Negative photosensitive resin composition

Abstract

Provided is a photosensitive resin composition with which a cured film having high visible light shielding properties can be obtained even when a colorant such as carbon black is reduced. A negative photosensitive resin composition containing the following components (A) to (E). (A) A novolac phenolic resin in which the molar ratio [(a1): (a2): (a3): (a4)] of a m-cresol-derived structural unit (a1), a catechol-derived structural unit (a2), a benzaldehyde-derived structural unit (a3), and a salicylaldehyde-derived structural unit (a4) is 1: (0.25-4.0): (0.25-4.0): (0.25-4.0); (B) one or more resins selected from the group consisting of a polyimide containing an ethylenically unsaturated group, a polyimide precursor containing an ethylenically unsaturated group, a polybenzoxazole containing an ethylenically unsaturated group, and a polybenzoxazole precursor containing an ethylenically unsaturated group; (C) a radical polymerizable compound; (D) a photopolymerization initiator; and (E) an organic solvent.

Description

Technical Field

[0001] The present invention relates to a negative photosensitive resin composition, a cured film and a resist film. Background Art

[0002] As the next generation of flat panel displays, organic EL displays have attracted much attention. Organic EL displays are self-luminous display devices that utilize electroluminescence based on organic compounds, and can achieve high-angle viewing and high-speed response image display. In addition, they can be made thinner and lighter. In recent years, with the high-precision of organic EL displays, there is a demand for further miniaturization of light-emitting elements.

[0003] Organic EL displays use the energy of electrons injected from the cathode and holes injected from the anode to recombine to make the elements emit light. Therefore, if there is a substance that forms an energy level that hinders the recombination of electrons and holes, the luminous efficiency of the light-emitting element is reduced, and the life of the organic EL display is reduced. On the other hand, in order to divide the pixels of the light-emitting element, an insulating layer called a pixel division layer is usually formed between the transparent electrode on the light output side and the metal electrode on the opposite side. Since the pixel division layer is formed at a position adjacent to the light-emitting element, degassing and outflow of ion components from the pixel division layer may become a reason for the reduction in the life of the organic EL display. Therefore, heat resistance and durability are required for the pixel division layer.

[0004] From the viewpoint of high heat resistance, the pixel division layer is made of a photosensitive resin composition using polyimide resin or polybenzoxazole resin (for example, Patent Document 1). Since the pixel division layer is required to be black, the photosensitive resin composition contains about 20% of a colorant such as carbon black in the solid content.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: International Publication No. 2022 / 070946 Summary of the invention

[0008] Problems to be solved by the invention

[0009] In the production of fine patterns, the colorant added to the photosensitive resin composition may become residue during development. In addition, since carbon black has conductivity, it is also preferred to use a small amount in order to improve the insulation of the cured film. With the high precision of organic EL displays, in order to be able to produce a finer pixel division layer without generating residue, a photosensitive resin composition with high visible light shielding ability is required even if the amount of colorant added is reduced.

[0010] An object of the present invention is to provide a photosensitive resin composition which can provide a cured film having a high visible light shielding ability even when the amount of a colorant added is reduced.

[0011] Means for solving problems

[0012] The present inventors have conducted intensive studies to solve the above-mentioned problems and, as a result, have found that a cured film obtained from a negative photosensitive resin composition comprising a novolak-type phenolic resin composition having specific structural units in combination with at least one of a polyimide containing an ethylenically unsaturated group and a polybenzoxazole containing an ethylenically unsaturated group has high visible light shielding properties even when the amount of colorant used is reduced, thereby completing the present invention.

[0013] That is, the present invention relates to a negative photosensitive resin composition containing the following components (A) to (E).

[0014] (A) a novolac-type phenolic resin in which the molar ratio of the structural unit (a1) derived from m-cresol, the structural unit (a2) derived from catechol, the structural unit (a3) ​​derived from benzaldehyde and the structural unit (a4) derived from salicylaldehyde [(a1):(a2):(a3):(a4)] is 1:0.25-4.0:0.25-4.0:0.25-4.0;

[0015] (B) one or more resins selected from the group consisting of polyimides containing ethylenically unsaturated groups, polyimide precursors containing ethylenically unsaturated groups, polybenzoxazoles containing ethylenically unsaturated groups, and polybenzoxazole precursors containing ethylenically unsaturated groups;

[0016] (C) a free radical polymerizable compound;

[0017] (D) a photopolymerization initiator;

[0018] (E) Organic solvent.

[0019] The present invention further relates to a cured film obtained from the negative photosensitive resin composition.

[0020] The present invention further relates to a resist film obtained from the negative photosensitive resin composition.

[0021] Effects of the Invention

[0022] According to the present invention, it is possible to provide a photosensitive resin composition that can provide a cured film having a high visible light shielding ability even when the amount of a colorant added is reduced. DETAILED DESCRIPTION

[0023] The following describes the mode for carrying out the invention.

[0024] In addition, in this specification, "x to y" represents a numerical range of "x or more and y or less." The upper limit value and the lower limit value described in the numerical range can be arbitrarily combined.

[0025] Furthermore, an embodiment in which two or more of the embodiments of the present invention described below are combined is also an embodiment of the present invention.

[0026] [Negative photosensitive resin composition]

[0027] The negative photosensitive resin composition according to one embodiment of the present invention contains the following components (A) to (E).

[0028] (A) a novolac-type phenolic resin in which the molar ratio of the structural unit (a1) derived from m-cresol, the structural unit (a2) derived from catechol, the structural unit (a3) ​​derived from benzaldehyde and the structural unit (a4) derived from salicylaldehyde [(a1):(a2):(a3):(a4)] is 1:0.25-4.0:0.25-4.0:0.25-4.0;

[0029] (B) one or more resins selected from the group consisting of polyimides containing ethylenically unsaturated groups, polyimide precursors containing ethylenically unsaturated groups, polybenzoxazoles containing ethylenically unsaturated groups, and polybenzoxazole precursors containing ethylenically unsaturated groups;

[0030] (C) a free radical polymerizable compound;

[0031] (D) a photopolymerization initiator;

[0032] (E) Organic solvent.

