Negative type photosensitive resin composition

Abstract

To provide a negative type photosensitive resin composition in which a resist film before exposure has alkali solubility and is excellent in film production, and a resist cured product after exposure is excellent in chemical resistance.SOLUTION: A negative type photosensitive resin composition contains the following components (A) to (F): (A) a novolak type phenol resin in which a molar ratio [(a1):(a2):(a3)] of a structural unit (a1) derived from cresol, a structural unit (a2) derived from benzaldehyde, and a structural unit (a3) derived from hydroxybenzaldehyde is 1.0:0.3 to 0.8:0.3 to 0.8; (B) at least one alkali soluble resin of a polymerizable unsaturated group-containing alkali soluble resin, and a (meth)acrylic alkali soluble resin; (C) a polymerizable compound; (D) a polymerization initiator; (E) a coloring component; and (F) an organic solvent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a negative photosensitive resin composition, a resist film, a resist underlayer film, and a permanent resist film. [Background technology]

[0002] Organic electroluminescence (EL) displays are attracting attention as next-generation flat panel displays. Organic EL displays are self-luminous display devices that utilize electroluminescence from organic compounds, and have the excellent features of wide-angle viewing, fast response, and the ability to display images, as well as being thin and lightweight. In recent years, as the resolution of organic EL displays has increased, there has been a demand for further miniaturization of light-emitting elements.

[0003] In organic EL displays, light-emitting elements emit light using the energy generated by the recombination of electrons injected from the cathode and holes injected from the anode. Therefore, the presence of a substance that creates an energy level that inhibits the recombination of electrons and holes reduces the light-emitting efficiency of the light-emitting element, thereby shortening the lifespan of the organic EL display. Therefore, to separate the pixels of the light-emitting element, an insulating layer called a pixel dividing layer made of a negative-type photosensitive resin composition is typically formed between the transparent electrode on the light extraction side and the metal electrode on the opposite side. Because this pixel dividing layer is formed adjacent to the light-emitting element, a decrease in insulation, deformation, or deterioration of the pixel dividing layer due to heat generation from light emission can contribute to a shortened lifespan of the organic EL display.

[0004] On the other hand, in addition to insulating properties, the pixel division layer is required to be black (highly light-shielding) for the purpose of improving the visibility and contrast of organic EL displays, and a photosensitive resin composition containing a black coloring material is used. Carbon black is a commonly known black coloring material, but because carbon black has high conductivity, there have been concerns that adding carbon black may reduce the insulating properties of the pixel division layer, causing malfunctions in display devices. Therefore, in order to improve the insulating properties of pixel division layers using carbon black, a method of coating the surface of carbon black with an epoxy resin has been proposed (for example, Patent Document 1). However, although the negative photosensitive resin composition using carbon black described in Patent Document 1 improves the insulating properties, it is not suitable for forming fine patterns.

[0005] Furthermore, the development of a photosensitive resin composition in which a pixel dividing layer mainly contains an alkali-soluble resin and a (meth)acrylated epoxy resin in which a portion of the epoxy resin is (meth)acrylated has also been considered (for example, Patent Document 2). However, although the photosensitive resin composition described in Patent Document 2 has improved insulation properties, it does not have sufficient alkali solubility, and the generation of residues has become an issue.

[0006] Furthermore, a negative photosensitive resin composition has been proposed in which an epoxy group and an alkali-soluble group are introduced into a (meth)acrylic resin skeleton (for example, Patent Document 3). However, the photosensitive resin composition described in Patent Document 3 still does not have sufficient alkali solubility, and the occurrence of pattern residues after development due to insufficient sensitivity is still observed. As described above, with the trend toward higher resolution organic EL displays, there is a demand for the development of negative photosensitive resin compositions that can form finer pixel dividing layer patterns without leaving residues. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2001-207079 [Patent Document 2] Japanese Patent Application Publication No. 2023-97382 [Patent Document 3] Japanese Patent Application Publication No. 2022-38599 Summary of the Invention [Problem to be solved by the invention]

[0008] An object of the present invention is to provide a negative photosensitive resin composition which provides a resist layer that is alkali-soluble before exposure, has excellent film-forming properties, and provides a cured resist that is excellent in chemical resistance after exposure. [Means for solving the problem]

[0009] The present invention relates to a negative photosensitive resin composition containing the following components (A) to (F): (A) A novolac phenolic resin in which the molar ratio of the structural unit (a1) derived from cresol, the structural unit (a2) derived from benzaldehyde, and the structural unit (a3) ​​derived from hydroxybenzaldehyde [(a1):(a2):(a3)] is 1.0:0.3-0.8:0.3-0.8. (B) At least one alkali-soluble resin selected from the group consisting of a polymerizable unsaturated group-containing alkali-soluble resin and a (meth)acrylic alkali-soluble resin. (C) Polymerizable compound (D) Polymerization initiator (E) Coloring component (F) Organic solvent

[0010] The present invention further relates to a cured film obtained from the above negative photosensitive resin composition. The present invention further relates to a resist film obtained from the negative photosensitive resin composition. The present invention further relates to a resist underlayer film obtained from the above negative photosensitive resin composition. The present invention further relates to a permanent resist film obtained from the negative photosensitive resin composition. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a negative photosensitive resin composition in which the resist layer before exposure has alkali solubility and excellent film formability, and the cured resist after exposure has excellent chemical resistance. [Brief explanation of the drawings]

[0012] [Figure 1] 1 is a GPC chart of the novolac phenolic resin obtained in Synthesis Example 1. [Figure 2] 1 is a GPC chart of the novolak phenolic resin obtained in Synthesis Example 2. [Figure 3] 1 is a GPC chart of the novolak phenolic resin obtained in Synthesis Example 3. [Figure 4] 1 is a GPC chart of the novolak phenolic resin obtained in Synthesis Example 4. [Figure 5] 1 is a GPC chart of the novolak phenolic resin obtained in Synthesis Example 5. [Figure 6] 1 is a GPC chart of the novolak phenolic resin obtained in Synthesis Example 6. [Figure 7] 1 is a GPC chart of the novolak phenolic resin obtained in Synthesis Example 7. DETAILED DESCRIPTION OF THE INVENTION

[0013] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The following describes the embodiments of the present invention. In this specification, "x to y" represents a numerical range of "not less than x and not more than y." The upper and lower limits of the numerical ranges can be combined in any way. Furthermore, a combination of two or more of the individual aspects of the present invention described below is also an aspect of the present invention.

[0014] A negative photosensitive resin composition according to one embodiment of the present invention contains the following components (A) to (F). (A) A novolac phenolic resin in which the molar ratio of the structural unit (a1) derived from cresol, the structural unit (a2) derived from benzaldehyde, and the structural unit (a3) ​​derived from hydroxybenzaldehyde [(a1):(a2):(a3)] is 1.0:0.3-0.8:0.3-0.8. (B) At least one alkali-soluble resin selected from the group consisting of a polymerizable unsaturated group-containing alkali-soluble resin and a (meth)acrylic alkali-soluble resin. (C) Polymerizable compound (D) Polymerization initiator (E) Coloring component (F) Organic solvent

[0015] In this embodiment, by using the novolac phenolic resin (A) described above, it is possible to suppress the occurrence of film formation defects, obtain a resist with high alkali solubility in unexposed areas, and improve the chemical resistance of the cured resist. The components of the negative photosensitive resin composition will be described below.

[0016] Ingredient (A) The novolac phenolic resin, which is component (A), has a molar ratio of the structural unit (a1) derived from cresol, the structural unit (a2) derived from benzaldehyde, and the structural unit (a3) ​​derived from hydroxybenzaldehyde [(a1):(a2):(a3)] of 1.0:0.3-0.8:0.3-0.8.

[0017] The molar ratio of the structural unit (a1) derived from cresol, the structural unit (a2) derived from benzaldehyde, and the structural unit (a3) ​​derived from hydroxybenzaldehyde contained in component (A) [(a1):(a2):(a3)] is preferably 1.0:0.5-0.7:0.3-0.5, and more preferably 1.0:0.55-0.65:0.35-0.45, from the viewpoint of obtaining a cured film that not only has high sensitivity but also has chemical resistance when cured at low temperature.

[0018] Component (A) may contain structural units other than the structural unit (a1) derived from cresol, the structural unit (a2) derived from benzaldehyde, and the structural unit (a3) ​​derived from hydroxybenzaldehyde. Examples of structural units other than (a1) to (a3) ​​include structural units derived from phenols or aldehydes other than cresol, benzaldehyde, and hydroxybenzaldehyde.

[0019] Examples of the phenols include phenol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, and 3,4,5-trimethylphenol.

[0020] Examples of the aldehydes include formalin, paraformaldehyde, acetaldehyde, chloroacetaldehyde, 4-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 2-methoxybenzaldehyde, 3-nitrobenzaldehyde, phenylaldehyde, cinnamaldehyde, 1-naphthaldehyde, 2-naphthaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, and 4-biphenylaldehyde.

