JP7574576B2 - Negative photosensitive resin composition, cured film, and organic EL display device - Google Patents

Description

The present invention relates to a negative photosensitive resin composition, a cured film, and an organic EL display device.

In recent years, many products using organic electroluminescence (hereinafter "EL") display devices have been developed for use in thin display devices such as smartphones, tablet PCs, and televisions.

In general, an organic EL display device has a transparent electrode such as indium tin oxide (hereinafter referred to as "ITO") on the light extraction side of the light emitting element, and a metal electrode such as an alloy of magnesium and silver on the non-light extraction side of the light emitting element. In addition, an insulating layer called a pixel division layer is formed between the transparent electrode and the metal electrode to divide the pixels of the light emitting element.

In recent years, attempts have been made to impart light-shielding properties to pixel division layers to reduce the reflection of external light such as sunlight and improve the visibility and contrast of organic EL display devices. Specific examples of such attempts include positive-type photosensitive resin compositions using black dyes or black pigments (see, for example, Patent Documents 1 and 2) and negative-type black photosensitive resin compositions using polyimide and/or polybenzoxazole (see, for example, Patent Document 3).

Patent No. 6689434 International Publication No. 2017-069172 JP 2019-023728 A

However, in the positive type black photosensitive resin composition as in Patent Documents 1 and 2, since the black material absorbs the exposure wavelength, it is difficult to achieve both high light blocking properties and sensitivity, and the OD value per unit film thickness is up to about 0.5. On the other hand, in the negative type black photosensitive resin composition as in Patent Document 3, it is possible to achieve both high light blocking properties and sensitivity, but in the hole pattern processing of 10 μm or less required for high-definition display applications, the absolute value of the difference in the hole pattern formation width from the mask design width (hereinafter, sometimes referred to as mask bias) becomes too large, making it difficult to form the desired pattern. Furthermore, when a cured film of a negative type black photosensitive resin composition is used in an organic EL display device, there is a problem that unreacted components remain, deteriorating the long-term reliability of the organic EL display device.

A negative photosensitive resin composition comprising an alkali-soluble resin (A) containing a repeating unit represented by general formula (1) and/or general formula (2) and a repeating unit represented by general formula (3) and/or general formula (4), a radically polymerizable compound (B), a radical polymerization initiator (C), a color pigment (D) and an organic solvent (E).

In general formula (1), ^R1 represents a hydrogen atom or a methyl group, ^R2 represents a single bond or an alkylene group having 1 to 5 carbon atoms or an alkylene ether group having 1 to 5 carbon atoms and 1 oxygen atom, and ^R3 represents an alkyl group, alkoxy group, or acyl group having 1 to 5 carbon atoms. Furthermore, l represents an integer of 0 to 4, and m represents an integer of 1 to 4. When two or more ^R3s are present, these ^R3s may be different from each other or may be the same.
In general formula (2), ^R4 represents a hydrogen atom or a methyl group, and ^R5 represents an alkyl group, an alkoxy group, or an acyl group having 1 to 5 carbon atoms. In addition, n represents an integer of 0 to 4, and o represents an integer of 1 to 4. When two or more ^R5s are present, these ^R5s may be different from each other or may be the same.
In general formula (3), ^R6 represents a hydrogen atom or a methyl group, ^R7 represents a single bond, an alkylene group having 1 to 5 carbon atoms, or an alkylene ether group having 1 to 5 carbon atoms and 1 oxygen atom. ^R8 represents an alkyl group having 1 to 5 carbon atoms. Furthermore, p represents an integer of 1 to 5, and q represents an integer of 0 to 5. When two or more ^R8s are present, these ^R8s may be different from each other or may be the same.
In formula (4), R ⁹ represents a hydrogen atom or a methyl group, and R ¹⁰ represents a single bond, an alkylene group having 1 to 5 carbon atoms, or an alkylene ether group having 1 to 5 carbon atoms and 1 oxygen atom.

The negative-type photosensitive resin composition of the present invention can provide a negative-type photosensitive resin composition that has both high light-shielding properties and sensitivity, has a small mask bias, and has high long-term reliability when the cured film is used in an organic EL display device.

1 is a schematic diagram illustrating a procedure for producing an organic EL display device according to an embodiment of the present invention.

The present invention is a negative photosensitive resin composition comprising an alkali-soluble resin (A) containing a repeating unit represented by general formula (1) and/or general formula (2) and a repeating unit represented by general formula (3) and/or general formula (4), a radically polymerizable compound (B), a radical polymerization initiator (C), a color pigment (D), and an organic solvent (E).

In general formula (1), ^R1 represents a hydrogen atom or a methyl group, ^R2 represents a single bond or an alkylene group having 1 to 5 carbon atoms or an alkylene ether group having 1 to 5 carbon atoms and 1 oxygen atom, and ^R3 represents an alkyl group, alkoxy group, or acyl group having 1 to 5 carbon atoms. Furthermore, l represents an integer of 0 to 4, and m represents an integer of 1 to 4. When two or more ^R3s are present, these ^R3s may be different from each other or may be the same.
In general formula (2), ^R4 represents a hydrogen atom or a methyl group, and ^R5 represents an alkyl group, an alkoxy group, or an acyl group having 1 to 5 carbon atoms. In addition, n represents an integer of 0 to 4, and o represents an integer of 1 to 4. When two or more ^R5s are present, these ^R5s may be different from each other or may be the same.

In general formula (3), ^R6 represents a hydrogen atom or a methyl group, ^R7 represents a single bond, an alkylene group having 1 to 5 carbon atoms, or an alkylene ether group having 1 to 5 carbon atoms and 1 oxygen atom. ^R8 represents an alkyl group having 1 to 5 carbon atoms. Furthermore, p represents an integer of 1 to 5, and q represents an integer of 0 to 5. When two or more ^R8s are present, these ^R8s may be different from each other or may be the same.
In formula (4), R ⁹ represents a hydrogen atom or a methyl group, and R ¹⁰ represents a single bond, an alkylene group having 1 to 5 carbon atoms, or an alkylene ether group having 1 to 5 carbon atoms and 1 oxygen atom.