[0033] In the present embodiment, by using the linear phenolic resin of (A), a cured film having high visible light shielding properties can be obtained even if the amount of colorant added is reduced. In addition, by using the resins of (A) and (B) in combination, the compatibility of the two resins is improved. Thus, the occurrence of poor film formation (scum) can be suppressed. In addition, a negative photosensitive resin composition can be obtained that has high alkali solubility in the non-exposed portion and excellent elastic modulus of the resist film and cured film.

[0034] Hereinafter, the constituent components of the negative photosensitive resin composition will be described.

[0035] ■Ingredients (A)

[0036] In the novolac-type phenolic resin as component (A), the molar ratio of the structural unit (a1) derived from m-cresol, the structural unit (a2) derived from catechol, the structural unit (a3) ​​derived from benzaldehyde and the structural unit (a4) derived from salicylaldehyde [(a1):(a2):(a3):(a4)] is 1:0.25-4.0:0.25-4.0:0.25-4.0.

[0037] In this embodiment, by making the linear phenolic resin as component (A) contain the structural unit (a2) derived from catechol, the visible light shielding property of the cured film is improved. Therefore, the amount of colorant used can be reduced. The visible light shielding property of the cured film can be adjusted by the molar ratio of the structural unit (a2).

[0038] The molar ratio [(a1):(a2):(a3):(a4)] is preferably 1:0.3-3.5:0.8-3.0:0.5-2.0 from the viewpoint of obtaining a cured film having high sensitivity, excellent compatibility with the resins and visible light shielding properties.

[0039] In one embodiment, the molar ratio of the total of the structural units (a1) derived from meta-cresol and the structural units (a2) derived from catechol in the component (A) [(a1) + (a2)] to the total of the structural units (a3) ​​derived from benzaldehyde and the structural units (a4) derived from salicylaldehyde [(a3) + (a4)] [(a1) + (a2): (a3) ​​+ (a4)] is 1: 0.8 to 1.2, preferably 1: 0.9 to 1.1. Thus, it is easy to adjust the weight average molecular weight of the component (A) to a suitable range. In addition, when the negative photosensitive resin composition of the present embodiment is made into a photosensitive film, the alkali solubility (sensitivity) can be improved.

[0040] In one embodiment, the molar ratio [(a2) / ((a1)+(a2))] of the structural unit (a2) in the component (A) relative to the total [(a1)+(a2)] of the structural unit (a1) derived from meta-cresol and the structural unit (a2) derived from catechol is 0.01 to 0.8. Both the structural unit (a1) and the structural unit (a2) are derived from a compound having a hydroxyl group. By increasing the molar ratio of the structural unit (a2), the visible light shielding property of the cured film can be improved. On the other hand, the alkali solubility can be adjusted by using the molar ratio of the structural unit (a1). From the viewpoint of both alkali solubility and visible light shielding property, the molar ratio [(a2) / ((a1)+(a2))] is preferably 0.1 to 0.7, and more preferably 0.3 to 0.6.

[0041] In one embodiment, the molar ratio [(a3) / ((a3)+(a4))] of the structural unit (a3) ​​in the component (A) relative to the total [(a3)+(a4)] of the structural unit (a3) ​​derived from benzaldehyde and the structural unit (a4) derived from salicylaldehyde is 0.2 to 0.8. Both the structural unit (a3) ​​and the structural unit (a4) are derived from a compound having an aldehyde group. The alkaline solubility can be appropriately adjusted using the molar ratio [(a3) / ((a3)+(a4))]. The molar ratio [(a3) / ((a3)+(a4))] is preferably 0.3 to 0.7.

[0042] Component (A) may contain structural units other than the structural units (a1) to (a4). Examples of structural units other than the structural units (a1) to (a4) include structural units derived from phenols other than m-cresol and catechol, and aldehydes other than benzaldehyde and salicylaldehyde.

[0043] Examples of the phenols include phenol, o-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, and 3,4,5-trimethylphenol.

[0044] Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, chloroacetaldehyde, 4-hydroxybenzaldehyde, and 3-hydroxybenzaldehyde.

[0045] The total content of the above-mentioned structural units (a1), (a2), (a3) ​​and (a4) in component (A) is preferably 30% by mass or more, more preferably 50% by mass or more, and further preferably 90% by mass or more, from the viewpoint of obtaining an anti-etching film and a cured film having high sensitivity, excellent resin compatibility and visible light shielding properties.

[0046] The total content of the structural units (a1), (a2), (a3) ​​and (a4) may be substantially 100% by mass. It should be noted that the term "substantially 100% by mass" means that structural units other than the structural units (a1), (a2), (a3) ​​and (a4) are inevitably included.

[0047] The weight average molecular weight of the linear phenolic resin as component (A) is preferably 1000 or more, more preferably 1500 or more. In addition, it is preferably 7000 or less, more preferably 6000 or less, and further preferably 5000 or less. If the weight average molecular weight is 1000 or more, it is highly heat-resistant, so it is preferred. On the other hand, if the weight average molecular weight is 7000 or less, it is highly sensitive, so it is preferred. It should be noted that in this specification, the weight average molecular weight is measured according to the conditions described in the examples.

[0048] Component (A) is obtained by polycondensing m-cresol, catechol, benzaldehyde and salicylaldehyde in an organic solvent at a molar ratio (m-cresol: catechol: benzaldehyde: salicylaldehyde) of 1:0.25-4.0:0.25-4.0:0.25-4.0 using an acid catalyst.

[0049] The molar ratio of meta-cresol, catechol, benzaldehyde and salicylaldehyde (meta-cresol: catechol: benzaldehyde: salicylaldehyde) is preferably in the range of 1:0.3 to 3.5:0.8 to 3.0:0.5 to 2.0 from the viewpoint of obtaining a resist film and a cured film having high sensitivity, excellent resin compatibility and visible light shielding properties.

[0050] In one embodiment, the molar ratio of the total of meta-cresol and catechol to the total of benzaldehyde and salicylaldehyde ((meta-cresol+catechol):(benzaldehyde+salicylaldehyde)) is 1:0.8-1.2.

