid and 89% by weight phosphoric acid are generally preferred.

The condensation reaction is carried out without solvent or in an organic solvent. Organic solvents include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, butanediol, pentanediol, ethylene glycol, propylene glycol and diethylene glycol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone. Cellosolves such as , methyl cellosolve, ethyl cellosolve and butyl cellosolve, cellosolve esters such as methyl cellosolve acetate and ethyl cellosolve acetate, and cyclic ethers such as 1-4-dioxane are preferably used.

The amount of water in the reaction system affects the phase separation effect and production efficiency, but it is generally 40% or less on a weight basis. If the amount of water exceeds 40%, production efficiency may decrease.

In addition, the reaction temperature between phenols and aldehydes is important for enhancing the phase separation effect, and is generally 40°C to reflux temperature, preferably 80°C to reflux temperature, more preferably reflux temperature. The reaction time varies depending on, for example, the reaction temperature, raw material compounding ratio, acid catalyst compounding amount, etc., but is generally about 1 to 30 hours. As the reaction environment, normal pressure is suitable, but if the heterogeneous reaction is maintained, the reaction may be carried out under increased pressure or reduced pressure.

In the present invention, the weight average molecular weight (Mw) of the novolak-type phenolic resin (b) is 3,000 or more and 15,000 or less, and the dispersion ratio (Mw)/ (Mn) is preferably 1.1 to 3.5, more preferably 1.8 to 2.8. Within this range, patterning workability of the flattening layer material and the insulating layer material by ultraviolet irradiation is excellent.

In the resin composition of the present invention, the content of the novolak-type phenolic resin (b) having a molecular weight of 1,000 or less is 0.1 to 20% by weight in the novolak-type phenolic resin (b). , preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight. If the content of the novolak-type phenolic resin having a molecular weight of 1,000 or less exceeds 20 parts by weight in the (b) novolak-type phenolic resin, a large amount of outgassing is generated, causing deterioration in long-term reliability of the organic EL display device. On the other hand, if the content is less than 0.1% by weight, the production yield is lowered, which is not preferable.

The content of the novolak-type phenolic resin (b) is preferably 17-50 parts by weight, more preferably 25-40 parts by weight, relative to 100 parts by weight of the alkali-soluble resin (a). When the content of the novolak-type phenolic resin (b) is within the above preferred range with respect to 100 parts by weight of the alkali-soluble resin (a), the sensitivity can be appropriately expressed, while the amount of outgassing is small, and the organic EL display device can be used. Less likely to cause deterioration of long-term reliability.

<Photosensitive compound (c)>
The resin composition of the present invention preferably contains a photosensitive compound (c). If the photosensitive compound (c) is contained, a resin composition having photosensitivity can be obtained, so that the exposure and development steps can be performed without applying a photoresist, and then the photoresist is removed. No need. Examples of the photosensitive compound (c) include a photoacid generator (c1) and a photopolymerization initiator (c2). The photoacid generator (c1) is a compound that generates an acid upon irradiation with light, and the photopolymerization initiator (c2) is a compound that undergoes bond cleavage and/or reaction upon irradiation with light to generate radicals.

The content of the photosensitive compound (c) is preferably 0.01 to 100 parts by weight with respect to 100 parts by weight of the alkali-soluble resin (a). If the content of the photosensitive compound (c) is 0.01 parts by weight or more and 100 parts by weight or less, photosensitivity can be imparted while maintaining heat resistance, chemical resistance and mechanical properties of the cured product. .

By containing the photoacid generator (c1), an acid is generated in the light-irradiated area and the solubility of the light-irradiated area in an alkaline aqueous solution increases, so that a positive relief pattern in which the light-irradiated area dissolves can be obtained. can. Further, by containing the photoacid generator (c1) and an epoxy compound or a thermal cross-linking agent described later, the acid generated in the light-irradiated portion accelerates the cross-linking reaction of the epoxy compound and the thermal cross-linking agent, and the light-irradiated portion becomes insoluble. A negative relief pattern can be obtained. On the other hand, by containing a photopolymerization initiator (c2) and a radically polymerizable compound described later, radical polymerization proceeds in the light-irradiated areas, and a negative relief pattern in which the light-irradiated areas become insoluble can be obtained.

Examples of the photoacid generator (c1) include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts. It is preferable to contain two or more kinds of photoacid generators (c1), and it is more preferable to contain one more kind of quinonediazide compound as an essential component, so that a highly sensitive photosensitive resin composition can be obtained. A quinonediazide compound is particularly preferable as the photoacid generator (c1) from the viewpoint of light emission reliability when the cured product of the present invention, which will be described later, is used as a planarizing layer and/or an insulating layer of an organic EL display device.

As the quinonediazide compound, a compound in which naphthoquinonediazide sulfonic acid is bonded to a compound having a phenolic hydroxyl group via an ester is preferable. As the compound having a phenolic hydroxyl group used here, known compounds may be used, and those into which 4-naphthoquinonediazidesulfonic acid or 5-naphthoquinonediazidesulfonic acid is introduced via an ester bond are preferred. Examples can be given, but compounds other than these can also be used. Moreover, it is preferable that 50 mol % or more of all the functional groups of the compound having a phenolic hydroxyl group are substituted with quinonediazide. By using a quinonediazide compound substituted by 50 mol % or more, the affinity of the quinonediazide compound for an alkaline aqueous solution is lowered. As a result, the solubility of the resin composition in the unexposed area in an alkaline aqueous solution is greatly reduced. Further, the quinonediazide sulfonyl group is converted to indenecarboxylic acid by exposure, and a high dissolution rate in an alkaline aqueous solution of the photosensitive resin composition in the exposed area can be obtained. That is, as a result, the dissolution rate ratio between the exposed area and the unexposed area of the composition can be increased, and a pattern with high resolution can be obtained.

A quinonediazide compound obtained by introducing 4-naphthoquinonediazide sulfonic acid through an ester bond has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. A quinonediazide compound in which 5-naphthoquinonediazide sulfonic acid is introduced via an ester bond has absorption extending to the g-line region of a mercury lamp, and is suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinonediazide sulfonyl ester compound or a 5-naphthoquinone diazidesulfonyl ester compound depending on the exposure wavelength.

By using these quinone diazide compounds, the resolution, sensitivity, and film retention rate are further improved.

Among the photoacid generators (c1), sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts are preferable because they moderately stabilize the acid component generated by exposure. Among them, sulfonium salts are preferred. Furthermore, a sensitizer and the like can be contained as necessary.

In the present invention, the content of the photoacid generator (c1) is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the alkali-soluble resin (a) from the viewpoint of increasing sensitivity. Among them, the quinonediazide compound is preferably 3 to 40 parts by weight. The total amount of sulfonium salt, phosphonium salt, diazonium salt and iodonium salt is preferably 0.5 to 20 parts by weight.

Examples of the photopolymerization initiator (c2) include benzyl ketal photopolymerization initiators, α-hydroxyketone photopolymerization initiators, α-aminoketone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, and oxime esters. photoinitiator, acridine photoinitiator, titanocene photoinitiator, benzophenone photoinitiator, acetophenone photoinitiator, aromatic ketoester photoinitiator, benzoic acid ester photoinitiator agents and the like. Two or more photopolymerization initiators (c2) may be contained. From the viewpoint of further improving sensitivity, it is more preferable to contain any of an α-aminoketone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, and an oxime ester photopolymerization initiator.

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

Examples of acylphosphine oxide photopolymerization initiators include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl). )-(2,4,4-trimethylpentyl)phosphine oxide.

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

In the present invention, the content of the photopolymerization initiator (c2) is 0.1 parts by weight with respect to a total of 100 parts by weight of the alkali-soluble resin (a) and the radically polymerizable compound described later, from the viewpoint of further improving sensitivity. 1 part by weight or more is preferable, and 1 part by weight or more is more preferable. On the other hand, from the viewpoint of further improving the resolution and reducing the taper angle, it is preferably 25 parts by weight or less, more preferably 15 parts by weight or less.
<Radical polymerizable compound>
The resin composition of the present invention may further contain a radically polymerizable compound.