[0021] The total content of the structural units (a1), (a2), and (a3) ​​in component (A) is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 90% by mass or more, from the viewpoint of obtaining a cured film that not only has high sensitivity but also has chemical resistance when cured at low temperature. The total content of the structural units (a1), (a2), and (a3) ​​may be substantially 100% by mass, which means that structural units other than the structural units (a1), (a2), and (a3) ​​are inevitably contained.

[0022] The weight-average molecular weight of the novolac phenolic resin, component (A), is preferably 1,000 or more, more preferably 1,500 or more. It is also preferably 15,000 or less, more preferably 10,000 or less, and even more preferably 5,000 or less. A weight-average molecular weight of 1,000 or more is preferred because it provides high heat resistance. On the other hand, a weight-average molecular weight of 15,000 or less is preferred because it provides high sensitivity. In this specification, the weight-average molecular weight is measured according to the conditions described in the Examples.

[0023] Component (A) is obtained by polycondensing cresol, benzaldehyde, and hydroxybenzaldehyde in an organic solvent at a molar ratio (cresol:benzaldehyde:hydroxybenzaldehyde) of 1.0:0.3-0.8:0.3-0.8 using an acid catalyst. Preferably, the cresol is m-cresol, and the hydroxybenzaldehyde is salicylaldehyde.

[0024] The molar ratio of cresol, benzaldehyde, and hydroxybenzaldehyde in the reaction solvent (cresol:benzaldehyde:hydroxybenzaldehyde) is preferably in the range of 1.0:0.5-0.7:0.3-0.5, more preferably 1.0:0.55-0.65:0.35-0.45, from the viewpoint of obtaining a cured film that not only has high sensitivity but also has chemical resistance when cured at low temperature.

[0025] The molar ratio of benzaldehyde is preferably smaller than the molar ratio of hydroxybenzaldehyde, i.e., it is preferable to satisfy the molar ratio benzaldehyde<hydroxybenzaldehyde.

[0026] When cresol, benzaldehyde, and hydroxybenzaldehyde are polycondensed in an organic solvent to obtain the novolac phenolic resin, which is component (A), as described above, the organic solvent may contain phenols and aldehydes other than cresol, benzaldehyde, and hydroxybenzaldehyde.

[0027] The proportion of the total mass of cresol, benzaldehyde, and hydroxybenzaldehyde in the reaction solvent relative to the total mass of all starting materials that can become structural units constituting component (A) is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably substantially 100% by mass, from the viewpoint of obtaining a cured film that not only has high sensitivity but also has chemical resistance when cured at low temperature.

[0028] Examples of reaction solvents used in producing 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, and toluene. Among these, one or more selected from ethanol, 1-propanol, and 2-propanol are preferred, and ethanol is more preferred.

[0029] From the viewpoint of uniformity of the reaction, the amount of the reaction solvent used is preferably 20 parts by mass or more, more preferably 50 parts by mass or more, per 100 parts by mass of the raw materials from which the structural units constituting component (A) are derived, and is preferably 500 parts by mass or less, more preferably 300 parts by mass or less.

[0030] Examples of the acid catalyst used in producing 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 paratoluenesulfonic acid. Among these, inorganic acids and paratoluenesulfonic acid are preferred, and paratoluenesulfonic acid is more preferred, in order to further promote the reaction. The amount of acid catalyst added is not particularly limited, but is preferably at least 5 parts by mass, more preferably at least 20 parts by mass, per 100 parts by mass of the raw materials from which the structural units constituting component (A) are derived, and is preferably at most 150 parts by mass, more preferably at most 100 parts by mass.

[0031] The reaction temperature during polycondensation of the raw materials for component (A) is preferably 30°C or higher, more preferably 40°C or higher, in order to promote the reaction and efficiently increase the molecular weight, and is preferably 100°C or lower, more preferably 80°C or lower. The reaction time is preferably 4 hours or more, more preferably 12 hours or more, and is preferably 32 hours or less, more preferably 24 hours or less.

[0032] The component (A) is preferably blended in an amount of 1.0 to 40 mass % of the solid content of the negative photosensitive resin composition, and more preferably 5 to 40 mass %.

[0033] ·Component (B) The polymerizable unsaturated group-containing alkali-soluble resin (B-1) and (meth)acrylic alkali-soluble resin (B-2) that are component (B) can improve the alkali solubility of the unexposed areas.

[0034] The polymerizable unsaturated group-containing alkali-soluble resin (B-1) may be a resin having a polymerizable unsaturated group and an acidic group in the molecule. For example, an epoxy (meth)acrylate acid adduct obtained by reacting a compound having two or more epoxy groups with (meth)acrylic acid ("(meth)acrylic acid" means acrylic acid and / or methacrylic acid) to obtain an epoxy (meth)acrylate compound having a hydroxy group, with one or more carboxylic acid compounds selected from dicarboxylic acids, tricarboxylic acids, tricarboxylic acid monoanhydrides, tetracarboxylic acids, and tetracarboxylic acid dianhydrides is preferred.

[0035] Examples of compounds having two or more epoxy groups that can be converted into epoxy (meth)acrylate acid adducts include bisphenol-type epoxy compounds and novolac-type epoxy compounds. Specifically, bisphenol-type epoxy compounds represented by the following general formula (I) are preferred.

[0036] [ka]

[0037] In the formula, R1, R2, R3, and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a phenyl group. A represents -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a fluorene-9,9-diyl group, or a direct bond. 1 is an integer from 0 to 10.

[0038] R1 to R4 are preferably hydrogen atoms. A is preferably a fluorene-9,9-diyl group. 1 usually has a mixture of multiple values, and has an average value of 0 to 10 (not necessarily an integer), but a preferred average value of 1 is 0 to 3. The following explanation will be given representatively for the case where 1=0.

[0039] Bisphenol-type epoxy compounds are epoxy compounds having two glycidyl ether groups obtained by reacting bisphenols with epichlorohydrin. This reaction generally involves oligomerization of the diglycidyl ether compound, and therefore includes epoxy compounds containing two or more bisphenol skeletons. The bisphenols used in this reaction include bis(4-hydroxyphenyl) ketone, bis(4-hydroxy-3,5-dimethylphenyl) ketone, bis(4-hydroxy-3,5-dichlorophenyl) ketone, bis(4-hydroxyphenyl) sulfone, bis(4-hydroxy-3,5-dimethylphenyl) sulfone, bis(4-hydroxy-3,5-dichlorophenyl) sulfone, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane, bis(4-hydroxyphenyl) 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3- chlorophenyl)propane, bis(4-hydroxyphenyl)ether, bis(4-hydroxy-3,5-dimethylphenyl)ether, bis(4-hydroxy-3,5-dichlorophenyl)ether, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene, 9, 9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 4,4'-biphenol, 3,3'-biphenol, etc. Among these, bisphenols having a fluorene-9,9-diyl group are preferred.

[0040] Examples of the acid monoanhydride of a dicarboxylic acid or tricarboxylic acid to be reacted with the epoxy (meth)acrylate include acid monoanhydrides of chain hydrocarbon dicarboxylic acids or tricarboxylic acids, acid monoanhydrides of alicyclic dicarboxylic acids or tricarboxylic acids, and acid monoanhydrides of aromatic dicarboxylic acids or tricarboxylic acids. Examples of acid monoanhydrides of chain hydrocarbon dicarboxylic or tricarboxylic acids include acid monoanhydrides of succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, etc. Acid monoanhydrides of dicarboxylic or tricarboxylic acids having any substituent introduced therein may also be used.

[0041] Examples of acid monoanhydrides of alicyclic dicarboxylic acids or tricarboxylic acids include acid monoanhydrides of cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, hexahydrotrimellitic acid, norbornanedicarboxylic acid, etc. Acid monoanhydrides of dicarboxylic acids or tricarboxylic acids into which any substituent has been introduced may also be used.

[0042] Furthermore, examples of the acid monoanhydrides of aromatic dicarboxylic acids or tricarboxylic acids include the acid monoanhydrides of phthalic acid, isophthalic acid, trimellitic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, etc. Acid monoanhydrides of dicarboxylic acids or tricarboxylic acids into which any substituent has been introduced may also be used.