[0051] The molar ratio of catechol to the total of meta-cresol and catechol (catechol / (meta-cresol+catechol)) is 0.01 to 0.8.

[0052] The molar ratio of salicylaldehyde to the total of salicylaldehyde and benzaldehyde (salicylicaldehyde / (salicylicaldehyde+benzaldehyde)) is 0.2 to 0.8.

[0053] When the novolac-type phenolic resin as the component (A) is obtained by polycondensing m-cresol, catechol, benzaldehyde and salicylaldehyde in an organic solvent, the organic solvent may contain phenols and aldehydes other than m-cresol, catechol, benzaldehyde and salicylaldehyde as described above.

[0054] The ratio of the total mass of m-cresol, catechol, benzaldehyde and salicylaldehyde to the total mass of all starting materials that can become structural units constituting component (A) in the organic solvent is preferably 30 mass % or more, more preferably 50 mass % or more, and even more preferably substantially 100 mass % from the viewpoint of obtaining a resist film and a cured film having high sensitivity, excellent compatibility with the resin and visible light shielding properties.

[0055] Examples of the organic solvent used in the production of component (A) include methanol, ethanol, 1-propanol, 2-propanol, butanol, hexanol, ethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, toluene, and the like. Among them, preferably, at least one selected from ethanol, 1-propanol and 2-propanol is used, and more preferably, ethanol is used.

[0056] The amount of the organic solvent used is preferably 20 parts by mass or more, more preferably 50 parts by mass or more, based on 100 parts by mass of the raw material from which the structural units of component (A) are derived, from the viewpoint of uniformity of the reaction, and is preferably 500 parts by mass or less, more preferably 300 parts by mass or less.

[0057] Examples of the acid catalyst used in the production of component (A) include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and boric acid; and organic acids such as oxalic acid, acetic acid, and p-toluenesulfonic acid. Among them, inorganic acids and p-toluenesulfonic acid are preferred, and p-toluenesulfonic acid is more preferred in order to further promote the reaction.

[0058] The amount of the acid catalyst added is not particularly limited, but is preferably 5 parts by mass or more, more preferably 20 parts by mass or more, and preferably 150 parts by mass or less, more preferably 100 parts by mass or less, based on 100 parts by mass of the raw material from which the structural units of component (A) are derived.

[0059] The reaction temperature when polycondensing the raw materials of component (A) is preferably 30°C or higher, more preferably 40°C or higher, and preferably 100°C or lower, more preferably 80°C or lower, from the viewpoint of promoting the reaction and efficiently increasing the molecular weight.

[0060] The reaction time is preferably 4 hours or longer, more preferably 12 hours or longer, and preferably 32 hours or shorter, more preferably 24 hours or shorter.

[0061] ■Ingredient (B)

[0062] Component (B) is one or more resins selected from polyimide containing ethylenically unsaturated groups, polyimide precursor containing ethylenically unsaturated groups, polybenzoxazole containing ethylenically unsaturated groups, and polybenzoxazole precursor containing ethylenically unsaturated groups. Component (B) is a substance obtained by introducing ethylenically unsaturated groups into each of polyimide, polyimide precursor, polybenzoxazole or polybenzoxazole precursor. Component (B) can use resins that have been used in photosensitive resin compositions.

[0063] <Polyimide and polyimide precursor>

[0064] As a polyimide precursor, for example, a substance obtained by reacting tetracarboxylic acid, a corresponding tetracarboxylic dianhydride or a tetracarboxylic diester dichloride, etc. with a diamine, a corresponding diisocyanate compound or a trimethylsilylated diamine, etc., can be cited, and it has a tetracarboxylic acid and / or its derivative residue and a diamine and / or its derivative residue. As a polyimide precursor, for example, polyamic acid, polyamic acid ester, polyamic acid amide or polyisoimide can be cited.

[0065] Examples of the polyimide include those obtained by dehydration ring closure of the above-mentioned polyamic acid, polyamic acid ester, polyamic acid amide or polyisoimide by heating or reaction using an acid or a base, and having a tetracarboxylic acid and / or a derivative residue thereof and a diamine and / or a derivative residue thereof.

[0066] As for the tetracarboxylic dianhydride used for synthesis of the polyimide, pyromellitic anhydride is preferable from the viewpoint of heat resistance. As for the diamine used for synthesis of the polyimide, 4,4-diaminodiphenyl ether is preferable from the viewpoint of heat resistance.

[0067] The polyimide containing unsaturated groups and the polyimide precursor containing unsaturated groups used in the present invention have the above-mentioned polyimide or polyimide precursor and an ethylenically unsaturated group as a free radical polymerizable group. By having an ethylenically unsaturated group, the sensitivity during exposure can be improved. As the polyimide containing unsaturated groups and the polyimide precursor containing unsaturated groups, it is preferably a substance obtained by reacting a part of phenolic hydroxyl and / or carboxyl of the polyimide and the polyimide precursor with a compound having an ethylenically unsaturated group described later. Utilizing the above-mentioned reaction, it is possible to introduce an ethylenically unsaturated group into the resin.

[0068] <Polybenzoxazole and polybenzoxazole precursor>

[0069] As a polybenzoxazole precursor, for example, a substance obtained by reacting a dicarboxylic acid, a corresponding dicarboxylic acid dichloride or a dicarboxylic acid active diester with a bisaminophenol compound as a diamine, etc., having a dicarboxylic acid and / or its derivative residue and a bisaminophenol compound and / or its derivative residue. As a polybenzoxazole precursor, for example, a polyhydroxyamide can be mentioned.

[0070] Examples of polybenzoxazoles include those obtained by subjecting a dicarboxylic acid and a bisaminophenol compound as a diamine to dehydration ring closure reaction using polyphosphoric acid, and those obtained by subjecting the above-mentioned polyhydroxyamide to dehydration ring closure reaction using heating or using phosphoric anhydride, a base or a carbodiimide compound, etc., and having a dicarboxylic acid and / or its derivative residue and a bisaminophenol compound and / or its derivative residue.