The negative photosensitive resin composition of the present invention contains an alkali-soluble resin (A) (hereinafter sometimes referred to as component (A)) that contains repeating units represented by general formula (1) and/or general formula (2) and general formula (3) and/or general formula (4).

The component (A) can be obtained by copolymerizing a monomer constituting the repeating unit represented by general formula (1) and/or general formula (2) with a monomer constituting the repeating unit represented by general formula (3) and/or general formula (4). Examples of the copolymerization method include the method described in JP-A-5-19467, but any known method can also be used.
Specific examples of monomers constituting the repeating unit represented by general formula (1) include 4-hydroxyphenyl methacrylate (hereinafter, PQMA), (4-hydroxyphenyl)methyl methacrylate, (4-hydroxyphenyl)ethyl methacrylate (hereinafter, PEMA), and (4-hydroxyphenyl)propyl methacrylate.

Specific examples of monomers constituting the repeating unit represented by general formula (2) include 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, 2,4-dihydroxystyrene, 2,6-dihydroxystyrene, 2,4,6-trihydroxystyrene, 2,3,4,5-tetrahydroxystyrene, pentahydroxystyrene, 2-hydroxy-α-methylstyrene, 3-hydroxy-α-methylstyrene, 4-hydroxy-α-methylstyrene, 1-(2-hydroxyphenyl)propylene, 1-(3-hydroxyphenyl)propylene, and 1-(4-hydroxyphenyl)propylene.

By containing the repeating units represented by general formula (1) and/or general formula (2), the component (A) exhibits the effect of suppressing radical chain reactions, the mask bias of the negative photosensitive resin composition is reduced, and a pattern as intended can be formed, but among these, it is preferable that the component (A) has a repeating unit represented by general formula (1). It is also more preferable that ^R2 in general formula (1) is a single bond.

In addition, examples of monomers constituting the repeating unit represented by general formula (3) include glycidyl acrylate, glycidyl methacrylate (hereinafter sometimes referred to as GMA), 4-hydroxybutyl acrylate glycidyl ether (hereinafter sometimes referred to as 4HBAGE), (3-ethyloxetan-3-yl)methyl acrylate, (3-methyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, (3-methyloxetan-3-yl)methyl methacrylate, tetrahydrofurfuryl acrylate, and tetrahydro-2H-pyran-2-yl acrylate, with glycidyl methacrylate being preferred.

In addition, examples of monomers constituting the repeating unit represented by general formula (4) include 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylethyl methacrylate, and 3,4-epoxycyclohexylethyl acrylate, with 3,4-epoxycyclohexylmethyl methacrylate being preferred.

When component (A) contains repeating units represented by general formula (3) and/or general formula (4), the crosslink density is improved in the process of thermally curing the negative photosensitive resin composition after pattern processing, making it possible to obtain an organic EL display device with excellent long-term reliability.

When the total molar ratio of the repeating units represented by general formula (1) and the repeating units represented by general formula (2) and the total molar ratio of the repeating units represented by general formula (3) and the repeating units represented by general formula (4) are M1 and M2, respectively, relative to 100 mol% of all repeating units in component (A), it is preferable that M1 is 30 mol% or more and less than 70 mol%. By setting M1 in this range, it is possible to achieve both reduced mask bias and high sensitivity of the negative photosensitive resin composition.
The ratio M1/M2 is preferably 0.4 or more, more preferably 0.6 or more, from the viewpoints of storage stability of the negative photosensitive resin composition and minimizing mask bias, while the ratio M1/M2 is preferably 1.5 or less from the viewpoints of long-term reliability of the organic EL display device.

Component (A) can further be copolymerized with any (meth)acrylic monomer as a monomer, if necessary. Specifically, monomers having a carboxy group such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, phthalic acid, phthalic anhydride, crotonic acid, 2-carboxyethyl acrylate oligomer, 2-carboxyethyl methacrylate oligomer, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, It may also include unsaturated monomers having an aromatic ring, such as acrylic acid esters or methacrylic acid esters, such as butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, benzyl methacrylate, and 2-ethylhexyl methacrylate, or their (fluoro)alkyl ester monomers, styrene, α-methylstyrene, 4-vinyltoluene and its structural isomers, 4-methoxystyrene and its structural isomers, 4-butoxystyrene and its structural isomers, 4-tert-butoxystyrene and its structural isomers, 4-vinylbiphenyl, 2-vinylnaphthalene and its structural isomers, 9-vinylanthracene, and 9-vinylcarbazole.

From the viewpoint of minimizing mask bias, the content of component (A) in the negative photosensitive resin composition is preferably 5 parts by weight or more, and more preferably 10 parts by weight or more, per 100 parts by weight of the total of components other than the solvent in the negative photosensitive resin composition. On the other hand, from the viewpoint of improving sensitivity during exposure, the content of component (A) is preferably 60 parts by weight or less, and more preferably 50 parts by weight or less, per 100 parts by weight of the total of components other than the solvent in the negative photosensitive resin composition.

The negative photosensitive resin composition contains a radically polymerizable compound (B) (hereinafter, sometimes referred to as component (B)). Here, the solvent refers to the organic solvent (E) and water.