[0043] Furthermore, examples of the acid dianhydride of a tetracarboxylic acid to be reacted with an epoxy (meth)acrylate include acid dianhydrides of chain hydrocarbon tetracarboxylic acids, acid dianhydrides of alicyclic tetracarboxylic acids, and acid dianhydrides of aromatic tetracarboxylic acids. Examples of the acid dianhydrides of chain hydrocarbon tetracarboxylic acids include butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, etc. Acid dianhydrides of tetracarboxylic acids obtained by introducing any substituent into these may also be used. Examples of the acid dianhydrides of alicyclic tetracarboxylic acids include acid dianhydrides such as cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, and norbornane tetracarboxylic acid. Acid dianhydrides of tetracarboxylic acids obtained by introducing any substituent into these may also be used. Furthermore, examples of the acid dianhydride of an aromatic tetracarboxylic acid include acid dianhydrides such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, and naphthalene-2,3,6,7-tetracarboxylic acid. Acid dianhydrides of tetracarboxylic acids obtained by introducing any substituent into these may also be used.

[0044] In one embodiment, the carboxylic acid compound to be reacted with the epoxy (meth)acrylate is preferably (a) an acid anhydride of a dicarboxylic acid or tricarboxylic acid, and (b) an acid dianhydride of a tetracarboxylic acid. The molar ratio (a) / (b) of (a) the dicarboxylic or tricarboxylic acid anhydride to (b) the tetracarboxylic acid dianhydride to be reacted with the epoxy (meth)acrylate is preferably 0.01 to 10.0, and more preferably 0.02 or more and less than 3.0. When the molar ratio (a) / (b) is within the above range, it is easy to obtain an optimum molecular weight for obtaining a photosensitive resin composition having good photopatterning properties, and the composition also has high alkali solubility.

[0045] Epoxy (meth)acrylate acid adducts can be produced, for example, by the methods described in Japanese Patent Application Laid-Open Nos. 8-278629 and 2008-9401. First, a method for reacting an epoxy compound with (meth)acrylic acid involves adding (meth)acrylic acid in an amount equimolar to the epoxy groups of the epoxy compound to a solvent, and then heating and stirring the mixture to 90-120°C while blowing in air in the presence of a catalyst (e.g., triethylbenzylammonium chloride, 2,6-diisobutylphenol, etc.). Next, a method for reacting an acid anhydride with the hydroxyl groups of the epoxy acrylate compound, the reaction product, involves adding predetermined amounts of the epoxy acrylate compound, acid dianhydride, and acid monoanhydride to a solvent, and then heating and stirring the mixture to 90-130°C in the presence of a catalyst (e.g., tetraethylammonium bromide, triphenylphosphine, etc.). The epoxy acrylate acid adduct obtained by this method has a skeleton represented by general formula (II).

[0046] [ka] (In formula (II), R1, R2, R3, and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a phenyl group. A represents -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a fluorene-9,9-diyl group, or a direct bond. X represents a tetravalent carboxylic acid residue. Y1 and Y2 each independently represent a hydrogen atom or -OC-Z-(COOH)k (wherein Z represents a divalent or trivalent carboxylic acid residue, and k represents a number of 1 or 2). j represents an integer of 1 to 20. R5 represents a hydrogen atom or a methyl group.)

[0047] Another example of component (B-1) is a resin containing a (meth)acrylic group and a carboxyl group, which is a copolymer of (meth)acrylic acid, a (meth)acrylic acid ester, etc. For example, a polymerizable unsaturated group-containing alkali-soluble resin can be obtained by copolymerizing a (meth)acrylic acid ester containing glycidyl (meth)acrylate in a solvent in a first step to obtain a copolymer, reacting the copolymer with (meth)acrylic acid in a second step, and reacting the copolymer with an anhydride of a dicarboxylic acid or tricarboxylic acid in a third step.

[0048] Another example of component (B-1) is a urethane compound obtained by reacting a polyol compound having an ethylenically unsaturated bond in the molecule as the first component, a diol compound having a carboxyl group in the molecule as the second component, and a diisocyanate compound as the third component. For examples of resins of this type, see JP 2017-76071 A.

[0049] The weight-average molecular weight (Mw) of component (B-1) is preferably between 2,000 and 10,000, and more preferably between 3,000 and 7,000. If Mw is less than 2,000, the pattern adhesion during development cannot be maintained, resulting in pattern peeling. If Mw exceeds 10,000, development residues and residual films in unexposed areas are likely to remain. Furthermore, the acid value of component (B-1) is preferably in the range of 30 to 200 KOHmg / g. If this value is less than 30 KOHmg / g, alkaline development may not proceed smoothly or special development conditions, such as a strong alkali, may be required. If it exceeds 200 KOHmg / g, penetration of the alkaline developer may be too rapid, resulting in peeling. The component (B-1) may be used alone or in a mixture of two or more.

[0050] Examples of the (meth)acrylic alkali-soluble resin (B-2) include alkali-soluble resins containing a repeating unit represented by at least one of the following general formulas (III) and (IV) and a repeating unit represented by at least one of the following general formulas (V) and (VI):

[0051] [ka]

[0052] In formula (III), R 1 represents a hydrogen atom or a methyl group, and 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, an alkoxy group, or an acyl group having 1 to 5 carbon atoms. l represents an integer of 0 to 4, and m represents an integer of 1 to 4. R 3 If there are two or more R 3 may be different from each other or may be the same.

[0053] In formula (IV), R 4 represents a hydrogen atom or a methyl group, and R 5 represents an alkyl group, an alkoxy group, or an acyl group having 1 to 5 carbon atoms. n represents an integer of 0 to 4, and o represents an integer of 1 to 4. R 5 If there are two or more R 5 may be different from each other or may be the same.

[0054] [ka]

[0055] In formula (V), R 6 represents a hydrogen atom or a methyl group, and R 7 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. 8represents an alkyl group having 1 to 5 carbon atoms, p represents an integer of 1 to 5, and q represents an integer of 0 to 5. R 8 If there are two or more R 8 may be different from each other or may be the same.

[0056] In formula (VI), 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.

[0057] The alkali-soluble (meth)acrylic resin (B-2) can be obtained by copolymerizing a monomer constituting the repeating unit represented by general formula (III) and / or general formula (IV) with a monomer constituting the repeating unit represented by general formula (V) and / or general formula (VI). Examples of the copolymerization method include the method described in JP-A-5-19467.

[0058] Specific examples of the monomer constituting the repeating unit represented by general formula (III) include 4-hydroxyphenyl methacrylate (hereinafter, PQMA), (4-hydroxyphenyl)methyl methacrylate, (4-hydroxyphenyl)ethyl methacrylate (hereinafter, PEMA), and (4-hydroxyphenyl)propyl methacrylate.

[0059] Specific examples of monomers constituting the repeating unit represented by general formula (IV) 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.

[0060] The alkali-soluble (meth)acrylic resin (B-2) contains a repeating unit represented by general formula (III) and / or general formula (IV), which exhibits the effect of suppressing a radical chain reaction, reduces the mask bias of the negative-tone photosensitive resin composition, and enables the formation of a pattern as intended. The (meth)acrylic alkali-soluble resin (B-2) preferably has a repeating unit represented by general formula (III). 2 It is more preferred that is a single bond.

[0061] Examples of monomers constituting the repeating unit represented by general formula (V) 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, tetrahydro-2H-pyran-2-yl acrylate, etc. Among these, glycidyl methacrylate is preferred.

[0062] Examples of the monomer constituting the repeating unit represented by general formula (VI) include 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylethyl methacrylate, 3,4-epoxycyclohexylethyl acrylate, etc. Among these, 3,4-epoxycyclohexylmethyl methacrylate is preferred.

[0063] When the (meth)acrylic alkali-soluble resin (B-2) contains a repeating unit represented by general formula (V) and / or general formula (VI), the crosslink density is improved in the step of thermally curing the negative-type photosensitive resin composition after patterning, and an organic EL display device with excellent long-term reliability can be obtained.

[0064] When the total molar ratio of the repeating units represented by general formula (III) and the repeating units represented by general formula (IV) and the total molar ratio of the repeating units represented by general formula (V) and the repeating units represented by general formula (VI) are M1 and M2, respectively, relative to 100 mol% of all repeating units in the alkali-soluble (meth)acrylic resin (B-2), M1 is preferably 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-type 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 viewpoint of long-term reliability of the organic EL display device.

[0065] The (meth)acrylic alkali-soluble resin (B-2) can 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, isopropyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, t-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, It may contain unsaturated monomers having an aromatic ring, such as acrylate or methacrylate monomers or (fluoro)alkyl esters thereof, such as butyl, t-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, benzyl methacrylate, and 2-ethylhexyl methacrylate, as well as unsaturated monomers having an aromatic ring, such as 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.

[0066] The component (B) is preferably an alkali-soluble (meth)acrylic resin (B-2). The component (B) is preferably blended in an amount of 1.0 to 40 mass % of the solid content of the negative photosensitive resin composition, and more preferably 5 to 40 mass %.