[0071] As for the bisaminophenol used for the synthesis of polybenzoxazole, 3,3-hydroxybenzidine is preferable from the viewpoint of heat resistance. As for the dicarboxylic acid used for the synthesis of polybenzoxazole, 4,4-biphenyldicarboxylic acid is preferable from the viewpoint of heat resistance.

[0072] In the polybenzoxazole containing ethylenically unsaturated groups used in the present invention and the polybenzoxazole precursor containing ethylenically unsaturated groups, as free radical polymerizable groups, there are ethylenically unsaturated groups. By having ethylenically unsaturated groups, the sensitivity during exposure can be improved. As the polybenzoxazole containing ethylenically unsaturated groups and the polybenzoxazole precursor containing ethylenically unsaturated groups, it is preferably a material obtained by reacting a part of phenolic hydroxyl and / or carboxyl of polybenzoxazole and polybenzoxazole precursor with the compound having ethylenically unsaturated groups described later. Utilizing the above reaction, it is possible to import ethylenically unsaturated groups into resin.

[0073] <Compounds Having Ethylenically Unsaturated Groups>

[0074] Examples of the compound having an ethylenically unsaturated group include isocyanate compounds, isothiocyanate compounds, epoxy compounds, aldehyde compounds, thialdehyde compounds, ketone compounds, thione compounds, acetate compounds, carboxylic acid chlorides, carboxylic anhydrides, carboxylic acid active ester compounds, carboxylic acid compounds, halogenated alkyl compounds, azidated alkyl compounds, trifluoromethanesulfonate compounds, methanesulfonate compounds, toluenesulfonate compounds, and cyanated alkyl compounds.

[0075] <Synthesis Method of Polyimide, Polybenzoxazole, Polyimide Precursor or Polybenzoxazole Precursor>

[0076] Polyimide, polyimide precursor, polybenzoxazole or polybenzoxazole precursor can be synthesized by known methods. As a specific method, for example, diamines or bisaminophenol compounds are first dissolved in a reaction solvent, and carboxylic anhydrides are slowly added to the solution in substantially equimolar amounts. Using a mechanical stirrer, the mixed solution is preferably stirred at a temperature of 0 to 200° C., more preferably at a temperature of 40 to 150° C. for 0.5 to 50 hours, more preferably for 2 to 24 hours. When using an end-capping agent, after adding the carboxylic anhydrides, stir at a given temperature for a given time, then slowly add the end-capping agent and stir.

[0077] The reaction solvent used in the polymerization reaction can dissolve the diamines or bisaminophenol compounds and carboxylic anhydrides as raw materials, preferably a polar solvent. As the reaction solvent, for example, amides such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methyl-2-pyrrolidone, cyclic esters such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone or α-methyl-γ-butyrolactone, carbonates such as ethylene carbonate or propylene carbonate, glycols such as triethylene glycol, phenols such as m-cresol or p-cresol, or acetophenone, 1,3-dimethyl-2-imidazolidinone, cyclopentane, dimethyl sulfoxide, etc. can be cited. Regarding the reaction solvent amount, when the total of diamines or bisaminophenol compounds and carboxylic anhydrides is set to 100 parts by mass, it is preferably 100 to 1900 parts by mass, and more preferably 150 to 950 parts by mass.

[0078] One or more selected from polyimide, polybenzoxazole, polyimide precursor and polybenzoxazole precursor is preferably obtained by the following operation, that is, after the polymerization reaction is completed, precipitation occurs in a poor solvent such as methanol, water, etc. for one or more selected from polyimide, polybenzoxazole, polyimide precursor and polybenzoxazole precursor, and then washing and drying are performed. By performing reprecipitation treatment, low molecular weight components can be removed, so the mechanical properties (elastic modulus) of the cured film are greatly improved.

[0079] <Synthesis Method of Polyimide Containing Ethylenically Unsaturated Groups, Polyimide Precursor Containing Ethylenically Unsaturated Groups, Polybenzoxazole Containing Ethylenically Unsaturated Groups, or Polybenzoxazole Precursor Containing Ethylenically Unsaturated Groups>

[0080] The polyimide containing an ethylenically unsaturated group, the polyimide precursor containing an ethylenically unsaturated group, the polybenzoxazole containing an ethylenically unsaturated group, or the polybenzoxazole precursor containing an ethylenically unsaturated group can be synthesized by a known method.

[0081] As reaction conditions for further introducing ethylenically unsaturated groups into polyimide, polybenzoxazole, polyimide precursor or polybenzoxazole precursor, preferred conditions are: for example, after fully replacing the reaction container with nitrogen under air or by bubbling, decompression degassing, etc., polyimide, polyimide precursor, polybenzoxazole or polybenzoxazole precursor and a compound having an ethylenically unsaturated group are added to a reaction solvent, and reacted at 20 to 110° C. for 30 to 500 minutes. In addition, a polymerization inhibitor such as a phenol compound, an acid catalyst or a base catalyst can be used as needed.

[0082] In component (B), for specific descriptions of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyimide containing an ethylenically unsaturated group, polyimide precursor containing an ethylenically unsaturated group, polybenzoxazole containing an ethylenically unsaturated group, and polybenzoxazole precursor containing an ethylenically unsaturated group, reference can be made to the contents of

[0074] to

[0210] of International Publication No. 2017 / 159876 as appropriate.

[0083] The weight average molecular weight of component (B) is preferably 5000 or more, more preferably 10000 or more. In addition, it is preferably 50000 or less, more preferably 40000 or less. If the weight average molecular weight is 5000 or more, it is highly heat-resistant, so it is preferred. On the other hand, if the weight average molecular weight is 50000 or less, it is preferred from the viewpoint of solvent solubility.

[0084] The amount of component (B) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, relative to 100 parts by mass of component (A), from the perspective of obtaining good sensitivity and obtaining a cured film having excellent visible light shielding properties. In addition, it is preferably 2000 parts by mass or less, more preferably 1000 parts by mass or less.