A radically polymerizable compound is a compound that has multiple ethylenically unsaturated double bonds in its molecule. During exposure, the radicals generated from the photopolymerization initiator (c2) described above promote radical polymerization of the radically polymerizable compound, and insolubilization of the light-irradiated portion can yield a negative pattern. Furthermore, by containing a radically polymerizable compound, the photocuring of the light-irradiated portion is accelerated, and the sensitivity can be further improved. In addition, since the crosslink density after thermosetting is improved, the hardness of the cured product can be improved.

As the radically polymerizable compound, a compound having a (meth)acrylic group, which facilitates the progress of radical polymerization, is preferable. Compounds having two or more (meth)acrylic groups in the molecule are more preferable from the viewpoint of improving the sensitivity at the time of exposure and improving the hardness of the cured product. The double bond equivalent of the radically polymerizable compound is preferably 80 to 400 g/mol from the viewpoint of improving the sensitivity during exposure and improving the hardness of the cured product.

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

In the present invention, the content of the radically polymerizable compound is 15% by weight with respect to the total 100% by weight of the alkali-soluble resin (a) and the radically polymerizable compound, from the viewpoint of further improving the sensitivity and reducing the taper angle. The above is preferable, and 30% by weight or more is more preferable. On the other hand, from the viewpoint of further improving the heat resistance of the cured product and reducing the taper angle, it is preferably 65% by weight or less, more preferably 50% by weight or less.

<Thermal cross-linking agent>
The resin composition of the present invention may contain a thermal cross-linking agent. A thermal cross-linking agent refers to a compound having at least two thermally reactive functional groups such as an alkoxymethyl group, a methylol group, an epoxy group, and an oxetanyl group in the molecule. By containing a thermal cross-linking agent, it is possible to cross-link the alkali-soluble resin (a) or other additive components and improve the heat resistance, chemical resistance and hardness of the film after thermal curing. In addition, the amount of outgassing from the cured product can be further reduced, and the long-term reliability of the organic EL display device can be improved.

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

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

Preferable examples of compounds having at least two oxetanyl groups include Ethanacol EHO, Ethanacol OXBP, Ethanacol OXTP, Ethanacol OXMA (manufactured by Ube Industries, Ltd.), and oxetaneated phenol novolak.

The thermal cross-linking agent may be contained in combination of two or more.

The content of the thermal cross-linking agent is preferably 1% by weight or more and 30% by weight or less with respect to 100% by weight of the total amount of the resin composition excluding the organic solvent. If the content of the thermal cross-linking agent is 1% by weight or more, the chemical resistance and hardness of the cured product can be further enhanced. In addition, if the content of the thermal crosslinking agent is 30% by weight or less, the amount of outgassing from the cured product can be further reduced, the long-term reliability of the organic EL display device can be further improved, and the storage stability of the resin composition can be improved. Also excellent.

<Organic solvent>
The resin composition of the present invention may contain an organic solvent. By containing an organic solvent, a varnish state can be obtained, and coatability can be improved.

Organic solvents include polar aprotic solvents such as γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol. Monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl Ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene Ethers such as glycol monoethyl ether, tetrahydrofuran, and dioxane, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and diacetone alcohol, 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, ethyl lactate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, 3-methoxypropionate ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate , 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-propionate -butyl, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyrate Esters such as butyl, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate, aromatic hydrocarbons such as toluene and xylene, N-methylpyrrolidone, Amides such as N,N-dimethylformamide, N,N-dimethylpropionamide, 3-methoxy-N,N-dimethylpropionamide, N,N-dimethylacetamide, and the like are included. You may contain 2 or more types of these.

Although the content of the organic solvent is not particularly limited, it is preferably 100 to 3,000 parts by weight, more preferably 150 to 2,000 parts by weight, based on 100 parts by weight of the total resin composition excluding the organic solvent. The ratio of the solvent having a boiling point of 180° C. or higher to the total amount of the organic solvent is preferably 20 parts by weight or less, more preferably 10 parts by weight or less. By setting the proportion of the solvent having a boiling point of 180° C. or higher to 20 parts by weight or less, the amount of outgassing after heat curing can be further reduced, and as a result, the long-term reliability of the organic EL device can be further improved.

<Adhesion improver>
The resin composition of the present invention may contain an adhesion improver. Adhesion improvers include vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, Silane coupling agents such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, titanium chelating agents, aluminum chelating agents, aromatic amine compounds and alkoxy group-containing Examples thereof include compounds obtained by reacting silicon compounds. You may contain 2 or more types of these. By containing these adhesion improvers, it is possible to improve the adhesion to a base material such as a silicon wafer, ITO, SiO ₂ , or silicon nitride when developing a resin film. In addition, resistance to oxygen plasma and UV ozone treatment used for cleaning can be enhanced. The content of the adhesion improver is preferably 0.1 to 10% by weight with respect to 100% by weight of the total amount of the resin composition excluding the organic solvent.

<Surfactant>
The resin composition of the present invention may contain a surfactant as necessary to improve the wettability with the substrate. Examples of surfactants include SH series, SD series, and ST series from Dow Corning Toray Co., Ltd., BYK series from BYK Chemie Japan Co., Ltd., KP series from Shin-Etsu Chemical Co., Ltd., and NOF Corporation. Disform series of DIC Corporation, "Megafac (registered trademark)" series of DIC Corporation, Florard series of Sumitomo 3M Limited, "Surflon (registered trademark)" series of Asahi Glass Co., Ltd., "Asahi Guard (registered trademark)" series of Asahi Glass Co., Ltd. )" series, Omnova Solution's Polyfox series, etc., Kyoeisha Chemical Co., Ltd.'s Polyflow series, Kusumoto Kasei Co., Ltd.'s "Disparon (registered trademark)" series, etc. Alternatively, a methacrylic surfactant may be used.

The content of the surfactant is preferably 0.001 to 1% by weight with respect to 100% by weight of the total amount of the resin composition excluding the organic solvent.

<Inorganic particles>
The resin composition of the present invention may contain inorganic particles. Preferred specific examples of inorganic particles include silicon oxide, titanium oxide, barium titanate, alumina, and talc. The primary particle diameter of the inorganic particles is preferably 100 nm or less, more preferably 60 nm or less.

The content of the inorganic particles is preferably 5 to 90% by weight with respect to 100% by weight of the total amount of the resin composition excluding the organic solvent.

<Thermal acid generator>
The resin composition of the present invention may contain a thermal acid generator within a range that does not impair the long-term reliability of the organic EL display device. The thermal acid generator generates an acid when heated to accelerate the cross-linking reaction of the thermal cross-linking agent. It promotes cyclization and can further improve the mechanical properties of the cured product.

The thermal decomposition initiation temperature of the thermal acid generator used in the present invention is preferably 50°C to 270°C, more preferably 250°C or less. In addition, no acid is generated when the resin composition of the present invention is applied to a substrate and then dried (prebaking: about 70 to 140° C.), and the final heating (curing: about 100 to 100° C.) after patterning by subsequent exposure and development. It is preferable to select one that generates an acid at 400° C.), because it can suppress a decrease in sensitivity during development.

The acid generated from the thermal acid generator used in the present invention is preferably a strong acid, and examples thereof include arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid and butanesulfonic acid. and haloalkylsulfonic acids such as trifluoromethylsulfonic acid and the like are preferred. They are used as salts such as onium salts or as covalent compounds such as imidosulfonates. You may contain 2 or more types of these.

The content of the thermal acid generator is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, relative to 100% by weight of the total amount of the resin composition excluding the organic solvent. By containing 0.01% by weight or more of the thermal acid generator, the cross-linking reaction and cyclization of the unclosed ring structure of the resin are promoted, so that the mechanical properties and chemical resistance of the cured product can be further improved. From the viewpoint of long-term reliability of the organic EL display device, it is preferably 5% by weight or less, more preferably 2% by weight or less.