[0067] When using a polymerizable unsaturated group-containing alkali-soluble resin (B-1), it is preferable to further blend a partially (meth)acrylated epoxy resin (B-1-1) in which a portion of an epoxy resin is (meth)acrylated. Resin (B-1-1) is a partially (meth)acrylated epoxy resin in which a portion of an epoxy resin is (meth)acrylated, and is obtained by reacting a raw material epoxy resin (also referred to as an epoxy compound; the same applies hereinafter) with acrylic acid and / or methacrylic acid to (meth)acrylate a portion of the epoxy groups of the raw material epoxy resin. Since resin (B-1-1) has an epoxy group and a (meth)acrylic group in one molecule, it has both heat curing and UV curing properties, and therefore can be placed between a component having an ethylenically unsaturated group and a light-shielding material (coloring component) such as carbon black during heat curing, which is expected to suppress shrinkage during heat curing, and thereby suppress contact between the light-shielding materials.

[0068] The quantitative relationship of (meth)acrylation can be determined based on the number (moles) of epoxy groups in the raw epoxy resin, and can be calculated from the relationship between this and the number (moles) of (meth)acrylic groups after (meth)acrylation. More simply, it can be determined based on the number (moles) of epoxy groups in the raw epoxy resin and the number (moles) of functional groups in the (meth)acrylic acid to be reacted, depending on the charging ratio of each raw material. The number (moles) of epoxy groups in the raw epoxy resin can be calculated from the weight-average molecular weight and epoxy equivalent. The proportion of raw epoxy groups that are (meth)acrylated can also be expressed as a modification rate [% (mol%)]. The modification rate of resin (B-1-1) can be set widely without particular restrictions depending on the relationship with other components of the composition, the intended use, etc., but the preferred lower limit of the modification rate is 10%, more preferably 20%, even more preferably 30%, even more preferably 40%, and most preferably 50%. On the other hand, the upper limit of the modification rate is preferably 90%, more preferably 80%, even more preferably 70%, even more preferably 60%, and most preferably 50%. A mixture of multiple components with different modification rates may be used as the resin (B-1-1). When a mixture of multiple components with different modification rates is used, it is preferable that the average value of the modification rate falls within the above range. Resin (B-1-1) can be synthesized according to a known method described in JP-A-2019-52273, for example. Although raw material epoxy resins in which the epoxy groups are unmodified and those in which all the epoxy groups are modified are not included as individual components in the definition of resin (B-1-1), these components may also be included in the negative-type photosensitive resin composition of this embodiment. A mixture including these components can also be defined as resin (B-1-1) having the above-mentioned properties such as the modification rate. Examples of the resin (B-1-1) include compounds represented by the following general formulas (1) to (5).

[0069] [ka]

[0070] In formula (1), Cy is an aromatic hydrocarbon group having 6 to 12 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms, Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, and R 11 are independently a hydrocarbon group having 1 to 10 carbon atoms, and R 12 R independently represents a group represented by the following formula (*) and / or formula (**), and contains at least one each of (*) and (**). 17 is a hydrogen atom or a methyl group. a, m, and n each independently represent the number of repetitions, where a is 1 or more, m is 1 or 2, and n is 0 to 7.

[0071] [ka]

[0072] In general formula (1), Cy is preferably a benzene ring, a naphthalene ring, a biphenyl ring, a cyclopentane ring, a cyclohexane ring, or a ring partially substituted with an alkyl group having 1 to 6 carbon atoms, a halogen atom, or the like, and more preferably a benzene ring, a naphthalene ring, or a biphenyl ring.

[0073] Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, and is preferably -R 18 -, a group represented by φ-R 18 -Cy2-R 18 -φ (φ is the joint). R 18 is preferably a group selected from a methylene group, an ethylene group, and a propylene group. Cy2 is preferably a group selected from a phenylene group, a naphthalenediyl group, a biphenyldiyl group, a dicyclopentanediyl group, a dicyclopentenediyl group, and a group formed by combining two or more of these groups.

[0074] R 11 are substituents of Cy, each independently representing a hydrocarbon group having 1 to 10 carbon atoms, and preferred R 11 is a methyl group.

[0075] R 12 are independently an epoxy group represented by formula (*) and / or a group in which an epoxy group has been (meth)acrylated, such as represented by formula (**). As described above, the (meth)acrylated partially (meth)acrylated epoxy resin (B-1-1) is obtained by (meth)acrylating a portion of the raw material epoxy resin, and therefore contains at least one each of the (*) and (**) groups in one molecule.

[0076] a, m, and n each independently represent the number of repeating units, and a is 1 or more, preferably 1 to 50, and more preferably 2 to 45. m is 1 or 2, and when m is 1, a is preferably 2 or more. n is 0 to 7.

[0077] Specific examples of the compound represented by general formula (1) include compounds represented by the following general formulae (1-1) to (1-3).

[0078] [ka]

[0079] In general formulas (1-1) and (1-2), a1 and b each independently represent the number of repetitions. a is usually 0 to 45, but preferably 1 to 40, and b is usually 0 to 45, but preferably 1 to 40. a1+b is 1 or more, and the bonding order of a1 and b may be random. In addition, q in the general formula (1-3) is also the number of repetitions, and q is usually 1 or more.

[0080] [ka]

[0081] In formula (2), R 14 R represents the residue of an organic compound having d active hydrogen groups. 12 independently represent the same formula (*) and / or formula (**) as the above formula (1), and each molecule contains at least one (*) and one (**). d is an integer of 1 to 100. c is each independently an integer of 0 to 100, and the sum of all c's is 2 to 100.

[0082] In general formula (2), R 14 R represents the residue of an organic compound having d active hydrogen groups. 12 is the same as above and represents an epoxy group represented by the formula (*) and / or a group in which an epoxy group is (meth)acrylated, such as represented by the formula (**). As in the case of general formula (1), a resin according to general formula (2) can be obtained by (meth)acrylate- ing some of the epoxy groups represented by the formula (*) in the raw material epoxy resin of general formula (2). Therefore, general formula (2) also contains at least one each of the groups (*) and (**) in one molecule. c and d each independently represent the number of repetitions, and d is an integer of 1 to 100, preferably an integer of 2 to 10, and more preferably an integer of 3 to 6. Each c is independently an integer of 0 to 100. Preferably, it is an integer of 2 to 10, and more preferably an integer of 3 to 6. From the viewpoint of handling, such as the degree of crosslinking after curing and solubility, the sum of all c's is 2 to 100, preferably 3 to 30, and more preferably 4 to 20.

[0083] In addition, the above R 14 Regarding the residue of R, examples of organic compounds having an active hydrogen group, which are precursors of R, include alcohols, phenols, carboxylic acids, amines, thiols, and known compounds described in Japanese Patent No. 5744528. 14 Examples of commercially available raw material epoxy compounds having a group include, but are not limited to, EHPE3150 (1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol) manufactured by Daicel Corporation.

[0084] [ka]

[0085] In formula (3), f, g, h, and i each independently represent 0 or 1, and f+g+h+i=1 to 3. 13 R independently represents the following formula (***) and / or formula (****), and contains at least one each of (***) and (****). 17 is a hydrogen atom or a methyl group.

[0086] [ka]

[0087] For the compound represented by general formula (3), each independent R 13The compound has 3,4-epoxycyclohexyl groups represented by the following formula (***) as groups, and a part of the groups has a group in which the epoxycyclohexyl group is (meth)acrylated as represented by formula (****), so that the compound contains at least one each of the groups (***) and (****). Commercially available epoxy compounds that can be used as raw materials for the compounds of general formula (3) include, but are not limited to, Epolead GT401 (butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl)-modified ε-caprolactone) manufactured by Daicel Corporation.

[0088] R 13 -WR 13 (4) In formula (4), W represents a single bond or a divalent organic group having 1 to 20 carbon atoms which may contain a hetero element inside. 13 independently represent the same formula (***) and / or formula (****) as the above general formula (3), and contain at least one each of (***) and (****).

[0089] Specific examples of W include divalent hydrocarbon groups, divalent groups having carboxy groups at one or two ends of the hydrocarbon group, and the like, which may have an ether bond oxygen atom or an ester bond inside. More specifically, those represented by formulas (14) to (20) described in JP-A-2020-166254 can be used as raw materials. For the compound represented by general formula (4), R 13Since the compound has a 3,4-epoxycyclohexyl group represented by the formula (***) as a group, and a portion of the group has a group in which the epoxycyclohexyl group is (meth)acrylated, as represented by the formula (****), it contains at least one of these groups (***) and (****). That is, the general formula (4) contains one group each of the formulas (***) and (****). Commercially available epoxy compounds that are the raw material for the compound of general formula (4) include, but are not limited to, Celloxide 2021P (3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate) manufactured by Daicel Corporation.