[0085] ■Ingredient (C)

[0086] Component (C) is a free radical polymerizable compound. The so-called free radical polymerizable compound refers to a compound having multiple ethylenically unsaturated groups in the molecule. By containing a free radical polymerizable compound, the curing of the exposed portion can be promoted and the sensitivity during exposure can be improved. In addition, the crosslinking density after thermal curing is increased, which can increase the hardness (elastic modulus) of the cured film.

[0087] The radical polymerizable compound is not particularly limited, and a known radical polymerizable compound can be used. However, a compound having a (meth)acrylic group that easily promotes radical polymerization is preferred.

[0088] From the viewpoint of improving sensitivity during exposure and improving hardness of a cured film, a compound having two or more (meth)acrylic groups in the molecule is more preferred.

[0089] Examples of the radical polymerizable compound include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane di(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate. Acid esters, 1,3-butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, dihydroxymethyl-tricyclodecane di(meth)acrylate, ethoxylated glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tri(meth)acrylate acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, pentapentaerythritol undec(meth)acrylate, pentapentaerythritol dodeca(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-(3-(meth)acrylate]

[0063] The invention can be selected from the group consisting of: 1,3,5-tris((meth)acryloyloxyethyl)isocyanurate, 1,3-bis((meth)acryloyloxyethyl)isocyanurate, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 9,9-bis[4-(3-(meth)acryloyloxypropoxy)phenyl]fluorene or 9,9-bis(4-(meth)acryloyloxyphenyl)fluorene or their acid-modified, ethylene oxide-modified or propylene oxide-modified products.

[0090] The amount of the radical polymerizable compound is preferably 1 part by mass or more, more preferably 10 parts by mass or more, further preferably 30 parts by mass or more, and particularly preferably 50 parts by mass or more relative to 100 parts by mass of component (A). On the other hand, the content of the radical polymerizable compound is preferably 500 parts by mass or less, more preferably 300 parts by mass or less, further preferably 200 parts by mass or less, and particularly preferably 150 parts by mass or less. If the content is within the above range, the sensitivity during exposure can be improved.

[0091] The radical polymerizable compound as the component (C) may be used alone or in combination of two or more.

[0092] ■Ingredient (D)

[0093] Component (D) is a photopolymerization initiator. The so-called photopolymerization initiator refers to a compound that generates free radicals by bond cleavage and / or reaction by exposure. Since the photopolymerization initiator is contained, the exposed part of the film of the negative photosensitive resin composition is insoluble in an alkaline developer, thereby forming a negative pattern. In addition, the curing of the exposed part is promoted, which can improve the sensitivity.

[0094] The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used. Examples of the photopolymerization initiator include benzyl ketal-based photopolymerization initiators, α-hydroxyketone-based photopolymerization initiators, α-aminoketone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, oxime ester-based photopolymerization initiators, acridine-based photopolymerization initiators, titanocene-based photopolymerization initiators, benzophenone-based photopolymerization initiators, acetophenone-based photopolymerization initiators, aromatic ketoester-based photopolymerization initiators, and benzoate-based photopolymerization initiators.

[0095] The photopolymerization initiator may be used alone or in combination of two or more.

[0096] The amount of the photopolymerization initiator is preferably 1 part by mass or more, more preferably 10 parts by mass or more, relative to 100 parts by mass of component (A), from the perspective of obtaining good sensitivity and obtaining a desired pattern. In addition, it is preferably 50 parts by mass or less, more preferably 30 parts by mass or less.

[0097] ■Ingredient (E)

[0098] Examples of the organic solvent as component (E) include polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide, ethers such as tetrahydrofuran, dioxane, propylene glycol monomethyl ether, and propylene glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone, and diisobutyl ketone, esters such as ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, and 3-methyl-3-methoxybutyl acetate, alcohols such as ethyl lactate, methyl lactate, diacetone alcohol, and 3-methyl-3-methoxybutanol, and aromatic hydrocarbons such as toluene and xylene. These solvents may be used alone or in combination of two or more.

[0099] The amount of component (E) in the negative photosensitive resin composition of the present embodiment is preferably such that the solid content concentration in the composition reaches 5% by mass or more, from the perspective of the fluidity of the composition and the ability to obtain a uniform coating film by a coating method such as a spin coating method. In addition, it is preferably such that the solid content concentration in the composition reaches 65% by mass or less.

[0100] ■Others

[0101] In one embodiment, in addition to the above-mentioned components (A) to (E), various additives may be added to the negative photosensitive resin composition within a range that does not hinder the effects of the present invention. Examples of additives include fillers, surfactants such as leveling agents, adhesion enhancers, and dissolution promoters.

[0102] Since the cured film obtained from the negative photosensitive resin composition of the present embodiment has visible light shielding properties, it is not necessary to separately mix a colorant. However, when higher visible light shielding properties are required, the negative photosensitive resin composition of the present embodiment may further contain a colorant.

[0103] Examples of the colorant include benzofuranone-based black pigments, perylene-based black pigments, azo-based black pigments, anthraquinone-based black pigments, aniline-based black pigments, azomethine-based black pigments, organic pigments such as carbon black and graphite, and inorganic pigments such as oxides, composite oxides, sulfides, sulfates, nitrates, carbonates, nitrides, carbides, and nitrogen oxides of metals (alloys) such as silver-tin alloys, titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver.

[0104] In one embodiment, the amount of the colorant is 0 to 30 parts by mass relative to 100 parts by mass of the solid content of the negative photosensitive resin composition. Since the negative photosensitive resin composition of this embodiment has visible light shielding properties, the amount of the colorant can be reduced compared to the past. The negative photosensitive resin composition may not contain a colorant, or it may contain it. When a colorant is contained, it may be greater than 0 parts by mass or more than 0.1 parts by mass relative to 100 parts by mass of the solid content of the negative photosensitive resin composition.

[0105] The negative photosensitive resin composition of the present embodiment can be prepared by stirring and mixing the above-mentioned components (A) to (E) and various additives used as necessary by a common method to prepare a uniform liquid.