<Method for producing resin composition>
Next, an example of a preferable manufacturing method for obtaining the resin composition of the present invention will be described. For example, the components (a) to (c) and, if necessary, a coloring agent, a thermal cross-linking agent, an organic solvent, an adhesion improver, a surfactant, a compound having a phenolic hydroxyl group, an inorganic particle, a thermal acid generator, etc. are dissolved. A resin composition can be obtained by allowing the Dissolution methods include stirring and heating. When heating, the heating temperature is preferably set within a range that does not impair the performance of the resin composition, and is usually room temperature to 80°C. In addition, the order of dissolving each component is not particularly limited, and for example, a method of dissolving compounds in order of low solubility can be mentioned. In addition, for ingredients that tend to generate bubbles during stirring and dissolution, such as surfactants and some adhesion improvers, by adding them at the end after dissolving the other ingredients, the other ingredients will not be dissolved due to the generation of bubbles. can be prevented. The obtained resin composition is preferably filtered using a filtration filter to remove dust and particles. Examples of filter pore sizes include, but are not limited to, 0.5 μm, 0.2 μm, 0.1 μm, 0.07 μm, 0.05 μm, 0.02 μm. Materials for the filter include polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), etc., and polyethylene and nylon are preferred.

<Cured product>
Next, the cured product of the present invention will be described in detail.

The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention.

The resin composition can be cured by heat treatment. The heat treatment may be performed by selecting a certain temperature and increasing the temperature stepwise, or by selecting a certain temperature range and continuously increasing the temperature for 5 minutes to 5 hours. For example, heat treatment is performed at 150° C. and 250° C. for 30 minutes each. Alternatively, a method of linearly raising the temperature from room temperature to 300° C. over 2 hours can be used. The heat treatment conditions in the present invention are preferably 300° C. or higher, more preferably 350° C. or higher, from the viewpoint of reducing the amount of outgas generated from the cured product. The temperature is preferably 500° C. or lower, more preferably 450° C. or lower, from the viewpoint of imparting sufficient film toughness to the cured product.

The cured product of the present invention can be suitably used as a gate insulating layer or interlayer insulating layer of a thin film transistor.

<Method for producing cured product>
The cured product of the present invention can be obtained by applying the resin composition to a substrate to form a resin film, drying the resin film as necessary, exposing the resin film to light, and developing the exposed resin film. and a step of heat-treating the developed resin film. Details of each step are described below.

First, the process of applying the resin composition on a substrate to form a resin film will be described.

The resin composition of the present invention is applied by a spin coating method, a slit coating method, a dip coating method, a spray coating method, a printing method, or the like to obtain a coating film of the resin composition. Among these, the slit coating method is preferably used. The slit coating method is advantageous in terms of cost reduction because it can be applied with a small amount of application liquid. The amount of the coating liquid required for the slit coating method is, for example, about 1/5 to 1/10 of that for the spin coating method. The slit nozzle used for coating is not particularly limited, and those marketed by multiple manufacturers can be used. Specifically, "Linear Coater" manufactured by Dainippon Screen Mfg. Co., Ltd., "Spinless" manufactured by Tokyo Ohka Kogyo Co., Ltd., "TS Coater" manufactured by Toray Engineering Co., Ltd., "Table Coater" manufactured by Chugai Ro Co., Ltd. , "CS Series" and "CL Series" manufactured by Tokyo Electron Ltd., "Inline Slit Coater" manufactured by Thermatronics Trading Co., Ltd., and "Head Coater HC Series" manufactured by Hirata Corporation. The coating speed is generally in the range of 10 mm/sec to 400 mm/sec. The film thickness of the coating film varies depending on the solid content concentration and viscosity of the resin composition, but it is usually applied so that the film thickness after drying is 0.1 to 10 μm, preferably 0.3 to 5 μm.

Prior to applying the resin composition, the base material to be coated with the resin composition may be pretreated with the above-described adhesion improver. For example, a solution obtained by dissolving 0.5 to 20% by weight of an adhesion improver in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate is used. and a method of treating the substrate surface. Methods for treating the substrate surface include spin coating, slit die coating, bar coating, dip coating, spray coating, vapor treatment, and the like.

After applying the resin composition, dry it as necessary. It is common to dry under reduced pressure together with the substrate on which the coating film is formed. For example, a substrate having a coating film formed thereon is placed on proxy pins placed in a vacuum chamber, and dried under reduced pressure by reducing the pressure in the vacuum chamber. At this time, if the substrate and the top plate of the vacuum chamber are separated from each other, a large amount of air between the substrate and the top plate of the vacuum chamber flows during drying under reduced pressure, which tends to cause unevenness. Therefore, it is preferable to adjust the proxy pin height so as to narrow the gap. The distance between the substrate and the top plate of the vacuum chamber is preferably about 2-20 mm, more preferably 2-10 mm.

The speed of drying under reduced pressure depends on the vacuum chamber volume, the vacuum pump capacity, the diameter of the pipe between the chamber and the pump, etc. For example, in the state where there is no coated substrate, the pressure in the vacuum chamber is reduced to 40 Pa after 60 seconds. set and used. A general vacuum drying time is often about 30 seconds to 100 seconds, and the ultimate pressure in the vacuum chamber at the end of the vacuum drying is usually 100 Pa or less with the coated substrate in place. By setting the ultimate pressure to 100 Pa or less, the surface of the coating film can be kept in a non-sticky and dry state, thereby suppressing surface contamination and generation of particles during subsequent substrate transport.

After applying the resin composition or drying the applied resin composition under reduced pressure, the coating film is generally dried by heating. This step is also called pre-baking. Heat drying uses a hot plate, an oven, an infrared ray, or the like. When a hot plate is used for drying by heating, the coating film is held and heated directly on the plate or on a jig such as a proxy pin installed on the plate. Materials for proxy pins include metal materials such as aluminum and stainless steel, and synthetic resins such as polyimide resin and "Teflon" (registered trademark). . The height of the proxy pin varies depending on the size of the substrate, the type of coating film, the purpose of heating, etc., but is preferably about 0.1 to 10 mm. The heating temperature varies depending on the type and purpose of the coating film, and is preferably in the range of 50° C. to 180° C. for 1 minute to several hours.

Next, the step of forming a pattern from the obtained resin film, that is, the step of exposing the resin film and the subsequent step of developing, will be described.

In the process of exposing the resin film, the photosensitive resin film is irradiated with actinic rays through a mask having a desired pattern. Actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, X-rays, etc. In the present invention, it is preferable to use i-rays (365 nm), h-rays (405 nm) and g-rays (436 nm) of a mercury lamp. . In the case of positive photosensitivity, the exposed portion dissolves in the developer. In the case of negative photosensitivity, the exposed areas are cured and rendered insoluble in the developer.

In the process of developing the exposed resin film, after exposure, a desired pattern is formed by removing the exposed portion in the case of a positive type and the non-exposed portion in the case of a negative type using a developer. As a developer for both positive and negative types, tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, Aqueous solutions of alkaline compounds such as dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine and hexamethylenediamine are preferred. In some cases, these alkaline aqueous solutions are added with a polar solvent such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, dimethylacrylamide, methanol, ethanol, Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone may be added alone or in combination. good. As a developing method, methods such as spray, puddle, immersion, and ultrasonic waves are possible.

For pattern processing of a resin composition that does not contain a photosensitive compound, there is a method in which the resin composition is applied, a photoresist is applied, exposed, developed, and the photoresist is peeled off.

Next, it is preferable to rinse the pattern formed by development with distilled water. Also here, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to the distilled water for rinsing.

Next, the process of heat-treating the developed resin film will be explained. Since heat treatment can remove components with low heat resistance, heat resistance and chemical resistance can be improved. In particular, when the resin composition of the present invention contains an alkali-soluble resin selected from polyimide precursors, polybenzoxazole precursors, copolymers thereof, or copolymers of them and polyimide, heat treatment Since it can form an imide ring or an oxazole ring, heat resistance and chemical resistance can be improved, and if it contains a compound having at least two alkoxymethyl groups, methylol groups, epoxy groups, or oxanyl groups, heat treatment is required. The thermal cross-linking reaction can be progressed, and the heat resistance and chemical resistance can be improved. For this heat treatment, a certain temperature is selected and the temperature is raised stepwise, or a certain temperature range is selected and the temperature is raised continuously for 5 minutes to 5 hours. For example, heat treatment is performed at 150° C. and 250° C. for 30 minutes each. Alternatively, a method of linearly raising the temperature from room temperature to 300° C. over 2 hours can be used. The heat treatment conditions in the present invention are preferably 300° C. or higher, more preferably 350° C. or higher, from the viewpoint of reducing the amount of outgas generated from the cured product. The temperature is preferably 500° C. or lower, more preferably 450° C. or lower, from the viewpoint of imparting sufficient film toughness to the cured product.