[0090] [ka]

[0091] In formula (5), Z represents -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a 9,9-fluorenyl group, or is absent. 12 R independently represents the following formula (*) and / or formula (**), and contains at least one (*) and one (**). 17 is a hydrogen atom or a methyl group. 15 and R 16 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. p represents the number of repetitions and represents an integer of 0 to 10. [ka]

[0092] In general formula (5), Z represents -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a 9,9-fluorenyl group or is absent, and is preferably a -CH2- or 9,9-fluorenyl group. R 12represents an epoxy group represented by the formula (*) and / or a group in which an epoxy group is (meth)acrylated, as represented by the formula (**). Therefore, general formula (5) also contains one each of the groups (*) and (**). R 15 and R 16 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and are preferably a hydrogen atom or a methyl group. p represents the number of repetitions and represents an integer of 0 to 10, preferably 0 to 8.

[0093] The end point of the synthesis of the partially (meth)acrylated epoxy resin (B-1-1) can be confirmed by measuring the acid value or the like.

[0094] The partially (meth)acrylated epoxy resin (B-1-1) preferably has a weight average molecular weight of 200 to 20,000, more preferably 250 to 15,000.

[0095] The amount of the partially (meth)acrylated epoxy resin (B-1-1) to be blended is preferably 0.2 to 60 mass %, more preferably 0.2 to 55 mass %, and even more preferably 0.3 to 50 mass %, based on the solid content of the negative-type photosensitive resin composition.

[0096] The amount of the partially (meth)acrylated epoxy resin (B-1-1) is preferably 0.8 to 1,000 parts by mass, more preferably 0.9 to 900 parts by mass, and even more preferably 1.5 to 800 parts by mass, per 100 parts by mass of the alkali-soluble resin containing a polymerizable unsaturated group (B-1) or the total of (B-1) and component (C) (a polymerizable compound) described below. By using the above amount per component (B-1) or the total of component (B-1) and component (C), sufficient photocurability can be imparted, and good patterning properties can be obtained, which is preferable.

[0097] Furthermore, the partially (meth)acrylated epoxy resin (B-1-1) is preferably blended in an amount of 0.5 to 180 parts by mass, more preferably 1.0 to 160 parts by mass, and even more preferably 1.0 to 140 parts by mass, per 100 parts by mass of the coloring component (E) described below. By optimizing the amount relative to component (E) in this way, it is possible to achieve both sufficient light-blocking properties and resistance while maintaining good affinity with component (E). The resin (B-1-1) may be used alone or in a mixture of two or more kinds.

[0098] For the polymerizable unsaturated group-containing alkali-soluble resin (B-1) and the partially (meth)acrylated epoxy resin (B-1-1), reference can be made to JP-A No. 2023-97382.

[0099] ·Component (C) The polymerizable compound, component (C), can serve to crosslink the molecules of component (B) together. Examples of component (C) include (meth)acrylic acid esters having a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxyhexyl (meth)acrylate; ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentane tri(meth)acrylate. Examples of the polymerizable compound include (meth)acrylic acid esters such as pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, glycerol (meth)acrylate, glycerol di(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide-modified hexa(meth)acrylate of phosphazene, and caprolactone-modified dipentaerythritol hexa(meth)acrylate, and dendritic polymers having a (meth)acryloyl group. The polymerizable compound may be used alone or in combination of two or more. Examples of dendritic polymers having (meth)acroyl groups include known dendritic polymers obtained by adding a thiol group in a polyvalent mercapto compound to a portion of the carbon-carbon double bond in the (meth)acroyl group of a polyfunctional (meth)acrylate compound.

[0100] It is more preferable to use a polymerizable compound having two or more ethylenically unsaturated bonds. In addition, the acrylic equivalent, which is the molecular weight of the monomer divided by the number of (meth)acryloyl groups in one molecule, may be 50 to 300.

[0101] The component (C) is preferably blended in an amount of 1.0 to 40 mass % of the solid content of the negative photosensitive resin composition, and more preferably 5 to 40 mass %.

[0102] ·Component (D) The polymerization initiator, component (D), is a compound that generates radicals through bond cleavage and / or reaction upon exposure. The inclusion of a polymerization initiator makes the exposed areas of the negative photosensitive resin composition film insoluble in alkaline developer, thereby forming a negative pattern. Furthermore, curing of the exposed areas is accelerated, improving sensitivity.

[0103] The polymerization initiator is not particularly limited, and known photopolymerization initiators can be used. For example, acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, and benzyl dimethyl ketal; benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone, 4,4'-bisdimethylaminobenzophenone (Michler's ketone), 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, ... benzophenones such as benzophenone and 4,4'-diethylaminobenzophenone; benzoin ethers such as benzil, benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; 2-(o-chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4,5-diphenylbiimidazole, 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, 2,4, Biimidazole compounds such as 5-triarylbiimidazole and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2-biimidazole; halomethyldiazole compounds such as 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, and 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole; 2,4,6-tris(trichloromethyl)-1,3,5-triazinyl 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,Halomethyl-s-triazine compounds such as 5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, and 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime), 1-(4-phenylsulfanylphenyl)butane-1,2-dione-2-oxime-O-benzoate, and 1-(4-methylsulfanylphenyl)butane-1,2-Dione-2-oxime-O-acetate, 1-(4-methylsulfanylphenyl)butan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-bicycloheptyl-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-adamantylmethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol- 3-yl]-adamantylmethan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-tetrahydrofuranylmethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-tetrahydrofuranylmethan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-thiophenylmethan-1-one Oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-thiophenylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-morphonylmethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-morphonylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2 -methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-bicycloheptanecarboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-tricyclodecanecarboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-adamantanecarboxylate, 1-[4-(phenylsulfanyl)phenyl]octane-1,2-Dione = 2-O-benzoyloxime, 1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethanone-O-acetyloxime, (2-methylphenyl)(7-nitro-9,9-dipropyl-9H-fluoren-2-yl)-acetyloxime, Ethanone, 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]-1-(o-acetyloxime), Ethanone, 1-(-9,9-dibutyl-7-nitro-9H-fluoren-2-yl)-1-O-acetate O-Acyloxime compounds such as acetyl oxime, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime); sulfur compounds such as thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone; 2-ethyl Anthraquinones such as 1,2-benzanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone; organic peroxides such as azobisisobutylnitrile, benzoyl peroxide, and cumene peroxide; 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, β-mercaptopropionic acid, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, and methoxybutyl-3- Mercaptopropionate, stearyl-3-mercaptopropionate, trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), 3,Examples of suitable initiators include thiol compounds such as 3'-thiodipropionic acid, dithiodipropionic acid, and laurylthiopropionic acid. Among these, O-acyloxime compounds are preferred because they are more likely to produce a highly sensitive photosensitive resin composition. Two or more types of polymerization initiators can also be used. In this application, the term "polymerization initiator" is used to include a sensitizer.

[0104] Alternatively, compounds that do not function as polymerization initiators or sensitizers by themselves but can enhance their polymerization initiator or sensitizer capabilities when used in combination with the above-mentioned compounds may be added. Examples of such compounds include amine compounds that are effective when used in combination with benzophenone. Examples of the amine compounds include triethylamine, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone.

[0105] The amount of component (D) added is preferably 2 to 40 parts by mass, and more preferably 3 to 30 parts by mass, per 100 parts by mass of the total of components (A), (B) and (C) which are the resin components.

[0106] ·Component (E) As the coloring component (E), any known coloring component can be used without limitation. Component (E) is preferably an organic pigment or an inorganic pigment, and more preferably a light-shielding material made of an organic black pigment, a mixed-color organic pigment, or an inorganic black pigment. Examples of black organic pigments include perylene black, aniline black, cyanine black, and lactam black. Examples of mixed-color organic pigments include those obtained by mixing two or more pigments selected from red, blue, green, purple, yellow, cyanine, magenta, and the like to produce a pseudo-black color. Examples of inorganic black pigments include carbon black, chromium oxide, iron oxide, and titanium black. These coloring components may be used alone or in combination. They can be appropriately selected and used depending on the purpose of the photosensitive resin composition. Among these coloring components, carbon black is more preferred from the viewpoints of light-shielding properties, surface smoothness, dispersion stability, and affinity with resins. On the other hand, titanium black is preferably used in applications where electrical resistance and light-shielding properties are important, while lactam black is preferably used in applications where infrared transmittance and low dielectric properties are important.

[0107] The carbon black is preferably untreated or oxidized. "Untreated" here means that no special surface treatment, such as oxidation or resin coating, has been performed, and "oxidized" means that the surface of the carbon black is treated with an oxidizing agent before the dispersion step. Such untreated or oxidized carbon black has many acidic functional groups on its surface, which react with the epoxy groups of the partially (meth)acrylated epoxy resin (B-1-1) during thermal curing to obtain a cured film, thereby allowing a large amount of resin (B-1-1) to be present near the carbon black. Furthermore, when using carbon black to further increase the resistance value of the cured film, surface-coated carbon black, in which the carbon black surface is coated with a dye, pigment, resin, or the like, may be used.