From the viewpoint of improving the sensitivity during exposure, the radical polymerizable group of the (B) component is preferably an acrylic group or a methacrylic group, and may have two of these. The (B) component is preferably a compound having two or more radical polymerizable groups. Examples of such (B) components include bisphenol A diglycidyl ether (meth)acrylate, poly(meth)acrylate carbamate, modified bisphenol A epoxy (meth)acrylate, adipic acid 1,6-hexanediol (meth)acrylic acid ester, phthalic anhydride propylene oxide (meth)acrylic acid ester, trimellitic acid diethylene glycol (meth)acrylic acid ester, rosin modified epoxy di(meth)acrylate, alkyd modified (meth)acrylate, fluorene diacrylate oligomer, tripropylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, triacrylformal, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, 2,2-bis[4-(3-acryloxy-2-hydroxypropoxy)phenyl]propane, bis[4-(3-acryloxy-2-hydroxypropoxy)phenyl]methane, bis[4-(3-acryloxy-2-hydroxypropoxy)phenyl]sulfone, bis[4-(3-acryloxy-2-hydroxypropoxy)phenyl]ether, 4,4' 9,9-bis[4-(3-acryloxy-2-hydroxypropoxy)phenyl]cyclohexane, 9,9-bis[4-(3-acryloxy-2-hydroxypropoxy)phenyl]fluorene, 9,9-bis[3-methyl-4-(3-acryloxy-2-hydroxypropoxy)phenyl]fluorene, 9,9-bis[3-chloro-4-(3-acryloxy-2-hydroxypropoxy)phenyl]fluorene, bisphenoxyethanol fluorene diacrylate, bisphenoxyethanol fluorene dimethacrylate, biscresol fluorene diacrylate, biscresol fluorene dimethacrylate, etc. may be included. Two or more of these may be contained. From the viewpoint of further improving the sensitivity, a compound having three or more radical polymerizable groups is more preferable, a compound having five or more radical polymerizable groups is more preferable, and dipentaerythritol hexa(meth)acrylate and dipentaerythritol penta(meth)acrylate are even more preferable.

From the viewpoint of improving sensitivity during exposure, the content of component (B) in the negative photosensitive resin composition is preferably 10 parts by weight or more, and more preferably 15 parts by weight or more, per 100 parts by weight of the total content of components (A) and (B). On the other hand, from the viewpoint of reflowability in the heating and baking process, the content of component (B) is preferably 80 parts by weight or less, and more preferably 60 parts by weight or less, per 100 parts by weight of the total content of alkali-soluble resin (A) and radically polymerizable compound (B).

The negative photosensitive resin composition contains a radical polymerization initiator (C) (hereinafter, sometimes referred to as component (C)).

Component (C) refers to a compound that generates radicals by bond cleavage and/or reaction upon exposure. Examples include carbazole-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, oxime ester-based photopolymerization initiators, and α-aminoalkylphenone-based photopolymerization initiators. Two or more of these may be contained. Among these, carbazole-based photopolymerization initiators and oxime ester-based photopolymerization initiators are preferred because they have high sensitivity to a mixed line consisting of i-lines (365 nm), h-lines (405 nm), and g-lines (436 nm) in the exposure step described below.

From the viewpoint of improving sensitivity to light exposure, the content of the (C) component in the negative photosensitive resin composition is preferably 1 part by weight or more, and more preferably 5 parts by weight or more, per 100 parts by weight of the (B) radical polymerizable compound. On the other hand, from the viewpoint of fine line processability, the content of the (C) component is preferably 60 parts by weight or less, and more preferably 40 parts by weight or less, per 100 parts by weight of the (B) radical polymerizable compound.

The negative photosensitive resin composition contains a color pigment (D) (hereinafter, sometimes referred to as component (D)).

As component (D), organic pigments and inorganic pigments commonly used in the field of electronic information materials can be used. Examples of organic pigments include diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, or polyazo, phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, or metal-free phthalocyanine, anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavanthrone, anthanthrone, indanthrone, pyranthrone, or violanthrone, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, threne pigments, or metal complex pigments.

Examples of inorganic pigments include titanium oxide, zinc oxide, zinc sulfide, white lead, calcium carbonate, precipitated barium sulfate, white carbon, alumina white, kaolin clay, talc, bentonite, black iron oxide, cadmium red, red iron oxide, molybdenum red, molybdate orange, chrome vermilion, yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, viridian, titanium cobalt green, cobalt green, cobalt chrome green, Victoria green, ultramarine, Prussian blue, cobalt blue, cerulean blue, cobalt silica blue, cobalt zinc silica blue, manganese violet, and cobalt violet.

Examples of red pigments include Pigment Red 9, 48, 97, 122, 123, 144, 149, 166, 168, 177, 179, 180, 192, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, and 254 (all numbers are Color Index (CI) numbers)).

Examples of orange pigments include Pigment Orange 13, 36, 38, 43, 51, 55, 59, 61, 64, 65, and 71.

Examples of yellow pigments include Pigment Yellow 12, 13, 17, 20, 24, 83, 86, 93, 95, 109, 110, 117, 125, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 168, and 185 (all numbers are CI numbers).

Examples of purple pigments include Pigment Violet 19, 23, 29, 30, 32, 37, 40, and 50 (all numbers are CI numbers).

Examples of blue pigments include Pigment Blue 15, 15:3, 15:4, 15:6, 22, 60, and 64 (all numbers are CI numbers).

Examples of green pigments include Pigment Green 7, 10, 36, and 58 (all numbers are CI numbers).

Examples of black pigments include black organic pigments, mixed-color organic pigments, and inorganic pigments. Examples of black organic pigments include carbon black, perylene black, aniline black, and benzofuranone pigments (described in JP-T 2012-515233).

By combining these color pigments, a negative photosensitive resin composition with the desired optical properties can be obtained, but from the standpoint of visible light blocking and insulating properties per unit weight, it is preferable to include a benzofuranone pigment.

From the viewpoint of light-shielding property per unit film thickness, the content of component (D) in the negative photosensitive resin composition is preferably 5 parts by weight or more, and more preferably 10 parts by weight or more, per 100 parts by weight of the total solid content of the negative photosensitive resin composition. On the other hand, from the viewpoint of improving sensitivity during exposure and fine line processability, the content of component (D) is preferably 50 parts by weight or less, and more preferably 40 parts by weight or less, per 100 parts by weight of the negative photosensitive resin composition.

The negative photosensitive resin composition contains an organic solvent (E) (hereinafter, sometimes referred to as component (E)).

Examples of component (E) include ethers, acetates, esters, ketones, aromatic hydrocarbons, amides, and alcohols.

Examples of ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tetrahydrofuran, etc. Examples of acetates include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA"), propylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, etc. Examples of esters include methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, etc. Examples of ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc. Examples of aromatic hydrocarbons include toluene and xylene, etc. Examples of amides include N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc. Examples of alcohols include butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, diacetone alcohol, etc. Two or more of these may be contained. Among these, the boiling point at 1 atmosphere is preferably 170°C or less, and more preferably 150°C or less, since the solvent is likely to volatilize even when low-temperature baking is performed after patterning.