The resin composition and cured product of the present invention can be used to flatten the insulating layer of an organic electroluminescence (EL) element and the driving thin film transistor (TFT) substrate of a display device using an organic EL element. It is suitable for use as a layer for protecting wiring on a circuit board, an insulating layer for protecting wiring on a circuit board, an on-chip microlens for a solid-state imaging device, and a flattening layer for various displays and solid-state imaging devices. For example, MRAM with low heat resistance, polymer memory (Polymer Ferroelectric RAM: PFRAM) and phase change memory (Phase Change RAM: PCRAM, Ovonics Unified Memory: OUM), etc., which are promising as next-generation memories. preferred. Further, a display device including a first electrode formed on a substrate and a second electrode provided opposite to the first electrode, for example, a display device using an LCD, ECD, ELD, or an organic electroluminescence device (Organic electroluminescence device) It can also be used as an insulating layer. An organic EL display device will be described below as an example.

<Organic EL display device>
The organic EL display device of the present invention has a drive circuit, a planarizing layer, a first electrode, an insulating layer, a light-emitting layer and a second electrode on a substrate, and the planarizing layer and/or the insulating layer are the above-described electrodes of the present invention. Including hardened material. Organic EL light-emitting materials are susceptible to deterioration due to moisture, and may have adverse effects such as a decrease in the area ratio of light-emitting portions to the area of light-emitting pixels. Luminescent properties are obtained. Taking an example of an active-matrix display device, a substrate made of glass, various plastics, or the like is provided with TFTs and wirings located on the sides of the TFTs and connected to the TFTs, and unevenness is covered thereon. A planarization layer is thus provided, and a display element is provided on the planarization layer. The display element and the wiring are connected through a contact hole formed in the planarization layer.

The film thickness of the flattening layer in the organic EL display device of the present invention is preferably 1.0 to 5.0 μm, more preferably 2.0 μm or more. By setting the thickness of the flattening layer within the range described above, the flatness of densely packed TFTs and wiring can be improved due to high definition. When the flattening layer is thickened, outgassing increases and causes deterioration of the light emission reliability of the organic EL display device. Further, the flattening layer is preferably multi-layered because TFTs and wiring can be arranged in the film thickness direction for high definition.

Fig. 1 shows a cross-sectional view of an example of an organic EL display device. Bottom gate type or top gate type TFTs (thin film transistors) 1 are provided in a matrix on a substrate 6 , and a TFT insulating layer 3 is formed to cover the TFTs 1 . A wiring 2 connected to the TFT 1 is provided on the TFT insulating layer 3 . Further, a flattening layer 4 is provided on the TFT insulating layer 3 so as to bury the wiring 2 therein. A contact hole 7 reaching the wiring 2 is provided in the planarization layer 4 . An ITO (transparent electrode) 5 is formed on the planarization layer 4 while being connected to the wiring 2 through the contact hole 7 . Here, the ITO 5 becomes an electrode of a display element (for example, an organic EL element). An insulating layer 8 is formed so as to cover the periphery of the ITO 5 . The organic EL element may be of a top emission type in which light is emitted from the side opposite to the substrate 6, or may be of a bottom emission type in which light is extracted from the substrate 6 side. In this manner, an active matrix type organic EL display device is obtained in which the TFTs 1 for driving the organic EL elements are connected to the respective organic EL elements.

The manufacturing method of the organic EL display device of the present invention having the TFT insulating layer 3, the planarizing layer 4 and/or the insulating layer 8 is formed from the resin composition on a substrate in the same manner as the above-described method of manufacturing the cured product. drying the resin film as necessary; exposing the resin film to light; developing the exposed resin film; and heat-treating the developed resin film. The organic EL display device of the present invention can be obtained by a manufacturing method including these steps.

The present invention will be described below with reference to examples, etc., but the present invention is not limited to these examples. The resin compositions in the examples were evaluated by the following methods.

(1) Sensitivity The varnish obtained in each example and comparative example was applied to an 8-inch silicon wafer by spin coating using a coating and developing apparatus ACT-8 (manufactured by Tokyo Electron Co., Ltd.) at 120°C. was baked for 3 minutes to prepare a prebaked film having a film thickness of 3.0 μm.

The film thickness was measured using Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd. under the condition of a refractive index of 1.63.

After that, using an exposure machine i-line stepper NSR-2005i9C (manufactured by Nikon Corporation), through a mask having a pattern of 10 μm contact holes, exposure dose ranged from 50 to 300 mJ/cm ² every 5 mJ/cm ² . bottom. After exposure, the ACT-8 developing device was used to reduce the film thickness to 0.5 μm by using a 2.38% by weight tetramethylammonium aqueous solution (hereinafter referred to as TMAH; manufactured by Tama Kagaku Kogyo Co., Ltd.) as a developer. After the development was completed, the film was rinsed with distilled water, shaken off and dried to obtain a pattern.

The resulting pattern was observed with an FDP microscope MX61 (manufactured by Olympus Corporation) at a magnification of 20 times to measure the opening diameter of the contact hole. The minimum exposure dose (mJ/cm ² ) at which the opening diameter of the contact hole reached 10 μm was obtained and defined as the sensitivity.

(2) Outgassing of cured product After applying the varnish obtained in each example and comparative example to a 6-inch silicon wafer by a spin coating method using a spin coater (MS-A100; manufactured by Mikasa Co., Ltd.) , a hot plate (SCW-636; manufactured by Dainippon Screen Mfg. Co., Ltd.) and prebaked at 120° C. for 120 seconds to prepare a prebaked film having a thickness of about 3.0 μm.

The resulting pre-baked film is heated to 250° C. using an inert oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.) at an oxygen concentration of 20 ppm by volume or less and a temperature increase of 5° C./min. Then, the resin composition was baked at 250° C. for 1 hour to prepare a cured product. 10 mg of the resulting cured product on a 6-inch silicon wafer was heated at 180° C. for 30 minutes using helium as a purge gas, and the desorbed components were collected on an adsorbent (Carbotrap 400) by a purge and trap method. bottom.

The collected components were thermally desorbed at 280° C. for 5 minutes, then using GC-MS apparatus 6890/5973N (manufactured by Agilent), column temperature: 40 to 300° C., carrier gas: helium (1.5 mL/min ), scanning range: GC-MS analysis was performed under the conditions of m / Z = 29 to 600. The amount of gas generated (weight ppm) was calculated from a calibration curve prepared by GC-MS analysis under the same conditions as above using n-hexadecane as a standard substance.

(3) 5% weight loss temperature A cured product of the resin composition was prepared on a 6-inch silicon wafer by the same method as in (2) so that the film thickness after curing was 10 μm, and 45% by weight of hydrogen fluoride was added. The cured product was peeled off from the wafer by immersion in acid for 5 minutes. After thoroughly washing the resulting cured product with pure water, it was dried in an oven at 60° C. for 5 hours to obtain a film. 10 mg of the obtained film was placed in a thermogravimetric analyzer TGA-50 (manufactured by Shimadzu Corporation), heated from room temperature to 100°C under a nitrogen atmosphere, then held at 100°C for 30 minutes, and weighed. It was measured. After that, the weight was measured while the temperature was raised to 400° C. at a heating rate of 10° C./min, and the temperature was measured when the weight decreased by 5% after holding at 100° C. for 30 minutes.

(4) Long-Term Reliability Evaluation of Organic EL Display Device FIG. 2 shows a schematic diagram of the manufacturing procedure of the organic EL display device.

First, an ITO transparent conductive film of 10 nm was formed on the entire surface of the alkali-free glass substrate 19 of 38 mm×46 mm by sputtering, and etched as the first electrode (transparent electrode) 20 . At the same time, an auxiliary electrode 21 for taking out the second electrode was also formed. (Upper left figure)
The obtained substrate was ultrasonically cleaned for 10 minutes with Semico Clean 56 (trade name, manufactured by Furuuchi Chemical Co., Ltd.) and then cleaned with ultrapure water.