[0108] The amount of component (E) added can be determined arbitrarily so as to achieve the desired light-blocking degree, and is preferably 30 to 70 mass % and more preferably 40 to 60 mass % relative to the solid content in the photosensitive resin composition.

[0109] Component (E) is preferably dispersed in a solvent together with a dispersant to form a colored dispersion, which is then blended into the photosensitive resin composition. The solvent used for dispersion becomes part of the organic solvent (F) described below, so any of the solvents listed for component (F) can be used. For example, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, etc. are preferably used.

[0110] The dispersant can be any known dispersant, such as various polymeric dispersants. Examples of dispersants include, without limitation, known compounds conventionally used in pigment dispersions (e.g., compounds commercially available under the names of dispersants, dispersing wetting agents, dispersion promoters, etc.), but examples include cationic polymeric dispersants, anionic polymeric dispersants, nonionic polymeric dispersants, and pigment derivative dispersants (dispersion aids). Cationic polymeric dispersants that have cationic functional groups, such as imidazolyl groups, pyrrolyl groups, pyridyl groups, or primary, secondary, or tertiary amino groups, as adsorption sites for the pigment, and that have an amine value of 1 to 100 mgKOH / g and a number-average molecular weight of 1,000 to 100,000, are particularly suitable. The amount of this dispersant to be added is preferably 1 to 30% by mass relative to the (E) coloring component.

[0111] Ingredient (F) Examples of the organic solvent as component (F) include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy-2-butanone, and diacetone alcohol; terpenes such as α- or β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, and propylene glycol monomethyl ether. Examples of suitable solvents include glycol ethers such as ethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; and esters such as ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, 3-methoxy-3-methyl-1-butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. These solvents can be used to dissolve, disperse, or mix components (A) to (E), etc., to prepare a uniform solution-like composition. The amount of organic solvent in the negative photosensitive resin composition is preferably an amount such that the solids concentration in the composition is 5% by mass or more, and preferably 65% ​​by mass or less, because the fluidity of the composition allows a uniform coating film to be obtained by a coating method such as spin coating.

[0112] Other ingredients The negative-type photosensitive resin composition of this embodiment may optionally contain additives such as an epoxy resin (other than the resin (B-1-1)), a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler, a leveling agent, an antifoaming agent, a coupling agent, a surfactant, and a viscosity modifier. Known epoxy resins may be used as the epoxy resin. Examples of the thermal polymerization inhibitor and antioxidant include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, and hindered phenol compounds. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. Examples of the filler include glass fiber, silica, mica, and alumina. Examples of the antifoaming agent and leveling agent include silicone-based, fluorine-based, and acrylic compounds. Examples of surfactants include anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether triethanolamine sulfate, cationic surfactants such as stearylamine acetate and lauryl trimethylammonium chloride, amphoteric surfactants such as lauryl dimethylamine oxide and lauryl carboxymethyl hydroxyethyl imidazolium betaine, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and sorbitan monostearate, silicone surfactants having a polydimethylsiloxane or the like as a main skeleton, and fluorine-based surfactants. Examples of coupling agents include silane coupling agents such as 3-(glycidyloxy)propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane and 3-ureidopropyltriethoxysilane.

[0113] The negative photosensitive resin composition of this embodiment can be prepared by stirring and mixing the above-mentioned components (A) to (F), and various additives as needed, in a conventional manner to form a homogeneous liquid. When solid materials such as fillers and pigments are blended into the composition, they are preferably dispersed and mixed using a dispersing device such as a dissolver, homogenizer, triple roll mill, etc. The composition can also be filtered using a mesh filter, membrane filter, etc. to remove coarse particles and impurities. The negative photosensitive resin composition of this embodiment can be suitably used for applications such as resist films, resist underlayer films, and permanent resist films.

[0114] The negative photosensitive resin composition of the present invention can be used in the same manner as a general negative photosensitive resin composition to form a resist film, a resist underlayer film, and a permanent resist film (hereinafter, the resist film, the resist underlayer film, and the permanent resist film may be collectively referred to as a resist film, etc.). Specifically, the negative photosensitive resin composition of the present invention is applied to an object to be subjected to photolithography, and then prebaked to obtain a film of the photosensitive resin composition (photosensitive film) from which the solvent has been removed.

[0115] Examples of application methods include spin coating, roll coating, flow coating, dip coating, spray coating, and doctor blade coating. Pre-baking may involve heating at a temperature of 60°C to 150°C for 30 to 600 seconds. The negative photosensitive resin composition of the present invention can be applied to a substrate appropriately selected from glass substrates, silicon substrates, aluminum substrates, silicon carbide substrates, silicon nitride substrates, gallium nitride substrates, transparent conductive films, copper substrates, copper-plated substrates, and the like.

[0116] By exposing the photosensitive film, the solubility of the exposed area in an alkaline developer is significantly reduced. Examples of light sources used for exposure include infrared light, visible light, ultraviolet light, far-ultraviolet light, X-rays, and electron beams. Among these light sources, ultraviolet light is preferred, and the g-line (wavelength 436 nm) and i-line (wavelength 365 nm) of a high-pressure mercury lamp are suitable. After exposure, the film may be heat-treated at approximately 100°C to 150°C.

[0117] The photosensitive film obtained from the negative photosensitive resin composition of the present invention has a large difference in alkali solubility between the exposed and unexposed areas, making it possible to pattern it with high resolution. Therefore, it can be suitably used as a resist film, etc. In this application, the term "resist film, etc." includes both a photosensitive film before exposure and a non-photosensitive film after exposure.

[0118] Examples of alkaline developers used for development after exposure include alkaline aqueous solutions of inorganic alkaline substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; 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; and cyclic amines such as pyrrole and piheridine. The alkaline developer may be used by adding alcohol, surfactant, etc. as needed. The alkaline concentration of the alkaline developer is usually preferably in the range of 2 to 5% by mass, and a 2.38% by mass aqueous solution of tetramethylammonium hydroxide is generally used.

[0119] When the negative-tone photosensitive resin composition of the present invention is used for a resist underlayer film (BARC film), the negative-tone photosensitive resin composition of the present invention may be used as it is as a composition for a resist underlayer film, or various additives such as other resin components, surfactants, dyes, fillers, crosslinking agents, and dissolution promoters may be added, if necessary.

[0120] Examples of other resin components include various novolak resins, addition polymerization resins of alicyclic diene compounds such as dicyclopentadiene and phenolic compounds, modified novolak resins of phenolic hydroxyl group-containing compounds and alkoxy group-containing aromatic compounds, phenol aralkyl resins (Zylok resins), naphthol aralkyl resins, trimethylolmethane resins, tetraphenylolethane resins, biphenyl-modified phenolic resins, biphenyl-modified naphthol resins, aminotriazine-modified phenolic resins, and various vinyl polymers. When other resin components are used, the blending ratio of the negative photosensitive resin composition of the present invention to the other resins can be set as desired depending on the application. For example, the blending ratio is preferably 0.5 to 100 parts by mass of the other resins per 100 parts by mass of component (A).

[0121] The composition for a resist underlayer film can be prepared by blending the above-mentioned components and mixing them using a stirrer, etc. Furthermore, when the composition for a resist underlayer film contains a filler or a pigment, it can be prepared by dispersing or mixing using a dispersing device such as a dissolver, a homogenizer, or a three-roll mill.

[0122] To form a resist underlayer film from the resist underlayer film composition, for example, the above-described resist underlayer film composition is applied to an object to be photolithographed, such as a silicon substrate, dried at a temperature of 100 to 200° C., and then further cured by heating at a temperature of 250 to 400° C. Next, a resist pattern is formed on this underlayer film by performing a normal photolithography operation, and then dry-etched with a halogen-based plasma gas or the like, thereby forming a resist pattern by a multilayer resist method.

[0123] When the negative photosensitive resin composition of the present invention is used for a permanent resist film, in addition to the components (A) to (F) of the present invention, additives such as other resins, surfactants, dyes, fillers, crosslinking agents, dissolution promoters, etc. may be added as needed. Examples of other resins used here include the same resins as those that can be used in compositions for resist underlayer films.

[0124] In a photolithography method using a composition for a permanent resist film, for example, other resin components and additive components are dissolved or dispersed in the negative photosensitive resin composition of the present invention, and the composition is applied to an object to be photolithographed, followed by pre-baking at a temperature of 60 to 150° C. The application method may be any of spin coating, roll coating, flow coating, dip coating, spray coating, doctor blade coating, etc. Next, the desired resist pattern is exposed through a predetermined mask, and the unexposed areas are dissolved in an alkaline developer to form a resist pattern.