The negative photosensitive resin composition may further contain a resin (F) (hereinafter sometimes referred to as component (F)) having a repeating unit represented by general formula (5) having a tertiary amino group in the side chain, a repeating unit having a carboxyl group, and a repeating unit having an ethylenically unsaturated group.

In general formula (5), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents a single bond, an alkyl group having 1 to 5 carbon atoms, or an alkylene ether group having 1 to 5 carbon atoms and 1 oxygen atom, R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms.

Specific examples of monomers constituting the repeating unit represented by general formula (5) include 2-dimethylaminoethyl acrylate, 2-diethylaminoethyl acrylate, 2-dipropylaminoethyl acrylate, 2-diphenylaminoethyl acrylate, 2-dibenzylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-diethylaminoethyl methacrylate, 2-dipropylaminoethyl methacrylate, 2-diphenylaminoethyl methacrylate, and 2-benzylaminoethyl methacrylate. These monomers may be used alone or in combination of two or more. By including an alkali-soluble resin having a repeating unit represented by general formula (5), a tertiary amino group is adsorbed on the color pigment surface, and the storage stability of the negative photosensitive resin composition can be further improved.

Specific examples of monomers constituting repeating units having a carboxy group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, phthalic acid, phthalic anhydride, crotonic acid, 2-carboxyethyl acrylate oligomer, and 2-carboxyethyl methacrylate oligomer.

As a method for synthesizing component (F), a method can be used in which the structural unit represented by general formula (5) and the carboxyl group-containing unit are polymerized, and then a repeating unit having a known ethylenically unsaturated group is introduced. For example, a method can be used in which a glycidyl group-containing polymerizable unsaturated monomer is subjected to an addition reaction with a (meth)acrylic copolymer in which a carboxyl group-containing unsaturated monomer is copolymerized. In this case, examples of the carboxyl group-containing unsaturated monomer to be copolymerized include acrylic acid and methacrylic acid, and examples of the glycidyl group-containing unsaturated monomer to be copolymerized include glycidyl acrylate and glycidyl methacrylate. These acrylic monomers may be used alone or in a mixture of two or more types.

The acid value of component (F) is preferably 50 to 120 mgKOH/g, and by setting it in this range, it is possible to achieve both color pigment dispersion stability and solubility in alkaline developer. In addition, the base value is preferably 5 to 70 mmol/100 g, and by setting it in this range, it is possible to improve color pigment dispersion stability while maintaining solubility in alkaline developer. The base value is defined as the number of moles of perchloric acid required to neutralize 100 g of component (F).

From the viewpoint of color pigment dispersion stability, the content of component (F) is preferably 5 parts by weight or more per 100 parts by weight of components (A) and (F) combined. On the other hand, from the viewpoint of minimizing mask bias, the content of component (F) is preferably 50 parts by weight or less per 100 parts by weight of components (A) and (F) combined.

The negative photosensitive resin composition may contain a surfactant, if necessary, to improve wettability with the substrate or to improve the thickness uniformity of the photosensitive resin film. Commercially available compounds can be used as the surfactant. Specifically, silicone surfactants include the SH series, SD series, and ST series from Dow Corning Toray Silicone, the BYK series from BYK Japan, the KP series from Shin-Etsu Silicone, the Disform series from Nippon Oil & Fats, and the TSF series from Toshiba Silicone. Fluorine surfactants include the Megafac (registered trademark) series from Dainippon Ink & Coatings, the Fluorard series from Sumitomo 3M, the Surflon (registered trademark) series and Asahi Guard (registered trademark) series from Asahi Glass, the EF series from Shin-Akita Kasei, and the Polyfox series from OmNova Solutions. Surfactants made of acrylic and/or methacrylic polymers include, but are not limited to, the Polyflow series from Kyoeisha Chemical and the Disparlon (registered trademark) series from Kusumoto Chemical.

The content of the surfactant is preferably 0.0001 parts by weight or more and 1 part by weight or less per 100 parts by weight of the negative photosensitive resin composition.

The negative photosensitive resin composition may contain a polymer dispersant. A polymer dispersant is one that has both an affinity group that has a chemical bond or adsorption action to the color pigment surface and a polymer chain or group that has solvent affinity, and differs from component (F) in that it does not contain an ethylenically unsaturated group. Since the polymer dispersant does not have an ethylenically unsaturated group, there is a concern that the target photosensitive performance may be deteriorated if a large amount is added, and it is desirable to add an appropriate amount taking into account dispersion stability and photosensitive performance. In the wet media dispersion treatment described below, the polymer dispersant improves the wettability of the color pigment to the dispersion medium, promotes the deagglomeration of the light-shielding material, stabilizes the particle size and viscosity by steric hindrance and/or electrostatic repulsion effects, and further has the effect of suppressing the occurrence of color separation during storage or application of the negative photosensitive resin composition.

Examples of polymer dispersants include polyester-based polymer dispersants, acrylic-based polymer dispersants, polyurethane-based polymer dispersants, polyallylamine-based polymer dispersants, and carbodiimide-based dispersants. Among these, polymer dispersants having amino groups are preferred in order to improve the long-term storage stability of color pigment dispersions.

Methods for producing a negative-type photosensitive resin composition include, for example, dispersing component (D) directly into a solution containing components (A), (B), and (C) using a disperser, dispersing component (D) into component (A) using a disperser to prepare a colored dispersion, and then mixing the colored dispersion with components (B) and (C).

Examples of dispersing machines include ball mills, sand grinders, three-roll mills, and high-speed impact mills. Among these, bead mills are preferred from the viewpoint of improving dispersion efficiency and fine dispersion. Examples of bead mills include coball mills, basket mills, pin mills, and dyno mills. Examples of beads for bead mills include titania beads, zirconia beads, and zircon beads. The bead diameter of the bead mill is preferably 0.03 to 1.0 mm. When the primary particle diameter of component (A) and the particle diameter of the secondary particles formed by aggregation of the primary particles are small, fine dispersion beads of 0.03 to 0.10 mm are preferred.