[0106] When solid materials such as fillers and pigments are combined in the composition, it is preferred to use dispersing devices such as a dissolver, a homogenizer, and a three-roll mill to disperse and mix. In addition, in order to remove coarse particles and impurities, a mesh filter, a membrane filter, etc. can also be used to filter the composition.

[0107] The negative photosensitive resin composition of this embodiment can be suitably used, for example, for the formation of pixel segmentation layers of negative photoresists, organic base films, thick film resists (bump forming resists), interlayer insulating films, liquid crystal alignment films, heat resistance imparting agents, polyimide, polybenzoxazole-based resists or display devices such as organic EL displays.

[0108] [Cured film / resist film]

[0109] The cured film according to one embodiment of the present invention can be obtained by curing the negative photosensitive resin composition of the present invention described above.

[0110] Specifically, the negative photosensitive resin composition of the present invention is applied onto an object to be photolithographically processed, and pre-baked to obtain a film (photosensitive film) of the photosensitive resin composition from which the solvent has been removed.

[0111] Examples of the coating method include spin coating, roll coating, flow coating, dip coating, spray coating, blade coating, etc. The pre-baking may be performed by heating at a temperature of 60° C. to 150° C. for 30 seconds to 600 seconds.

[0112] The photosensitive film is exposed to light, thereby significantly reducing the solubility of the exposed portion relative to the alkaline developer. As the light source used in the exposure, for example, infrared light, visible light, ultraviolet light, far ultraviolet light, X-rays, and electron beams can be cited. Among these light sources, ultraviolet light is preferred, and g-rays (wavelength 436nm) and i-rays (wavelength 365nm) of a high-pressure mercury lamp are suitable.

[0113] After the exposure, a heat treatment is performed at about 100° C. in order to promote the crosslinking reaction with the components (A), (B) and (C) by utilizing the catalytic reaction of the acid generated by the exposure.

[0114] Since the photosensitive film obtained from the negative photosensitive resin composition of the present invention has high alkali solubility, the difference in alkali solubility from the exposed portion is large, and patterning can be performed at a high resolution. Therefore, it can be suitably used as a resist film.

[0115] As the alkaline developer used in the development after exposure, there can be mentioned inorganic alkaline substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia water; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; alkaline aqueous solutions of cyclic amines such as pyrrole and piperidine.

[0116] Alcohol, surfactant, etc. may be appropriately added to the alkaline developer for use as needed. The alkali concentration of the alkaline developer is usually preferably in the range of 2 to 5% by mass, and a 2.38% by mass tetramethylammonium hydroxide aqueous solution is generally used.

[0117] After development with an alkaline developer, the cured film having crosslinked exposed portions is obtained by heating at a low temperature of, for example, 150° C. to 200° C. The cured film of the present embodiment is excellent in visible light shielding properties.

[0118] The cured film of the present embodiment can be used, for example, in a pixel segmentation layer of a display device such as an organic EL display.

[0119] Example

[0120] The present invention will be described in further detail below with reference to specific examples. The weight average molecular weight (Mw) of the synthesized resin was measured under the following GPC measurement conditions.

[0121] [GPC measurement conditions]

[0122] Measurement device: "HLC-8220 GPC" manufactured by TOSOH Corporation;

[0123] Chromatographic column: "Shodex KF802" manufactured by Showa Denko K.K.: 8.0 mm Φ × 300 mm,

[0124] + "Shodex KF802" manufactured by Showa Denko Co., Ltd.: 8.0mmΦ×300mm,

[0125] + "Shodex KF803" manufactured by Showa Denko Co., Ltd.: 8.0mmΦ×300mm,

[0126] + "Shodex KF804" manufactured by Showa Denko Co., Ltd.: 8.0mmΦ×300mm;

[0127] Column temperature: 40°C;

[0128] Detector: RI (differential refractometer);

[0129] Data processing: "GPC-8020Model II Version 4.30" manufactured by TOSOH Corporation;

[0130] Developing solvent: tetrahydrofuran;

[0131] Flow rate: 1.0 mL / min;

[0132] Sample: A tetrahydrofuran solution having a resin solid content of 0.5% by mass was filtered through a microfilter;

[0133] Injection volume: 0.1mL;

[0134] Standard sample: monodisperse polystyrene as follows;

[0135] (Standard sample: monodisperse polystyrene)

[0136] "A-500" manufactured by TOSOH Co., Ltd.

[0137] "A-2500" manufactured by TOSOH Co., Ltd.

[0138] "A-5000" manufactured by TOSOH Co., Ltd.

[0139] "F-1" manufactured by TOSOH Co., Ltd.

[0140] "F-2" manufactured by TOSOH Co., Ltd.

[0141] "F-4" manufactured by TOSOH Co., Ltd.

[0142] "F-10" manufactured by TOSOH Co., Ltd.

[0143] "F-20" manufactured by TOSOH Co., Ltd.

[0144] [Ingredients (A)]

[0145] Synthesis Example 1 (Synthesis of Novolac-type Phenolic Resin (A-1))

[0146] Into a 2000 mL 4-necked flask equipped with a condenser, 82 g (0.76 mol) of m-cresol, 84 g (0.76 mol) of catechol, 103 g (0.97 mol) of benzaldehyde, 74 g (0.61 mol) of salicylaldehyde, and 8 g of p-toluenesulfonic acid were added and dissolved in 300 g of ethanol as a reaction solvent. Thereafter, the mixture was heated to 80° C. with a mantle-type resistance heater and stirred under reflux for 16 hours to react. After the reaction was completed, ethyl acetate and water were added to perform liquid separation and washing five times. After the solvent was removed by reduced pressure distillation from the residual resin solution, vacuum drying was performed to obtain 279 g of a light red powder of linear phenolic resin (A-1).

[0147] The Mw of the novolac-type phenol resin (A-1) obtained by the GPC method was 3,820.

[0148] Synthesis Example 2 (Synthesis of Novolac-type Phenolic Resin (A-2))

[0149] 283 g of powder of novolac-type phenolic resin (A-2) was obtained in the same manner as in Synthesis Example 1 except that the charging amounts of the starting materials were set to 82 g (0.76 mol) of m-cresol, 84 g (0.76 mol) of catechol, 80 g (0.75 mol) of benzaldehyde, and 92 g (0.75 mol) of salicylaldehyde.