[0125] The permanent resist film of this embodiment can be suitably used, for example, in semiconductor devices, as solder resist, packaging material, underfill material, package adhesive layer for circuit elements, and adhesive layer between integrated circuit elements and circuit boards, and in thin-film displays such as LCDs and OLEDs, as thin-film transistor protective films, liquid crystal color filter protective films, black matrices, spacers, and the like. [Example]

[0126] The present invention will be described in more 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. [GPC measurement conditions] Measuring device: Tosoh Corporation "HLC-8220 GPC" Column: Showa Denko K.K. "Shodex KF802": 8.0mmΦ x 300mm +Showa Denko KF802: 8.0mmΦ x 300mm +Showa Denko KF803: 8.0mmΦ x 300mm +Showa Denko KF804: 8.0mmΦ x 300mm Column temperature: 40℃ Detector: RI (differential refractometer) Data processing: Tosoh Corporation "GPC-8020 Model II Version 4.30" Developing solvent: tetrahydrofuran Flow rate: 1.0mL / min Sample: 0.5% by mass of tetrahydrofuran solution converted to resin solids filtered through a microfilter Injection volume: 0.1mL Standard sample: monodisperse polystyrene as follows (Standard sample: monodisperse polystyrene) Tosoh Corporation "A-500" Tosoh Corporation "A-2500" Tosoh Corporation "A-5000" "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation "F-10" manufactured by Tosoh Corporation "F-20" manufactured by Tosoh Corporation

[0127] Synthesis Example 1 (Synthesis of Novolac Phenolic Resin (A-1)) A 2000 mL four-neck flask equipped with a condenser was charged with 164 g (1.52 mol) of m-cresol, 103 g (0.97 mol) of benzaldehyde, 74 g (0.61 mol) of salicylaldehyde, and 8 g of paratoluenesulfonic acid, which were then dissolved in 300 g of ethanol as the reaction solvent. The mixture was then heated to 80°C using a mantle heater and stirred under reflux for 16 hours to allow the reaction to proceed. After the reaction, ethyl acetate and water were added and the mixture was washed five times with a separation wash. The solvent was removed from the remaining resin solution by distillation under reduced pressure, followed by vacuum drying, yielding 281 g of a pale red powder of novolac-type phenolic resin (A-1). The Mw of the novolac phenolic resin (A-1) was 3,100. The GPC chart of the novolac phenolic resin (A-1) is shown in FIG.

[0128] Synthesis Example 2 (Synthesis of Novolac Phenolic Resin (A-2)) Except for changing the amounts of starting materials to 164 g (1.52 mol) of m-cresol, 80 g (0.75 mol) of benzaldehyde, and 92 g (0.75 mol) of salicylaldehyde, 280 g of powder of novolac type phenolic resin (A-2) was obtained in the same manner as in Synthesis Example 1. The Mw of the novolac type phenolic resin (A-2) was 2,370. The GPC chart of the novolac phenolic resin (A-2) is shown in FIG.

[0129] Synthesis Example 3 (Synthesis of Novolac Phenolic Resin (A-3)) Except for changing the amounts of starting materials to 164 g (1.52 mol) of m-cresol, 67 g (0.63 mol) of benzaldehyde, and 115 g (0.94 mol) of salicylaldehyde, the same procedure as in Synthesis Example 1 was repeated to obtain 279 g of powder of novolac phenolic resin (A-3). The Mw of the novolac phenolic resin (A-3) was 2,700. The GPC chart of the novolac phenolic resin (A-3) is shown in FIG.

[0130] Synthesis Example 4 (Synthesis of Novolac Phenolic Resin (A-4)) Except for changing the amounts of starting materials to 164 g (1.52 mol) of m-cresol, 117 g (1.10 mol) of benzaldehyde, and 58 g (0.47 mol) of salicylaldehyde, the same procedure as in Synthesis Example 1 was repeated to obtain 282 g of powder of novolac phenolic resin (A-4). The Mw of the novolac phenolic resin (A-4) was 2,900. The GPC chart of the novolac phenolic resin (A-4) is shown in FIG.

[0131] Synthesis Example 5 (Synthesis of Novolac Phenolic Resin (A-5)) Except for changing the reaction solvent to 250 g of ethanol, 30 g of 1-propanol, and 15 g of 2-propanol, the same procedure as in Synthesis Example 1 was repeated to obtain 282 g of powder of novolac phenolic resin (A-5). The Mw of the novolac phenolic resin (A-5) was 3,200. The GPC chart of the novolac phenolic resin (A-5) is shown in FIG.

[0132] Synthesis Example 6 (Synthesis of Novolac Phenolic Resin (A-6)) A 2000 mL four-neck flask equipped with a condenser was charged with 164 g (1.52 mol) of m-cresol, 70 g (0.66 mol) of benzaldehyde, 121 g (0.99 mol) of salicylaldehyde, and 8 g of paratoluenesulfonic acid, which were then dissolved in 300 g of methanol as the reaction solvent. The mixture was then heated in a mantle heater and stirred at 65°C under reflux for 16 hours. After the reaction, ethyl acetate and water were added and the mixture was washed five times with separation. The solvent was removed from the remaining resin solution under reduced pressure, followed by vacuum drying, yielding 286 g of a pale red novolac phenolic resin powder (A-6). The Mw of the novolac phenolic resin (A-6) was 6,800. The GPC chart of the novolac phenolic resin (A-6) is shown in FIG.

[0133] Synthesis Example 7 (Synthesis of Novolac Phenolic Resin (A-7)) Except for changing the amounts of starting materials to 164 g (1.52 mol) of m-cresol, 102 g (0.96 mol) of benzaldehyde, and 86 g (0.70 mol) of salicylaldehyde, the same procedure as in Synthesis Example 6 was repeated to obtain 283 g of powder of novolac phenolic resin (A-7). The Mw of the novolac phenolic resin (A-7) was 13,900. The GPC chart of the novolac phenolic resin (A-7) is shown in FIG.

[0134] Comparative Synthesis Example 1 (Synthesis of Novolac Phenolic Resin (A-8)) Under a dry nitrogen stream, 140 g (1.30 mol) of m-cresol, 76 g (0.7 mol) of p-cresol, 151 g of 37 wt% formaldehyde aqueous solution (1.86 mol of formaldehyde), and 1 g (0.01 mol) of oxalic acid dihydrate were charged into a 2000 mL three-neck flask equipped with a condenser and dissolved in 528 g of methyl isobutyl ketone (MIBK). The mixture was then heated in a mantle heater and refluxed for 4 hours while stirring. After the reaction, water was added and the mixture was washed five times with a separatory system. The methyl isobutyl ketone was removed under reduced pressure at 60°C using an evaporator, followed by vacuum drying to obtain 212 g of a pale red powder of novolac phenolic resin (A-8). The Mw of the novolac phenolic resin (A-8) was 3,600.

[0135] Synthesis Example 8 (Synthesis of Alkali-Soluble Resin (b-1) Having a Polymerizable Unsaturated Group) A polymerizable unsaturated group-containing alkali-soluble resin solution (b-1) (solids concentration 50%) was obtained with reference to Synthesis Example 1 of JP 2023-97382 A. Specifically, 114.4 g (0.23 mol) of the reaction product of 9,9-bis(4-hydroxyphenyl)fluorene and chloromethyloxirane, 33.2 g (0.46 mol) of acrylic acid, 157 g of PGMEA, and 0.48 g of tetraethylammonium bromide were charged into a 500 mL four-neck flask equipped with a reflux condenser, and the mixture was stirred and reacted for 20 hours at 100 to 105°C. Next, 35.3 g (0.12 mol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride and 18.3 g (0.12 mol) of 1,2,3,6-tetrahydrophthalic anhydride were charged into the flask, and the mixture was stirred for 6 hours while heating at 120 to 125°C to obtain a solution of a polymerizable unsaturated group-containing alkali-soluble resin (b-1).

[0136] Synthesis Example 9 (Synthesis of Partially Acrylated Epoxy Resin (b-1-1)) A partially acrylated epoxy resin solution (b-2) (solid content concentration 50%) was obtained with reference to Synthesis Example 2 of JP 2023-97382 A. Specifically, in the structure represented by general formula (1), Cy is a benzene ring, R 12 are all groups of the formula (*), Y is a methylene group, R 11A cresol novolac epoxy resin with a methyl group, m=1, n=1, a≒6.8, Mw=1574, and epoxy equivalent weight=203 g / eq was used as the raw resin. 282 parts by mass (1.389 equivalents) of this raw resin were added with 50 parts by mass (0.694 equivalents) of acrylic acid, 111 parts by mass of PGMEA, 1 part by mass of triphenylphosphine, and 0.1 part by mass of hydroquinone monomethyl ether, and 1 part by mass of phenolsulfonic acid, and the mixture was allowed to react at 80°C to 90°C for 10 hours. As a result, the R of the raw resin was 12 A partially acrylated epoxy resin (b-1-1) was obtained in which a portion of the functional groups (50% equivalent ratio) was acrylated.