In this case, a bead mill having a centrifugal separator capable of separating minute beads from the dispersion liquid is preferred. On the other hand, when dispersing component (D) containing coarse particles of the submicron order, beads with a bead diameter of 0.10 mm or more are preferred because they provide sufficient crushing power. The bead diameter can be calculated by measuring the circle equivalent diameter of 100 beads randomly selected by microscopic observation and calculating the number average value.

The cured film of the present invention is obtained by curing the negative photosensitive resin composition.
Methods for curing the negative photosensitive resin composition include photocuring and heat curing. Specifically, it is preferable to carry out both photocuring and heat curing, which will be described later.

The method for producing a cured film obtained by curing a negative-type photosensitive resin composition is described below.

The method for producing the cured film includes a step of applying a negative photosensitive resin composition to form a photosensitive resin film, a step of drying the photosensitive resin film, a step of exposing the photosensitive resin film, a step of developing the exposed photosensitive resin film, and a step of heat curing.
Specific methods for producing the cured film include, for example, the method described in JP-A-2019-023728, but the film can be produced by any known method.

The organic EL display device of the present invention comprises the cured film.
The organic EL display device has at least a substrate, a first electrode, a second electrode, a light-emitting pixel, a planarization layer, and a pixel division layer. An active matrix type organic EL display device having a plurality of pixels formed in a matrix is preferred. The active matrix type display device has light-emitting pixels on a substrate such as glass, and has a planarization layer provided so as to cover the lower parts of the light-emitting pixels and parts other than the light-emitting pixels. Furthermore, on the planarization layer, a first electrode provided so as to cover at least the lower parts of the light-emitting pixels, and a second electrode provided so as to cover at least the upper parts of the light-emitting pixels. In addition, the active matrix type display device has an insulating pixel division layer to divide the light-emitting pixels, and the cured film obtained from the negative type photosensitive resin composition of the present invention can be suitably used for the pixel division layer.

In addition, the negative photosensitive resin composition of the present invention can form highly precise patterns that do not leave residues in the openings, and can therefore be used for colored partition walls for solid-state imaging devices, micro LEDs, and mini LED display devices, as well as black matrices and black column spacers used in color filters for liquid crystal display devices.

The present invention will be described in detail below with reference to examples and comparative examples, but the aspects of the present invention are not limited to these.

<Evaluation method>
[Molecular weight]
The weight average molecular weight (Mw) was measured using gel permeation chromatography (GPC) "HLC-8220GPC" (a testing device manufactured by Tosoh Corporation) using tetrahydrofuran as a carrier and polystyrene as a molecular weight standard.

[sensitivity]
The negative photosensitive resin composition obtained in each Example and Comparative Example was applied onto an ITO substrate using a spinner (MS-A150) manufactured by Mikasa Co., Ltd., so that the OD value of the photosensitive resin film was 1.5, and the photosensitive resin film was heated and dried on a hot plate at 100 ° C. for 2 minutes. This photosensitive resin film was exposed to light using a mask aligner (PEM-6M) manufactured by Union Optical Co., Ltd., through a negative mask (stripe design line width 10 μm) manufactured by HOYA Co., Ltd., with a high-pressure mercury lamp as the light source at a maximum exposure of 500 mJ / cm ² , and the exposure amount was reduced every 10 mJ / cm ² , and a patterned substrate was obtained by developing for 60 seconds with an alkaline developer of a 2.38 wt% TMAH aqueous solution. Next, the obtained patterned substrate was baked in a hot air oven at 230 ° C. for 60 minutes to obtain a cured film.

The obtained cured film of the negative photosensitive resin composition was observed under an optical microscope, and the minimum exposure amount (mJ/cm ² ) at which a cured film could be formed without peeling was taken as the sensitivity.
[Light blocking properties]
Of the cured films of the negative photosensitive resin compositions obtained in each of the Examples and Comparative Examples, the OD value of the cured film at the minimum exposure dose at which a pattern could be formed was measured using an X-rite 361T (visual) densitometer to measure the intensities of incident light and transmitted light, and calculated according to the following formula (3).

OD value=log ₁₀ (I ₀ /I) Equation (3)
_I0 : Incident light intensity I: Transmitted light intensity Furthermore, the thickness of the cured film was measured using a contact type film thickness meter DEKTAK150 (manufactured by ULVAC, Inc.), and the light blocking ability per 1 μm of each cured film was evaluated by calculating the OD value/film thickness.

[Mask Bias]
Of the cured films of the negative photosensitive resin compositions obtained in each of the Examples and Comparative Examples, the opening width of a stripe pattern having a mask opening width of 10 μm at the minimum exposure dose that enabled pattern formation was measured using an optical microscope, and it was determined that the smaller the absolute value of the difference between the mask design value and the opening width of the cured film, the smaller the mask bias and the better the result.

Evaluation A: Mask bias less than 1.0 μm B: Mask bias 1.0 μm or more and less than 2.0 μm C: Mask bias 2.0 μm or more and less than 3.0 μm D: Mask bias 3.0 μm or more.

[Storage stability]
The initial sensitivity of the negative photosensitive resin compositions obtained in the Examples and Comparative Examples and the sensitivity after standing for 7 days at 23° C. were evaluated in the same manner as for the initial sensitivity. A smaller sensitivity change rate (%), which is the ratio of the sensitivity after aging to the initial sensitivity, was determined to be an indication of superior stability as a negative photosensitive resin composition.

Evaluation A: Sensitivity change rate less than 120% B: Sensitivity change rate 120% or more and less than 150% C: Sensitivity change rate 150% or more and less than 200% D: Sensitivity change rate 200% or more.