[0150] The Mw of the novolac-type phenol resin (A-2) obtained by the GPC method was 3,270.

[0151] Synthesis Example 3 (Synthesis of Novolac-type Phenolic Resin (A-3))

[0152] 279 g of powder of novolac phenolic resin (A-3) was obtained in the same manner as in Synthesis Example 1 except that the amount of starting materials charged was 82 g (0.76 mol) of m-cresol, 84 g (0.76 mol) of catechol, 117 g (1.10 mol) of benzaldehyde, and 58 g (0.47 mol) of salicylaldehyde. The Mw of novolac phenolic resin (A-3) was 3620.

[0153] Synthesis Example 4 (Synthesis of Novolac-type Phenolic Resin (A-4))

[0154] 286 g of powder of a linear phenolic resin (A-4) was obtained in the same manner as in Synthesis Example 1 except that the charging amounts of the starting materials were set to 82 g (0.76 mol) of m-cresol, 84 g (0.76 mol) of catechol, 67 g (0.63 mol) of benzaldehyde, and 115 g (0.94 mol) of salicylaldehyde.

[0155] The Mw of the novolak resin (A-4) obtained by the GPC method was 3,540.

[0156] Synthesis Example 5 (Synthesis of Novolac-type Phenolic Resin (A-5))

[0157] 282 g of powder of a linear phenolic resin (A-5) was obtained in the same manner as in Synthesis Example 1, except that the charging amounts of the starting materials were set to 123 g (1.14 mol) of m-cresol, 42 g (0.38 mol) of catechol, 103 g (0.97 mol) of benzaldehyde, and 74 g (0.61 mol) of salicylaldehyde.

[0158] The Mw of the novolak resin (A-5) obtained by the GPC method was 3,210.

[0159] Synthesis Example 6 (Synthesis of Novolac-type Phenolic Resin (A-6))

[0160] 281 g of powder of linear phenolic resin (A-6) was obtained in the same manner as in Synthesis Example 1, except that the charging amounts of the starting materials were set to 41 g (0.38 mol) of m-cresol, 126 g (1.14 mol) of catechol, 103 g (0.97 mol) of benzaldehyde, and 74 g (0.61 mol) of salicylaldehyde.

[0161] The Mw of the novolak resin (A-6) obtained by the GPC method was 3,790.

[0162] Comparative Synthesis Example 1 (Synthesis of Novolac-type Phenolic Resin (A-7))

[0163] 281 g of powder of novolac-type phenolic resin (A-7) was obtained in the same manner as in Synthesis Example 1 except that the charging amounts of the starting materials were changed to 164 g (1.52 mol) of m-cresol, 103 g (0.97 mol) of benzaldehyde, and 74 g (0.61 mol) of salicylaldehyde.

[0164] The Mw of the novolac-type phenol resin (A-7) obtained by the GPC method was 3,100.

[0165] [Ingredient (B)]

[0166] Synthesis Example 7 (Synthesis of polyimide precursor (B-1) containing ethylenically unsaturated groups)

[0167] Under a dry nitrogen stream, 125 g (0.023 mol) of pyromellitic anhydride and 115 g (0.023 mol) of 4,4-diaminodiphenyl ether were added to a 2000 mL 4-necked flask equipped with a condenser, and dissolved in 1602 g of N-methyl-2-pyrrolidone, and stirred at 100° C. for 4 hours to react. After the reaction was completed, the solution was put into 2000 g of water, and the precipitate of the polymer solid was collected by filtration. The polymer solid was dried in a vacuum dryer at 80° C. for 72 hours to obtain a polymer solid powder.

[0168] 32.8 g of the obtained solid powder is dissolved in 76.5 g of 3-methoxy-n-butyl acetate. After the mixed solution is cooled to 0°C, a solution in which 3.2 g of 2-methacryloyloxyethyl isocyanate is dissolved is added dropwise to 3.2 g of 3-methoxy-n-butyl acetate. After the addition is completed, stir at 80°C for 1 hour to obtain a polymer solution containing ethylenically unsaturated groups. After the reaction is completed, the obtained solution is put into 1000 g of water, and the precipitate of the polymer solid containing ethylenically unsaturated groups is collected by filtration. The precipitate of the polymer solid is collected by filtration. The polymer solid containing ethylenically unsaturated groups is dried at 80°C in a vacuum dryer for 72 hours to obtain a polymer powder of a polyimide precursor (B-1) containing ethylenically unsaturated groups.

[0169] [Negative photosensitive resin composition]

[0170] Example 1

[0171] 4.2 g of a powder of a linear phenol resin (CA-1) obtained in Synthesis Example 1 as component (CA), 1.8 g of a polymer powder of a polyimide precursor (B-1) containing an ethylenically unsaturated group obtained in Synthesis Example 7 as component (B), 4.0 g of a radical polymerizable compound (dipentaerythritol hexaacrylate: manufactured by Nippon Kayaku Co., Ltd.) as component (CC), and 0.9 g of a photopolymerization initiator (NCI-831: manufactured by ADEKA Corporation) as component (CD) were dissolved in 98 g of γ-butyrolactone as component (E), thereby obtaining a negative photosensitive resin composition (F-1).

[0172] Examples 2 to 6, Comparative Examples 1 and 2

[0173] In Examples 2 to 6 and Comparative Example 1, negative photosensitive resin compositions (F-2) to (F-7) were obtained in the same manner as in Example 1 except that the novolac resin (A-2) to (A-7) powders shown in Tables 1 and 2 were used as component (A).

[0174] In Comparative Example 2, a negative photosensitive resin composition (F-8) was obtained in the same manner as in Example 1 except that the novolac resin (A-7) shown in Table 2 was used as the component (A) and 3.4 g of a benzofuran black pigment (Bk-S0100CF manufactured by BASF) and 1.3 g of a dispersant (BYK-167 DISPERBYK manufactured by BYK-Chemie Japan Co., Ltd.) were dissolved in 140 g of a γ-butyrolactone solvent (E).