[0137] Synthesis Example 10 (Synthesis of (meth)acrylic alkali-soluble resin (b-2)) Epoxy group, hydroxyl group-containing methacrylic resin (b-2) (solid content concentration 20%) was obtained with reference to Synthesis Example 1 of JP 2022-38599 A. Specifically, 33.40 g of 4-hydroxyphenyl methacrylate ("PQMA" manufactured by Showa Denko K.K.) and 6.66 g of glycidyl methacrylate (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 added dropwise over 2 hours to 45.0 g of PGMEA heated to 85°C in a 300 mL three-neck flask under a nitrogen gas atmosphere, and after completion of the addition, the mixture was allowed to react at 85°C for 3 hours to obtain a 20 wt% solids solution of a (meth)acrylic alkali-soluble resin (b-2) with a PQMA / GMA ratio of 80 / 20.

[0138] [Negative-type photosensitive resin composition] Example 1 A negative photosensitive resin composition was obtained by mixing and dissolving 1.16 g of the novolak phenolic resin (A-1) powder obtained in Synthesis Example 1, 2.32 g of the polymerizable unsaturated group-containing alkali-soluble resin solution (b-1), 0.06 g of the partially acrylated epoxy resin solution (b-1-1), 1.57 g of the polymerizable compound (C) (dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd.), 0.46 g of the polymerization initiator (D) (NCI-831 manufactured by ADEKA Corporation), and 13.12 g of the carbon black dispersion (E) (25% carbon black, 6% dispersant in propylene glycol monomethyl ether acetate (PGMEA) solvent) in 23.59 g of propylene glycol monomethyl ether acetate (PGMEA) (F) (PMA-P manufactured by KH Neochem Co., Ltd.).

[0139] Examples 2 to 7, Comparative Example 1 Negative photosensitive resin compositions were obtained in the same manner as in Example 1, except that powders of novolac phenolic resins (A-2) to (A-8) shown in Table 1 were used as component (A).

[0140] Example 8 A negative photosensitive resin composition was obtained by mixing and dissolving 1.18 g of novolac phenolic resin (A-1) powder, 5.9 g of the (meth)acrylic alkali-soluble resin solution (b-2) synthesized in Synthesis Example 10, 1.76 g of polymerizable compound (C) (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.), 0.46 g of polymerization initiator (D) (NCI-831, manufactured by ADEKA Corporation), and 13.12 g of carbon black dispersion (E) (25% carbon black, 6% dispersant, propylene glycol monomethyl ether acetate (PGMEA) solvent) in 20.83 g of PGMEA (F) (PMA-P, manufactured by KH Neochem Co., Ltd.).

[0141] Examples 9 to 14, Comparative Example 2 Negative photosensitive resin compositions were obtained in the same manner as in Example 8, except that powders of novolac phenolic resins (A-2) to (A-8) shown in Table 2 were used as component (A).

[0142] Comparative Example 3 A negative photosensitive resin composition was obtained in the same manner as in Example 1, except that 2.32 g of the polymerizable unsaturated group-containing alkali-soluble resin solution (b-1) synthesized in Synthesis Example 8 was used instead of the novolac phenolic resin (A-1), and the amount of PGMEA (F) was 22.43 g.

[0143] Comparative Example 4 A negative photosensitive resin composition was obtained in the same manner as in Example 8, except that 5.9 g of the (meth)acrylic alkali-soluble resin solution (b-2) synthesized in Synthesis Example 10 was used instead of the novolac phenolic resin (A-1) and the amount of PGMEA (F) was 16.11 g.

[0144] [evaluation] Resist films were produced using the negative photosensitive resin compositions prepared in the Examples and Comparative Examples, and the film-forming properties, alkali solubility of the resist films before exposure, and chemical resistance of the cured resist films after exposure were evaluated. (1) Film formability The negative photosensitive resin composition was applied to a silicon wafer having a diameter of 5 inches using a bar coater (No. 02, manufactured by Daiichi Rika Co., Ltd.) to a thickness of approximately 5 μm, and the applied film was then dry prebaked at 100° C. for 60 seconds. The surface of the wafer obtained was observed using an optical microscope to evaluate the presence or absence of scum generation. Those without scum were rated as having good compatibility (◯), and those with scum were rated as having poor compatibility (×). The evaluation results are shown in Tables 1 and 2.

[0145] (2) Alkali solubility The negative photosensitive resin composition was applied to a silicon wafer with a diameter of 5 inches using a bar coater to a thickness of approximately 5 μm, and the coating film was then pre-baked at 100°C for 60 seconds. The resulting wafer was immersed for 10 seconds in a tray containing 250 mL of developer (2.38% aqueous tetramethylammonium hydroxide solution). The wafer was then removed and rinsed with pure water for 10 seconds, and the residue (resist film) on the wafer was evaluated. Those with no residue were rated as good (◯), and those with residue were rated as poor (×). The evaluation results are shown in Tables 1 and 2.

[0146] (3) Chemical resistance of the cured film The negative photosensitive resin composition was applied to a silicon wafer with a diameter of 5 inches to a thickness of approximately 5 μm using a bar coater (manufactured by Daiichi Rika Co., Ltd.: No. 02), and then dried at 100°C for 60 seconds. Thereafter, the wafer was irradiated with 200 mJ / cm using a UV irradiation device (manufactured by Minaga Electric Co., Ltd.: UVE-1001SD). 2 After irradiation with light, the wafer was baked at 230° C. for 180 seconds to obtain a wafer on which a cured film was formed. After measuring the film thickness of the resulting wafer, it was divided into two. One of the two pieces was immersed in 50 wt% sulfuric acid water (simulating plating solution), and the other in 2.38 wt% TMAH water solution for 15 minutes. After removing the wafer from the solution and washing it with pure water, the film thickness was measured again. Chemical resistance was evaluated based on the rate of change in film thickness before and after immersion in a solvent. A rate of change of less than 2% was rated as good (◯), and a rate of change of 2% or more was rated as insufficient (×). The evaluation results are shown in Tables 1 and 2. In the tables, (b-1) alkali-soluble resin is the alkali-soluble resin containing a polymerizable unsaturated group synthesized in Synthesis Example 8, and (b-2) alkali-soluble resin is the (meth)acrylic alkali-soluble resin synthesized in Synthesis Example 10.

[0147] [Table 1]

[0148] [Table 2]

[0149] In Table 1, the molar ratio of the structural units of component (A), "(a1) / (a2) / (a3)," is the molar ratio of the structural unit (a1) derived from m-cresol, the structural unit (a2) derived from benzaldehyde, and the structural unit (a3) ​​derived from salicylaldehyde.

[0150] From Tables 1 and 2, it can be seen that the resist film using the negative photosensitive resin composition of the present invention has high film formability, high alkali solubility, and excellent chemical resistance when cured.

Claims

1. A negative photosensitive resin composition comprising the following components (A) to (F): (A) A novolac phenolic resin in which the molar ratio of the structural unit (a1) derived from cresol, the structural unit (a2) derived from benzaldehyde, and the structural unit (a3) ​​derived from hydroxybenzaldehyde [(a1):(a2):(a3)] is 1.0:0.3-0.8:0.3-0.

8. (B) At least one alkali-soluble resin selected from the group consisting of a polymerizable unsaturated group-containing alkali-soluble resin and a (meth)acrylic alkali-soluble resin. (C) Polymerizable compound (D) Polymerization initiator (E) Coloring component (F) Organic solvent

2. 2. The negative photosensitive resin composition according to claim 1, wherein the component (A) is a novolak phenolic resin obtained by polycondensing cresol, benzaldehyde, and hydroxybenzaldehyde in an organic solvent in a molar ratio of cresol:benzaldehyde:hydroxybenzaldehyde = 1.0:0.3-0.8:0.3-0.8 using an acid catalyst.

3. 3. The negative photosensitive resin composition according to claim 2, wherein the cresol is m-cresol and the hydroxybenzaldehyde is salicylaldehyde.

4. 3. The negative photosensitive resin composition according to claim 1, wherein the total content of the structural unit (a1) derived from cresol, the structural unit (a2) derived from benzaldehyde, and the structural unit (a3) ​​derived from hydroxybenzaldehyde in the component (A) is 30% by mass or more.

5. 3. The negative photosensitive resin composition according to claim 1, wherein the weight average molecular weight of the component (A) is 1,000 or more and 15,000 or less.

6. A cured film obtained from the negative photosensitive resin composition according to claim 1 or 2.

7. A resist film obtained from the negative photosensitive resin composition according to claim 1 or 2.

8. A resist underlayer film obtained from the negative photosensitive resin composition according to claim 1 or 2.

9. A permanent resist film obtained from the negative photosensitive resin composition according to claim 1 or 2.

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