[Long-term reliability evaluation of organic EL display devices]
FIG. 1 shows a schematic diagram of the procedure for producing an organic EL display device using the negative photosensitive resin composition obtained in each Example and Comparative Example. First, a 10 nm ITO transparent conductive film was formed on the entire surface of a 38 mm x 46 mm alkali-free glass substrate 1 by sputtering, and etched as a first electrode (transparent electrode) 2. At the same time, an auxiliary electrode 3 for extracting a second electrode was also formed. The obtained substrate was ultrasonically cleaned with Semicoclean 56 (trade name, manufactured by Furuuchi Chemical Co., Ltd.) for 10 minutes, and then washed with ultrapure water. Next, a negative photosensitive resin composition (PB-1) was applied to the entire surface of the substrate by spin coating, and prebaked on a hot plate at 100 ° C. for 2 minutes. This film was exposed to the minimum exposure amount of each negative photosensitive resin composition using a high-pressure mercury lamp as a light source through a photomask, and then developed with a 2.38 wt % TMAH aqueous solution, unnecessary parts were dissolved, and rinsed with pure water. The obtained resin pattern was heat-treated at 230°C for 60 minutes in a hot air oven. In this way, an insulating layer 4 was formed in a limited area of the substrate, in which openings of 70 μm in width and 260 μm in length were arranged at a pitch of 155 μm in the width direction and a pitch of 465 μm in the length direction, and each opening had a shape that exposed the first electrode. In this way, an insulating layer with an insulating layer opening ratio of 25% was formed in the substrate effective area, which was a rectangle with one side of 16 mm. The thickness of the insulating layer was about 1.0 μm.

Next, after performing nitrogen plasma treatment as a pretreatment, an organic EL layer 5 including a light-emitting layer was formed by a vacuum deposition method. The degree of vacuum during deposition was 1×10 ⁻³ Pa or less, and the substrate was rotated relative to the deposition source during deposition. First, compound (HT-1) was deposited to a thickness of 10 nm as a hole injection layer, and compound (HT-2) was deposited to a thickness of 50 nm as a hole transport layer. Next, compound (GH-1) as a host material and compound (GD-1) as a dopant material were deposited to a thickness of 40 nm on the light-emitting layer so that the doping concentration was 10%. Next, compound (ET-1) and compound (LiQ) were laminated to a thickness of 40 nm at a volume ratio of 1:1 as electron transport materials. The structures of the compounds used in the organic EL layer are shown below.

Next, after depositing a compound (LiQ) to a thickness of 2 nm, Mg and Ag were deposited to a thickness of 10 nm at a volume ratio of 10:1 to form a second electrode (non-transparent electrode) 6. Finally, a cap-shaped glass plate was sealed by bonding it with an epoxy resin adhesive under a low-humidity nitrogen atmosphere, and four top-emission type organic EL display devices each having a square shape with a side length of 5 mm were fabricated on one substrate. The film thickness referred to here is the display value on a quartz crystal oscillation film thickness monitor.
The organic EL display device thus fabricated was placed on a hot plate heated to 80° C. with the light-emitting surface facing up, and was irradiated with UV light having a wavelength of 365 nm and an illuminance of 0.6 kmW/cm ^2. Immediately after irradiation (0 hours) and after 1000 hours had elapsed, the organic EL display device was driven by a direct current of 0.625 mA to emit light, and the area ratio of the light-emitting portion to the area of the light-emitting pixel (pixel light-emitting area ratio) was measured. If the pixel light-emitting area ratio after 1000 hours according to this evaluation method is 80% or more, it can be said that the long-term reliability is excellent, and if it is 90% or more, it is more preferable.

Evaluation A: pixel light emitting area ratio 95% or more B: pixel light emitting area ratio 90% or more and less than 95% C: pixel light emitting area ratio 80% or more and less than 90% D: pixel light emitting area ratio less than 80%.

<Production Example>
(Synthesis Example 1: Alkali-soluble resin A-1)
33.40 g of 4-hydroxyphenyl methacrylate ("PQMA" manufactured by Showa Denko K.K.) and 6.66 g of GMA were completely dissolved in 100.0 g of PGMEA, and 3.66 g of V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator was completely dissolved in 15.0 g of PGMEA. The two obtained solutions were simultaneously dropped over 2 hours into 45.0 g of PGMEA heated to 85° C. under a nitrogen gas atmosphere in a 300 mL three-neck flask, and after completion of the dropping, the mixture was reacted at 85° C. for 3 hours to obtain a 20 wt % solids solution of alkali-soluble resin A-1 with PQMA/GMA=80/20. The weight average molecular weight of the obtained reaction product was 8800.

(Synthesis Example 2: Alkali-soluble resin A-2)
A 20 wt % solids solution of alkali-soluble resin A-2 (PQMA/GMA=70/30) was obtained by changing the amount of PQMA to 29.80 g and the amount of GMA to 10.20 g in the same manner as in Synthesis Example 1. The weight average molecular weight of the resulting reaction product was 8,500.

(Synthesis Example 3: Alkali-soluble resin A-3)
A 20 wt % solids solution of alkali-soluble resin A-3 (PQMA/GMA=60/40) was obtained by changing the amount of PQMA to 26.10 g and the amount of GMA to 13.90 g in the same manner as in Synthesis Example 1. The weight average molecular weight of the resulting reaction product was 8,600.

(Synthesis Example 4: Alkali-soluble resin A-4)
A 20 wt % solids solution of alkali-soluble resin A-4 (PQMA/GMA=40/60) was obtained by changing the amount of PQMA to 18.20 g and the amount of GMA to 21.80 g in the same manner as in Synthesis Example 1. The weight average molecular weight of the resulting reaction product was 8,300.

(Synthesis Example 5: Alkali-soluble resin A-5)
A 20 wt % solids solution of alkali-soluble resin A-5 (PQMA/GMA=35/65) was obtained by changing the amount of PQMA to 16.11 g and the amount of GMA to 23.89 g in the same manner as in Synthesis Example 1. The weight average molecular weight of the resulting reaction product was 8,100.

(Synthesis Example 6: Alkali-soluble resin A-6)
A 20 wt % solids solution of alkali-soluble resin A-6 (PQMA/GMA=30/70) was obtained by changing the amount of PQMA to 13.97 g and the amount of GMA to 26.03 g in the same manner as in Synthesis Example 1. The weight average molecular weight of the resulting reaction product was 8,400.