[0175] [evaluate]

[0176] Using the negative photosensitive resin compositions prepared in Examples and Comparative Examples, resin compatibility, alkali solubility before exposure, visible light shielding properties, and elastic modulus of cured films were evaluated.

[0177] (1) Evaluation of resin compatibility (film forming properties)

[0178] The negative photosensitive resin composition was applied to a silicon wafer having a diameter of 5 inches using a spin coater to a thickness of about 5 μm. Thereafter, the wafer was pre-baked at 120° C. for 180 seconds to obtain a wafer having a photosensitive film formed thereon. The photosensitive film formed on the surface of the wafer was observed using an optical microscope to evaluate the presence or absence of cavitation (Japanese: はじき) and unevenness.

[0179] The photosensitive film having no shrinkage cavities and unevenness was regarded as having good compatibility with the resin (○), and the photosensitive film having shrinkage cavities and unevenness was regarded as having insufficient compatibility with the resin (×).

[0180] (2) Alkali solubility before exposure

[0181] A negative photosensitive resin composition was applied to a silicon wafer having a diameter of 5 inches using a spin coater to a thickness of about 5 μm. Thereafter, the wafer was pre-baked at 120°C for 180 seconds to obtain a wafer having a photosensitive film formed thereon. The obtained wafer was immersed in a vat injected with 250 mL of a developer (2.38 wt % tetramethylammonium hydroxide aqueous solution (TMAH)) for 10 seconds. The wafer taken out of the vat was rinsed with pure water for 10 seconds, and the residue of the photosensitive film on the wafer was observed to evaluate the alkali solubility. The case where there was no residue of the photosensitive film was set as good (○), and the case where there was residue was set as insufficient (×). The evaluation results are shown in Tables 1 and 2.

[0182] (3) Visible light shielding properties of the resin composition

[0183] The negative photosensitive resin composition was diluted with γ-butyrolactone to a solid content concentration of 1%, and the visible light shielding property was evaluated using UV-vis (SolidSpec-3700 DUV manufactured by Shimadzu Corporation). The case where the transmittance at 650nm was less than 10% was considered good (○), and the case where it was 10% or more was considered insufficient (×). The evaluation results are shown in Tables 1 and 2.

[0184] (4) Elastic modulus of cured film

[0185] A negative photosensitive resin composition was applied to a silicon wafer with a diameter of 5 inches using a spin coater to a thickness of about 5 μm. Thereafter, it was pre-baked at 120°C for 180 seconds to obtain a wafer with a photosensitive film formed thereon. The obtained wafer was irradiated with 200 mJ of ghi rays (g rays: wavelength 436 nm, h rays: wavelength 405 nm, i rays: wavelength 365 nm) using Multilight manufactured by USHIO, and then subjected to a pre-development bake (PEB) for 120 seconds on a hot plate at 130°C. Thereafter, the wafer with the coating was heat treated at 200°C for 1 hour in an inert atmosphere. When the temperature of the heating device was below 50°C, the wafer was taken out and the film thickness was measured. The film hardness was measured using a nanoindentation method (ENT-2100: manufactured by ELIONIX Co., Ltd.). The case where the indentation elastic modulus was 8 GPa or more was set as good (○), and the case where it was less than 8 GPa was set as insufficient (×). Tables 1 and 2 show the evaluation results.

[0186] [Table 1]

[0187]

[0188] [Table 2]

[0189]

[0190] In Tables 1 and 2, (a1), (a2), (a3) ​​and (a4) respectively represent the structural unit (a1) derived from m-cresol, the structural unit (a2) derived from catechol, the structural unit (a3) ​​derived from benzaldehyde and the structural unit (a4) derived from salicylaldehyde in the component (A) linear phenolic resin.

[0191] From Tables 1 and 2, it can be considered that the photosensitive film obtained by the negative photosensitive resin composition of the present invention has excellent compatibility, so there is no shrinkage cavity and unevenness. In addition, it can be confirmed that it has alkali solubility. In addition, it can be confirmed that even without adding black pigment, the visible light shielding property is also excellent.

Claims

1. A negative photosensitive resin composition comprising the following components A to E: A: a novolac-type phenolic resin in which the molar ratio of structural units a1 derived from m-cresol, structural units a2 derived from catechol, structural units a3 derived from benzaldehyde and structural units a4 derived from salicylaldehyde is 1: 0.25-4.0: 0.25-4.0: 0.25-4.0; B: one or more resins selected from the group consisting of polyimide containing an ethylenically unsaturated group, a polyimide precursor containing an ethylenically unsaturated group, a polybenzoxazole containing an ethylenically unsaturated group, and a polybenzoxazole precursor containing an ethylenically unsaturated group; C: free radical polymerizable compound; D: photopolymerization initiator; E: Organic solvent.

2. The negative photosensitive resin composition according to claim 1, wherein The component A is a novolac phenolic resin obtained by polycondensing m-cresol, catechol, benzaldehyde and salicylaldehyde in an organic solvent at a molar ratio of m-cresol: catechol: benzaldehyde: salicylaldehyde = 1: 0.25-4.0: 0.25-4.0: 0.25-4.0 using an acid catalyst.

3. The negative photosensitive resin composition according to claim 1 or 2, wherein The total content of the structural unit a1 derived from m-cresol, the structural unit a2 derived from catechol, the structural unit a3 derived from benzaldehyde, and the structural unit a4 derived from salicylaldehyde in the component A is 30% by mass or more.

4. The negative photosensitive resin composition according to claim 1 or 2, wherein The weight average molecular weight of the component A is 1,000 or more and 7,000 or less.

5. The negative photosensitive resin composition according to claim 1 or 2, wherein The negative photosensitive resin composition contains 0 to 30 parts by mass of a colorant based on 100 parts by mass of the solid content. 6 . A cured film obtained from the negative photosensitive resin composition according to claim 1 . 7 . A resist film obtained from the negative photosensitive resin composition according to claim 1 .

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