Next, the entire surface of the substrate was coated with a resin composition shown in Table 3, which will be described later, by spin coating, and prebaked on a hot plate at 120° C. for 2 minutes. This film was exposed to UV light through a photomask, developed with a 2.38% by weight TMAH aqueous solution to dissolve unnecessary portions, and rinsed with pure water. The resulting resin pattern was heat-treated at 250° C. for 1 hour in a nitrogen atmosphere using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.). In this manner, the insulating layer 22 having a width of 70 μm and a length of 260 μm is arranged at a pitch of 155 μm in the width direction and a pitch of 465 μm in the length direction, and each opening exposes the first electrode. Formed only in the effective area. In this manner, the insulating layer 22 having an insulating layer aperture ratio of 25% was formed in the effective area of the substrate, which was a square with one side of 16 mm. The thickness of the insulating layer was about 1.0 μm. (upper right figure)
Next, after performing a nitrogen plasma treatment as a pretreatment, an organic EL layer 23 including a light-emitting layer was formed by a vacuum deposition method (lower left figure). The degree of vacuum during vapor deposition was 1×10 ⁻³ Pa or less, and the substrate was rotated with respect to the vapor deposition source during vapor deposition. First, 10 nm of compound (HT-1) was deposited as a hole injection layer, and 50 nm of compound (HT-2) was deposited as a hole transport layer. Next, a compound (GH-1) as a host material and a 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%. Next, the compound (ET-1) and the compound (LiQ) as electron transport materials were laminated at a volume ratio of 1:1 to a thickness of 40 nm. Structures of compounds used in the organic EL layer are shown below.

Next, after vapor-depositing a compound (LiQ) to a thickness of 2 nm, Mg and Ag were vapor-deposited to a thickness of 10 nm at a volume ratio of 10:1 to form a second electrode (non-transparent electrode) 24 . (bottom right figure)
Finally, a cap-shaped glass plate was adhered with an epoxy resin-based adhesive under a low humidity nitrogen atmosphere for sealing. Four display devices were produced. Incidentally, the film thickness referred to here is a value displayed on a crystal oscillation type film thickness monitor.

The produced organic EL display device was placed on a hot plate heated to 80° C. with the light-emitting surface facing up, and irradiated with UV light having a wavelength of 365 nm and an illuminance of 0.6 mW/cm ² . Immediately after irradiation (0 hour), 250 hours, 500 hours, and 1,000 hours later, the organic EL display device was driven to emit light by direct current driving at 0.625 mA, and the area ratio of the light emitting portion to the area of the light emitting pixel (pixel light emitting area ratio). was measured. According to this evaluation method, when the pixel emission area ratio after 1,000 hours has passed is 80% or more, it can be said that the long-term reliability is excellent, and when it is 90% or more, it is more preferable.

(5) Weight-average molecular weight and dispersion ratio of novolac-type phenolic resin The resins obtained in Synthesis Examples 5 to 16 were analyzed using a GPC (gel permeation chromatography) apparatus Waters 2690-996 (manufactured by Japan Waters Co., Ltd.). , Using N-methyl-2-pyrrolidone (hereinafter, NMP) as a developing solvent, the polystyrene-equivalent weight-average molecular weight (Mw) and polystyrene-equivalent number-average molecular weight (Mn) are obtained, and the dispersion ratio (Mw/Mn) is calculated. bottom.

(6) Regarding the content of the novolac-type phenolic resin having a molecular weight of 1,000 or less In the same manner as in (5) above, the resins obtained in Synthesis Examples 5 to 16 were subjected to GPC (gel permeation chromatography) apparatus Waters 2690-996 ( NMP as the developing solvent, Empower3 software (manufactured by Nippon Waters Co., Ltd.) is used to plot the weight fraction (%) on the vertical axis and the polystyrene-equivalent molecular weight on the horizontal axis. From the obtained molecular weight distribution curve, the content of the novolak type phenolic resin having a polystyrene-equivalent molecular weight of 1,000 or less was obtained.

Synthesis Example 1 Synthesis of hydroxyl group-containing diamine compound (α) 18.3 g (0.05 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as BAHF) was added to 100 mL of acetone and propylene. It was dissolved in 17.4 g (0.3 mol) of oxide and cooled to -15°C. A solution prepared by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride in 100 mL of acetone was added dropwise thereto. After completion of the dropwise addition, the mixture was allowed to react at -15°C for 4 hours, and then returned to room temperature. The precipitated white solid was collected by filtration and vacuum dried at 50°C.

30 g of the solid was placed in a 300 mL stainless steel autoclave, dispersed in 250 mL of methyl cellosolve, and 2 g of 5% palladium-carbon was added. Hydrogen was introduced here with a balloon, and the reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated after confirming that the balloon did not deflate any more. After completion of the reaction, the palladium compound as a catalyst was removed by filtration and concentrated with a rotary evaporator to obtain a hydroxyl group-containing diamine compound (α) represented by the following formula.

Synthesis Example 2 Synthesis of alkali-soluble resin (a-1) 44.4 g (0.10 mol) of 4,4'-(hexafluoroisopropylidene) diphthalic dianhydride (hereinafter referred to as 6FDA) was added to 500 g of NMP under a dry nitrogen stream. was dissolved in 4.46 g (0.05 mol) of 3-aminophenol as a terminal blocker was added together with 5 g of NMP, and reacted at 40° C. for 30 minutes. Here, 30.2 g (0.05 mol) of the hydroxyl group-containing diamine compound (α) obtained in Synthesis Example 1, 7.32 g (0.02 mol) of BAHF and 1,3-bis(3-aminopropyl)tetramethyl 1.24 g (0.005 mol) of disiloxane was added along with 50 g of NMP and allowed to react at 40° C. for 2 hours. Then, a solution prepared by diluting 28.6 g (0.24 mol) of N,N-dimethylformamide dimethylacetal with 50 g of NMP was added. After charging, the mixture was stirred at 40°C for 3 hours. After the stirring was completed, the solution was cooled to room temperature and then poured into 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water three times, and dried in a vacuum dryer at 80° C. for 24 hours to obtain a polyimide precursor used as an alkali-soluble resin (a-1).

Synthesis Example 3 Synthesis of alkali-soluble resin (a-2) Under dry nitrogen stream, 29.3 g (0.08 mol) of BAHF, 1.24 g (0.005 g) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane mol), and as a terminal blocking agent, 3.27 g (0.03 mol) of 3-aminophenol was dissolved in 150 g of NMP. 3,3′,4,4′-Diphenylethertetracarboxylic dianhydride (hereinafter referred to as ODPA) 31.0 g (0.1 mol) was added together with NMP 50 g, stirred at 20° C. for 1 hour, and then stirred at 50° C. and stirred for 4 hours. After that, 15 g of xylene was added, and the mixture was stirred at 150° C. for 5 hours while azeotroping water with the xylene. After the stirring was completed, the solution was poured into 3 L of water and a white precipitate was collected. This precipitate was collected by filtration, washed with water three times, and dried in a vacuum dryer at 80° C. for 24 hours to obtain a polyimide used as an alkali-soluble resin (a-2).

Synthesis Example 4 Synthesis of alkali-soluble resin (a-3) Under a dry nitrogen stream, 18.3 g (0.05 mol) of BAHF was dissolved in 50 g of NMP and 26.4 g (0.3 mol) of glycidyl methyl ether, and the temperature of the solution was adjusted to Cool to -15°C. Here, 7.4 g (0.025 mol) of diphenyl ether dicarboxylic acid dichloride (manufactured by Nihon Nohyaku Co., Ltd.) and 5.1 g (0.025 mol) of isophthalic acid chloride (manufactured by Tokyo Kasei Co., Ltd.) are mixed with γ-butyrolactone (GBL ) was added dropwise so that the internal temperature did not exceed 0°C. After the dropwise addition was completed, stirring was continued at -15°C for 6 hours. After completion of the reaction, the solution was poured into 3 L of water containing 10% by weight of methanol to collect a white precipitate. This precipitate was collected by filtration, washed with water three times, and dried in a vacuum dryer at 80° C. for 24 hours to obtain a polybenzoxazole precursor used as an alkali-soluble resin (a-3).