(Synthesis Example 7: Alkali-soluble resin A-7)
A 20% by weight solids solution of alkali-soluble resin A-7 (PQMA/GMA=20/80) was obtained by changing the amount of PQMA to 9.54 g and the amount of GMA to 30.46 g in the same manner as in Synthesis Example 1. The weight average molecular weight of the resulting reaction product was 8,400.

(Synthesis Example 8: Alkali-soluble resin A-8)
A 20% by weight solids solution of alkali-soluble resin A-8 (PEMA/GMA=20/80) was obtained by using PEMA instead of PQMA as the monomer type to be added in the same manner as in Synthesis Example 1, with the amount of PEMA being 10.64 g and the amount of GMA being 29.36 g. The weight average molecular weight of the resulting reaction product was 8,800.

(Synthesis Example 9: Alkali-soluble resin A-9)
A 20 wt % solids solution of alkali-soluble resin A-9 (4-hydroxystyrene/GMA=20/80) was obtained by using 4-hydroxystyrene instead of PQMA as the monomer type to be added in the same manner as in Synthesis Example 1, with the amount of 4-hydroxystyrene being 6.97 g and the amount of GMA being 33.03 g. The weight average molecular weight of the resulting reaction product was 9,000.

(Synthesis Example 10: Alkali-soluble resin A-10)
A 20 wt % solids solution of alkali-soluble resin A-10 (PQMA/4HBAGE=40/60) was obtained by using 4HBAGE instead of GMA as the monomer type to be added in the same manner as in Synthesis Example 1, and changing the amount of PQMA to 14.90 g and the amount of 4HBAGE to 25.10 g. The weight average molecular weight of the resulting reaction product was 8,100.

(Synthesis Example 11: Alkali-soluble resin A-11)
A 20 wt % solids solution of alkali-soluble resin A-11 (PQMA/OXE-30=40/60) was obtained by using (3-ethyloxetan-3-yl)methyl methacrylate (OXE-30, manufactured by Osaka Organic Chemical Industry Co., Ltd.) instead of GMA as the type of monomer added in the same manner as in Synthesis Example 1, and changing the amount of PQMA to 17.08 g and the amount of OXE-30 to 22.92 g. The weight average molecular weight of the resulting reaction product was 9,200.

(Synthesis Example 12: Alkali-soluble resin A-12)
A 20 wt % solids solution of alkali-soluble resin A-12 with PQMA=100 was obtained by changing the type of monomer added to only 40.00 g of PQMA in the same manner as in Synthesis Example 1. The weight average molecular weight of the resulting reaction product was 7,500.

(Synthesis Example 13: Alkali-soluble resin A-13)
A 20 wt % solids solution of alkali-soluble resin A-13 having a GMA of 100 was obtained by changing the type of monomer added to 40.00 g of GMA in the same manner as in Synthesis Example 1. The weight average molecular weight of the resulting reaction product was 8,800.

(Synthesis Example 14: Tertiary Amino Group- and Ethylenically Unsaturated Group-Containing Resin (F-1))
400.0g of PGMEA was charged into a pressure vessel equipped with a stirrer, a thermometer, a reflux condenser, and a dropping pump, and the inside of the reaction vessel was filled with nitrogen, and then the temperature was raised to 90 ° C., and 2.0g of 2-dimethylaminoethyl methacrylate, 31.0g of methyl methacrylate, 20.0g of 2-ethylhexyl methacrylate, 30.0g of styrene, 17.0g of methacrylic acid, 2.0g of azobisisobutyronitrile as a polymerization initiator, and 3.0g of normal dodecyl mercaptan were mixed and dropped with a dropping pump over 3 hours to carry out copolymerization. Thereafter, the inside of the reaction vessel was replaced with air, and 10.0g of GMA was dropped with a dropping pump over 1 hour to carry out an addition reaction, and the vessel was further stirred for 2 hours. As a result, a tertiary amino group- and ethylenically unsaturated group-containing resin (F-1) solution having characteristic values of a base number of 11 mmol/100 g, an acid value of 73 mgKOH/g and a weight average molecular weight of 7,000 and a solid content concentration of 20% by weight was obtained.

(Synthesis Example 15: Resin (DP-1) that does not correspond to either component (A) or component (F))
By the method described in the literature (Japanese Patent No. 3120476, Example 1), a methyl methacrylate/methacrylic acid/styrene copolymer (weight ratio 30/40/30) was synthesized, and then 40 parts by weight of GMA was added thereto. The copolymer was then reprecipitated in purified water, filtered, and dried to obtain an acrylic copolymer (DP-1) having a weight average molecular weight (Mw) of 10,000 and an acid value of 110 (mgKOH/g).

(Production Example 1: Production of Color Pigment Dispersion (DB-1))
600 g of Irgaphor Black S0100CF (manufactured by BASF) as a color pigment, 468.5 g of a 20 wt% PGMEA solution of a resin (F-1) having a tertiary amino group, 56.3 g of a dispersant having an amine value of 20 mgKOH / g described in Synthesis Example 2 of JP-A-2020-070352 as a polymer dispersant, and 1875.2 g of PGMEA were charged in a tank and stirred with a homomixer for 20 minutes to obtain a preliminary dispersion. The obtained preliminary dispersion was supplied to a dispersing machine Ultra Apex Mill manufactured by Hiroshima Metal & Machinery Co., Ltd. equipped with a centrifugal separator filled with 70% by volume of 0.10 mmφ zirconia beads, and dispersed at a rotation speed of 10 m / s for 3 hours to obtain a color pigment dispersion (DB-1) with a solid content concentration of 25 wt%, color pigment / resin (by weight) = 80 / 20.

(Production Example 2: Production of Color Pigment Dispersion (DB-2))
A color pigment dispersion (DB-2) having a solid content of 25% by weight and a color pigment/resin (by weight) ratio of 80/20 was obtained by the same production method as DB-1, except that a 20% by weight PGMEA solution of resin (DP-1) was used.