Synthesis Example 5 Synthesis of novolac-type phenolic resin (b-1) 100 g of m-cresol, 81.9 g of 37% formalin, 60 g of 89% phosphoric acid, and 100 g of ethylene glycol were charged, and then cloudy by stirring and mixing. Under these conditions, the temperature was gradually raised to the reflux temperature, and the condensation reaction was carried out at the same temperature for 22 hours, after which the reaction was stopped. Then, while stirring and mixing, 50 g of methyl isobutyl ketone was added to dissolve the condensate, and then the stirring was stopped and the content was transferred to a separating flask and allowed to stand. The aqueous phase (lower layer) was allowed to separate. Next, the aqueous solution of phosphoric acid is removed, and the methyl isobutyl ketone solution is washed with water several times to remove the phosphoric acid, and then the contents are returned to the reaction vessel and subjected to distillation under reduced pressure of 10 KPa for 4 hours to remove methyl isobutyl ketone. 110 g of m-cresol novolac resin was obtained.

While stirring 1000 g of xylene, 150 g of a resin solution obtained by dissolving 100 g of the obtained m-cresol novolak resin in 50 g of methyl isobutyl ketone was added dropwise, and after sufficient stirring, the mixture was allowed to stand to form a sediment layer. After that, the sediment layer was taken out and the solvent was removed to obtain 95 g of m-cresol novolak resin (b-1), and the properties were evaluated. Table 1 shows the results.

Synthesis Example 6 Synthesis of novolac-type phenolic resin (b-2) After charging 100 g of phenol, 81.9 g of 37% formalin, 1 g of oxalic acid dihydrate, and 100 g of ethylene glycol, cloudiness formed by stirring and mixing Under these conditions, the temperature was gradually raised to the reflux temperature, and the condensation reaction was carried out at the same temperature for 14 hours, after which the reaction was stopped. Then, while stirring and mixing, 50 g of methyl isobutyl ketone was added to dissolve the condensate, and then the stirring was stopped and the content was transferred into a separating flask and allowed to stand. The aqueous phase (lower layer) was allowed to separate. Next, the aqueous oxalic acid solution is removed, and the methyl isobutyl ketone solution is washed with water several times to remove oxalic acid, and then the contents are returned to the reaction vessel and heated to 150° C. under atmospheric pressure to remove methyl isobutyl ketone. Removal yielded 95 g of phenolic novolac resin.

90 g of phenol novolac resin was dissolved in a mixed solution of 50 g of methyl isobutyl ketone/350 g of methanol, 350 g of distilled water was added dropwise while stirring, and after sufficient stirring, the solution was allowed to stand to separate into a resin solution phase and an aqueous solution phase. After that, the resin solution phase was taken out and the solvent was removed to obtain 55 g of phenol novolac resin (b-2), and the properties were evaluated. The results are also shown in Table 1.

Synthesis Example 7 Synthesis of Novolac Phenolic Resin (b-3) After charging 100 g of phenol, 81.9 g of 37% formalin, 60 g of 89% phosphoric acid, and 100 g of ethylene glycol, a cloudy state formed by stirring and mixing. Then, the temperature was gradually raised to the reflux temperature, and the condensation reaction was carried out at the same temperature for 10 hours, after which the reaction was stopped. Then, 50 g of methyl isobutyl ketone was added while stirring and mixing to dissolve the condensate, then the stirring was stopped and the content was transferred to a separating flask and allowed to stand. The aqueous phase (lower layer) was allowed to separate. Next, the aqueous solution of phosphoric acid was removed, and the methyl isobutyl ketone solution was washed with water several times to remove the phosphoric acid. After that, the contents were returned to the reaction vessel and subjected to distillation under reduced pressure of 25 KPa for 4 hours to remove methyl isobutyl ketone. Removal yielded 95 g of phenolic novolak resin.

90 g of phenol novolac resin was dissolved in a mixed solution of 50 g of methyl isobutyl ketone/300 g of methanol, 150 g of distilled water was added dropwise while stirring, and after sufficient stirring, the solution was allowed to stand to separate into a resin solution phase and an aqueous solution phase. After that, the resin solution phase was taken out and the solvent was removed to obtain 85 g of phenol novolac resin (b-3), and the properties were evaluated. The results are also shown in Table 1.

Synthesis Example 8 Synthesis of novolak-type phenol resin (b-4) 100 g of m-cresol, 81.9 g of 37% formalin, and 60 g of 89% phosphoric acid were charged, and then stirred and mixed to form a cloudy state. Then, the temperature was gradually raised to the reflux temperature, and the condensation reaction was carried out at the same temperature for 9 hours, after which the reaction was stopped. Then, while stirring and mixing, 50 g of methyl ethyl ketone was added to dissolve the condensate, and then the stirring was stopped and the contents were transferred to a separating flask and allowed to stand. lower layer). Next, the aqueous solution of phosphoric acid is removed, and the methyl ethyl ketone solution is washed with water several times to remove the phosphoric acid, and then the contents are returned to the reaction vessel and heated to 150° C. under atmospheric pressure to remove the methyl ethyl ketone. - 95 g of cresol novolac resin were obtained.

90 g of m-cresol novolak resin was dissolved in a mixed solution of 50 g of methyl ethyl ketone and 300 g of methanol, 120 g of distilled water was added dropwise while stirring, and after sufficient stirring, the mixture was allowed to stand to separate into a resin solution phase and an aqueous solution phase. Thereafter, the resin solution phase was taken out and the solvent was removed to obtain 85 g of m-cresol novolac resin (b-4), and the properties were evaluated. The results are also shown in Table 1.

Synthesis Example 9 Synthesis of novolak-type phenolic resin (b-5) 105 g of m-cresol, 81.9 g of 37% formalin, 60 g of 89% phosphoric acid, and 100 g of ethylene glycol are charged, and then cloudy by stirring and mixing. Under these conditions, the temperature was gradually raised to the reflux temperature, and the condensation reaction was carried out at the same temperature for 17 hours, after which the reaction was stopped. Next, 50 g of methyl isobutyl ketone was added while stirring and mixing to dissolve the condensate, then the stirring was stopped and the contents were transferred into a separating flask and allowed to stand. The aqueous acid phase (lower layer) was allowed to separate. Next, the aqueous solution of phosphoric acid is removed, and the methyl isobutyl ketone solution is washed with water several times to remove the phosphoric acid, and then the contents are returned to the reaction vessel and heated to 150° C. under atmospheric pressure to remove methyl isobutyl ketone. Removal gave 100 g of m-cresol novolac resin.

95 g of m-cresol novolac resin is dissolved in a mixed solution of 100 g of methyl isobutyl ketone and 1,000 g of xylene, and after sufficiently stirring, the resin phase is separated by allowing to stand still, followed by filtering and removing the solvent to obtain m-cresol novolak. 90 g of resin (b-5) was obtained and its properties were evaluated. The results are also shown in Table 1.

Synthesis Example 10 Synthesis of Novolac Phenolic Resin (b-6) 105 g of m-cresol, 81.9 g of 37% formalin, and 60 g of 89% phosphoric acid were charged, and then stirred and mixed to form a cloudy state. Then, the temperature was gradually raised to the reflux temperature, and after the condensation reaction was carried out at the same temperature for 13 hours, the reaction was stopped. Next, 50 g of methyl isobutyl ketone was added while stirring and mixing to dissolve the condensate, then the stirring was stopped and the contents were transferred into a separating flask and allowed to stand. The aqueous acid phase (lower layer) was allowed to separate. Next, the aqueous solution of phosphoric acid was removed, and the methyl isobutyl ketone solution was washed with water several times to remove the phosphoric acid. The ketone was removed to obtain 100 g of m-cresol novolak resin.

95 g of m-cresol novolac resin is dissolved in a mixed solution of 100 g of methyl isobutyl ketone and 1,000 g of xylene, and after sufficiently stirring, the resin phase is separated by allowing to stand still, followed by filtering and removing the solvent to obtain m-cresol novolak. 60 g of resin (b-6) was obtained and its properties were evaluated. The results are also shown in Table 1.

Synthesis Example 11 Synthesis of novolak-type phenolic resin (b-7) 100 g of m-cresol, 81.9 g of 37% formalin, 60 g of 89% phosphoric acid, and 100 g of ethylene glycol were charged, and then cloudy by stirring and mixing. Under these conditions, the temperature was gradually raised to the reflux temperature, and the condensation reaction was carried out at the same temperature for 24 hours, after which the reaction was stopped. Next, 50 g of methyl isobutyl ketone was added while stirring and mixing to dissolve the condensate, then the stirring was stopped and the contents were transferred into a separating flask and allowed to stand. The aqueous acid phase (lower layer) was allowed to separate. Next, the aqueous solution of phosphoric acid is removed, and the methyl isobutyl ketone solution is washed with water several times to remove the phosphoric acid. After that, the content is returned to the reaction vessel and subjected to distillation under reduced pressure of 20 KPa for 4 hours to remove the methyl isobutyl ketone. Thus, 100 g of m-cresol novolac resin was obtained.

95 g of m-cresol novolac resin is dissolved in a mixed solution of 100 g of methyl isobutyl ketone and 1,000 g of xylene, and after sufficiently stirring, the resin phase is separated by allowing to stand still, followed by filtering and removing the solvent to obtain m-cresol novolak. 50 g of resin (b-7) was obtained and its properties were evaluated. The results are also shown in Table 1.

Synthesis Example 12 Synthesis of novolac-type phenolic resin (b-8) After charging 100 g of phenol, 81.9 g of 37% formalin, 1 g of oxalic acid dihydrate, and 100 g of ethylene glycol, cloudiness formed by stirring and mixing. Under these conditions, the temperature was gradually raised to the reflux temperature, and the condensation reaction was carried out at the same temperature for 12 hours, after which the reaction was stopped. Then, while stirring and mixing, 50 g of methyl isobutyl ketone was added to dissolve the condensate, and then the stirring was stopped and the content was transferred into a separating flask and allowed to stand. The aqueous phase (lower layer) was allowed to separate. Next, the aqueous oxalic acid solution is removed, and the methyl isobutyl ketone solution is washed with water several times to remove oxalic acid, and then the contents are returned to the reaction vessel and heated to 150° C. under atmospheric pressure to remove methyl isobutyl ketone. Removal yielded 95 g of phenolic novolac resin.

90 g of phenol novolac resin was dissolved in a mixed solution of 50 g of methyl isobutyl ketone/350 g of methanol, 250 g of distilled water was added dropwise while stirring, and after sufficient stirring, the solution was allowed to stand to separate into a resin solution phase and an aqueous solution phase. Thereafter, the resin solution phase was taken out and the solvent was removed to obtain 55 g of phenol novolac resin (b-8), and the properties were evaluated. Table 2 shows the results.

Synthesis Example 13 Synthesis of novolac-type phenolic resin (b-9) After charging 100 g of phenol, 81.9 g of 37% formalin, 1 g of oxalic acid dihydrate, and 100 g of ethylene glycol, cloudiness formed by stirring and mixing. Under these conditions, the temperature was gradually raised to the reflux temperature, and the condensation reaction was carried out at the same temperature for 24 hours, after which the reaction was stopped. Then, while stirring and mixing, 50 g of methyl isobutyl ketone was added to dissolve the condensate, and then the stirring was stopped and the content was transferred into a separating flask and allowed to stand. The aqueous phase (lower layer) was allowed to separate. Next, the aqueous oxalic acid solution was removed, and the methyl isobutyl ketone solution was washed with water several times to remove the oxalic acid. After that, the content was returned to the reaction vessel and subjected to distillation under reduced pressure of 25 KPa for 10 hours to remove methyl isobutyl ketone. Removal yielded 95 g of phenolic novolac resin.

85 g of phenol novolac resin was dissolved in a mixed solution of 50 g of methyl isobutyl ketone/350 g of methanol, 250 g of distilled water was added dropwise while stirring, and after sufficient stirring, the solution was allowed to stand to separate into a resin solution phase and an aqueous solution phase. Thereafter, the resin solution phase was taken out and the solvent was removed to obtain 45 g of phenol novolac resin (b-9), and the properties were evaluated. The results are also shown in Table 2.

Synthesis Example 14 Synthesis of novolak-type phenolic resin (b-10) After charging 100 g of p-cresol, 81.9 g of 37% formalin, 60 g of 89% phosphoric acid, and 100 g of ethylene glycol, cloudiness formed by stirring and mixing. Under these conditions, the temperature was gradually raised to the reflux temperature, and the condensation reaction was carried out at the same temperature for 9 hours, after which the reaction was stopped. Then, 50 g of methyl isobutyl ketone was added while stirring and mixing to dissolve the condensate, then the stirring was stopped and the content was transferred to a separating flask and allowed to stand. The aqueous phase (lower layer) was allowed to separate. Next, the aqueous solution of phosphoric acid was removed, and the methyl isobutyl ketone solution was washed with water several times to remove the phosphoric acid. After that, the contents were returned to the reaction vessel and subjected to distillation under reduced pressure of 25 KPa for 8 hours to remove methyl isobutyl ketone. Removal yielded 95 g of p-cresol novolac resin.

90 g of p-cresol novolac resin is dissolved in a mixed solution of 50 g of methyl isobutyl ketone/300 g of methanol, 200 g of distilled water is added dropwise while stirring, and after sufficient stirring, the solution is allowed to stand to separate into a resin solution phase and an aqueous solution phase. bottom. After that, the resin solution phase was taken out and the solvent was removed to obtain 45 g of p-cresol novolac resin (b-10), and the properties were evaluated. The results are also shown in Table 2.

Synthesis Example 15 Synthesis of novolak-type phenolic resin (b-11) 100 g of p-cresol, 81.9 g of 37% formalin, 60 g of 89% phosphoric acid, and 100 g of ethylene glycol were charged, followed by stirring and mixing to form cloudiness. Under these conditions, the temperature was gradually raised to the reflux temperature, and the condensation reaction was carried out at the same temperature for 9 hours, after which the reaction was stopped. Then, 50 g of methyl isobutyl ketone was added while stirring and mixing to dissolve the condensate, then the stirring was stopped and the content was transferred to a separating flask and allowed to stand. The aqueous phase (lower layer) was allowed to separate. Next, the aqueous phosphoric acid solution is removed, and the methyl isobutyl ketone solution is washed with water several times to remove the phosphoric acid, and then the contents are returned to the reaction vessel and heated to 150° C. under atmospheric pressure to remove methyl isobutyl ketone. Removal yielded 95 g of p-cresol novolak resin.

90 g of p-cresol novolac resin is dissolved in a mixed solution of 50 g of methyl isobutyl ketone/350 g of methanol, 300 g of distilled water is added dropwise while stirring, and after sufficient stirring, the mixture is allowed to stand to separate into a resin solution phase and an aqueous solution phase. bottom. After that, the resin solution phase was taken out and the solvent was removed to obtain 85 g of p-cresol novolac resin (b-11), and the properties were evaluated. The results are also shown in Table 2.

Synthesis Example 16 Synthesis of novolac-type phenolic resin (b-12) 100 g of m-cresol, 81.9 g of 37% formalin, 60 g of 89% phosphoric acid, and 100 g of ethylene glycol were charged, followed by stirring and mixing to form cloudiness. Under these conditions, the temperature was gradually raised to the reflux temperature, and the condensation reaction was carried out at the same temperature for 8 hours, after which the reaction was stopped. Then, 50 g of methyl isobutyl ketone was added while stirring and mixing to dissolve the condensate, then the stirring was stopped and the content was transferred to a separating flask and allowed to stand. The aqueous phase (lower layer) was allowed to separate. Next, the aqueous solution of phosphoric acid was removed, and the methyl isobutyl ketone solution was washed with water several times to remove the phosphoric acid. After that, the contents were returned to the reaction vessel and subjected to distillation under reduced pressure of 25 KPa for 8 hours to remove methyl isobutyl ketone. Removal gave 95 g of m-cresol novolac resin.

90 g of m-cresol novolac resin is dissolved in a mixed solution of 50 g of methyl isobutyl ketone/350 g of methanol, 100 g of distilled water is added dropwise while stirring, and after sufficient stirring, the mixture is allowed to stand to separate into a resin solution phase and an aqueous solution phase. bottom. After that, the resin solution phase was taken out and the solvent was removed to obtain 45 g of m-cresol novolak resin (b-12), and the properties were evaluated. The results are also shown in Table 2.

Synthesis Example 17 Synthesis of quinonediazide compound (c-1) TrisP-PA (trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.) 21.22 g (0.05 mol) and 5-naphthoquinonediazide sulfonyl chloride 36 under a stream of dry nitrogen. .27 g (0.135 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. To this, 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the inside of the system did not reach 35° C. or higher. After dropping, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. After that, the deposited precipitate was collected by filtration. This precipitate was dried in a vacuum dryer to obtain a quinonediazide compound (c-1) represented by the following formula.