Example 1
180.9 g of color pigment dispersion (DB-1), 284.3 g of 20 wt% PGMEA solution of alkali-soluble resin (A-1), 5.3 g of Adeka Arcles (registered trademark) NCI-831 as a photopolymerization initiator, 42.4 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a radical polymerizable compound, 0.2 g of silicone surfactant "BYK" (registered trademark) 333 (manufactured by BYK-Chemie Co., Ltd.), and 486.9 g of PGMEA were added to obtain a negative photosensitive resin composition (PB-1) with a total solids concentration of 15 wt%, color pigment / resin (weight ratio) = 25/75. Further, a cured film of the obtained negative photosensitive resin composition and an organic EL display device equipped with the cured film were prepared according to the above-mentioned method.

(Examples 2 to 11)
In the same manner as in Example 1, negative type photosensitive resin compositions (PB-2) to (PB-11), cured films thereof, and organic EL display devices comprising the cured films were obtained by using A-2 to A-10 as the alkali-soluble resins to be added, respectively.

Example 12
In the same manner as in Example 1, DB-2 was used as the color pigment dispersion liquid and A-4 was used as the alkali-soluble resin to be added, thereby obtaining a negative type photosensitive resin composition (PB-12), a cured film thereof, and an organic EL display device having the cured film thereof.

(Comparative Examples 1 to 3)
In the same manner as in Example 12, negative type photosensitive resin compositions (PB-13) to (PB-15) and cured films thereof, as well as organic EL display devices using these compositions as insulating layers, were obtained by using A-12, A-13 and DP-1 as the alkali-soluble resins to be added, respectively.
The compositions of the examples and comparative examples are shown in Table 1, and the evaluation results are shown in Table 2.

The negative type photosensitive resin compositions of the Examples achieved both high light-shielding properties and sensitivity, while reducing the mask bias during fine pattern processing. In addition, they had excellent storage stability as negative type photosensitive resin compositions, and the long-term reliability of organic EL display devices using the cured films thereof was excellent.
On the other hand, the negative photosensitive resin compositions of the comparative examples, Comparative Example 1 containing a homopolymer of general formula (1), had good mask bias but poor long-term reliability of the organic EL display device using the cured film, and Comparative Example 2 containing a homopolymer of general formula (3) had poor storage stability as a negative photosensitive resin composition, had a large mask bias, and was unable to process with the target pattern dimensions. Moreover, Comparative Example 3 not containing the repeating units represented by general formulas (1) to (4) was inferior to the examples in all of storage stability, mask bias, and long-term reliability of the organic EL display device.

1: Non-alkali glass substrate 2: First electrode (transparent electrode)
3: auxiliary electrode 4: insulating layer 5: organic EL layer 6: second electrode (non-transparent electrode)

Claims (7)

A negative type photosensitive resin composition comprising: an alkali-soluble resin (A) containing a repeating unit represented by general formula (1) and/or general formula (2) and a repeating unit represented by general formula (3) and/or general formula (4); a radical polymerizable compound (B); a radical polymerization initiator (C); a coloring pigment (D) ; an organic solvent (E); and a resin (F) having a repeating unit represented by general formula (5) having a tertiary amino group in a side chain, a repeating unit having a carboxy group, and a repeating unit having an ethylenically unsaturated group .

In general formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents a single bond, an alkylene group having 1 to 5 carbon atoms, or an alkylene ether group having 1 to 5 carbon atoms and 1 oxygen atom, and R ³ represents an alkyl group, alkoxy group, or acyl group having 1 to 5 carbon atoms. Furthermore, l represents an integer of 0 to 4, and m represents an integer of 1 to 4. When two or more R ^3s are present, these R ^3s may be different from each other or may be the same.
In general formula (2), ^R4 represents a hydrogen atom or a methyl group, and ^R5 represents an alkyl group, an alkoxy group, or an acyl group having 1 to 5 carbon atoms. In addition, n represents an integer of 0 to 4, and o represents an integer of 1 to 4. When two or more ^R5s are present, these ^R5s may be different from each other or may be the same.
In general formula (3), ^R6 represents a hydrogen atom or a methyl group, ^R7 represents a single bond, an alkylene group having 1 to 5 carbon atoms, or an alkylene ether group having 1 to 5 carbon atoms and 1 oxygen atom. ^R8 represents an alkyl group having 1 to 5 carbon atoms. Furthermore, p represents an integer of 1 to 5, and q represents an integer of 0 to 5. When two or more ^R8s are present, these ^R8s may be different from each other or may be the same.
In formula (4), R ⁹ represents a hydrogen atom or a methyl group, and R ¹⁰ represents a single bond, an alkylene group having 1 to 5 carbon atoms, or an alkylene ether group having 1 to 5 carbon atoms and 1 oxygen atom.
In general formula (5), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents a single bond, an alkyl group having 1 to 5 carbon atoms, or an alkylene ether group having 1 to 5 carbon atoms and 1 oxygen atom, and R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The negative photosensitive resin composition according to claim 1, wherein the total molar ratio M1 of the repeating units represented by general formula (1) and the repeating units represented by general formula (2) relative to 100 mol% of all repeating units in the alkali-soluble resin (A) is 30 mol% or more and less than 70 mol%. The negative photosensitive resin composition according to claim 1 or 2, wherein M1/M2 is 0.4 to 1.5, where M1 is the total molar ratio of the repeating units represented by general formula (1) and the repeating units represented by general formula (2) and M2 is the total molar ratio of the repeating units represented by general formula (3) and the repeating units represented by general formula (4) relative to 100 mol% of all repeating units in the alkali-soluble resin (A). The negative photosensitive resin composition according to any one of claims 1 to 3, wherein the alkali-soluble resin (A) has a repeating unit of general formula (1). The negative type photosensitive resin composition according to any one of claims 1 to 4, wherein R ² in the general formula (1) is a single bond. A cured film obtained by curing the negative photosensitive resin composition according to any one of claims 1 to 5 . An organic electroluminescence display device comprising the cured film according to claim 6 .