Example 1
10.0 g of alkali-soluble resin (a-1) and 3.5 g of m-cresol novolak resin (b-1) were added to 40 g of PGME to obtain a varnish of a resin composition. Using the obtained varnish, the outgassing of the cured product, the 5% weight loss temperature, and the long-term reliability of the organic EL display device were evaluated as described above.

Example 2
10.0 g of alkali-soluble resin (a-1), 3.0 g of m-cresol novolac resin (b-1), and 2.0 g of quinonediazide compound (c-1) were added to 40 g of PGME to prepare a varnish of a positive photosensitive resin composition. got Using the obtained varnish, the sensitivity, outgassing of the cured product, 5% weight loss temperature, and long-term reliability of the organic EL display device were evaluated as described above.

Example 3
10.0 g of an alkali-soluble resin (a-2), 1.8 g of a phenol novolac resin (b-2), and 2.0 g of a quinonediazide compound (c-1) were added to 40 g of PGME to obtain a varnish of a positive photosensitive resin composition. rice field. Using the obtained varnish, the sensitivity, outgassing of the cured product, 5% weight loss temperature, and long-term reliability of the organic EL display device were evaluated as described above.

Example 4
10.0 g of an alkali-soluble resin (a-3), 4.9 g of a phenol novolac resin (b-3), and 2.0 g of a quinonediazide compound (c-1) were added to 40 g of PGME to obtain a varnish of a positive photosensitive resin composition. rice field. Using the obtained varnish, the sensitivity, outgassing of the cured product, 5% weight loss temperature, and long-term reliability of the organic EL display device were evaluated as described above.

Example 5
10.0 g of alkali-soluble resin (a-1), 2.5 g of m-cresol novolac resin (b-4), and 2.0 g of quinonediazide compound (c-1) were added to 40 g of PGME to prepare a varnish of a positive photosensitive resin composition. got Using the obtained varnish, the sensitivity, outgassing of the cured product, 5% weight loss temperature, and long-term reliability of the organic EL display device were evaluated as described above.

Example 6
10.0 g of alkali-soluble resin (a-1), 3.1 g of m-cresol novolak resin (b-5), and 2.0 g of quinonediazide compound (c-1) were added to 40 g of PGME to prepare a varnish of a positive photosensitive resin composition. got Using the obtained varnish, the sensitivity, outgassing of the cured product, 5% weight loss temperature, and long-term reliability of the organic EL display device were evaluated as described above.

Example 7
10.0 g of alkali-soluble resin (a-1), 4.2 g of m-cresol novolac resin (b-6), and 2.0 g of quinonediazide compound (c-1) were added to 40 g of PGME to prepare a varnish of a positive photosensitive resin composition. got Using the obtained varnish, the sensitivity, outgassing of the cured product, 5% weight loss temperature, and long-term reliability of the organic EL display device were evaluated as described above.

Example 8
10.0 g of alkali-soluble resin (a-1), 2.2 g of m-cresol novolac resin (b-7), and 2.0 g of quinonediazide compound (c-1) were added to 40 g of PGME to prepare a varnish of a positive photosensitive resin composition. got Using the obtained varnish, the sensitivity, outgassing of the cured product, 5% weight loss temperature, and long-term reliability of the organic EL display device were evaluated as described above.

Example 9
10.0 g of alkali-soluble resin (a-1), 2.2 g of m-cresol novolak resin (b-12), and 2.0 g of quinonediazide compound (c-1) were added to 40 g of PGME to prepare a varnish of a positive photosensitive resin composition. got Using the obtained varnish, the sensitivity, outgassing of the cured product, 5% weight loss temperature, and long-term reliability of the organic EL display device were evaluated as described above.

Comparative example 1
10.0 g of alkali-soluble resin (a-1) and 5.5 g of phenol novolac resin (b-8) were added to 40 g of PGME to obtain a varnish of a resin composition. Using the obtained varnish, the outgassing of the cured product, the 5% weight loss temperature, and the long-term reliability of the organic EL display device were evaluated as described above.

Comparative example 2
10.0 g of an alkali-soluble resin (a-1), 5.5 g of a phenol novolac resin (b-8), and 2.0 g of a quinonediazide compound (c-1) were added to 40 g of PGME to obtain a varnish of a positive photosensitive resin composition. rice field. Using the obtained varnish, the sensitivity, outgassing of the cured product, 5% weight loss temperature, and long-term reliability of the organic EL display device were evaluated as described above.

Comparative example 3
10.0 g of alkali-soluble resin (a-1), 1.6 g of phenol novolac resin (b-9) and 2.0 g of quinonediazide compound (c-1) were added to 40 g of PGME to obtain a varnish of a positive photosensitive resin composition. rice field. Using the obtained varnish, the sensitivity, outgassing of the cured product, 5% weight loss temperature, and long-term reliability of the organic EL display device were evaluated as described above.

Comparative example 4
10.0 g of alkali-soluble resin (a-1), 5.1 g of p-cresol novolac resin (b-10), and 2.0 g of quinonediazide compound (c-1) were added to 40 g of PGME to prepare a varnish of a positive photosensitive resin composition. got Using the obtained varnish, the sensitivity, outgassing of the cured product, 5% weight loss temperature, and long-term reliability of the organic EL display device were evaluated as described above.

Comparative example 5
10.0 g of alkali-soluble resin (a-1), 5.2 g of p-cresol novolak resin (b-11), and 2.0 g of quinonediazide compound (c-1) were added to 40 g of PGME to prepare a varnish of a positive photosensitive resin composition. got Using the obtained varnish, the sensitivity, outgassing of the cured product, 5% weight loss temperature, and long-term reliability of the organic EL display device were evaluated as described above.

The resin composition and cured product of the present invention can be used for insulating layers of organic EL elements, flattening layers of thin TFT substrates for driving display devices using organic EL elements, wiring protection insulating layers of circuit boards, and solid-state imaging elements. It is suitably used for chip microlenses, various displays, and flattening layers for solid-state imaging devices. For example, it is suitable as a surface protective layer or an interlayer insulating layer for MRAM with low heat resistance, polymer memory (PFRAM) and phase change memory (PCRAM, OUM) that are promising as next-generation memory. Further, a display device including a first electrode formed on a substrate and a second electrode provided opposite to the first electrode, for example, a display device using an LCD, ECD, ELD, or an organic electroluminescence device (Organic electroluminescence device) It can also be preferably used as an insulating layer.

1 TFT
2 wiring 3 TFT insulating layer 4 planarization layer 5 ITO
6 substrate 7 contact hole 8 insulating layer 19 alkali-free glass substrate 20 first electrode (transparent electrode)
21 auxiliary electrode 2
22 insulating layer 23 organic EL layer 24 second electrode (non-transparent electrode)

Claims

Alkali-soluble resin (a) containing one or more selected from the group consisting of polyimide, polybenzoxazole, polyamideimide, precursors of any of these and copolymers thereof, and novolac-type phenolic resin (b) A resin composition, wherein the content of the novolak-type phenolic resin (b) having a molecular weight of 1,000 or less is 0.1 to 20% by weight of the novolak-type phenolic resin (b). A certain resin composition.
The weight average molecular weight (Mw) of the novolak-type phenol resin (b) is 3,000 or more and 15,000 or less, and the dispersion ratio (Mw)/ 2. The resin composition according to claim 1, wherein (Mn) is from 1.1 to 3.5.
3. The resin composition according to claim 1, wherein the novolac-type phenolic resin (b) contains an m-cresol novolak resin.
2. The resin composition according to claim 1, wherein the novolak-type phenolic resin (b) is 17 to 50 parts by weight per 100 parts by weight of the alkali-soluble resin (a).
The resin composition according to claim 1, further comprising a photosensitive compound (c).
A cured product obtained by curing the resin composition according to claim 1 .
7. An organic EL display device having a drive circuit, a planarizing layer, a first electrode, an insulating layer, a light-emitting layer and a second electrode on a substrate, wherein the planarizing layer and/or the insulating layer are according to claim 6. An organic EL display device containing a cured product.
A step of applying the resin composition according to any one of claims 1 to 5 on a substrate to form a resin film, a step of exposing the resin film, a step of developing the exposed resin film, and a developed resin A method for producing a cured product, comprising the step of heat-treating a film.