Negative photosensitive resin composition, cured film, resist film, resist underlayer film, and resist permanent film

Abstract

The invention provides a negative photosensitive resin composition, a cured film, a resist film, a resist underlayer film and a resist permanent film. The resist film before exposure has alkali solubility and excellent film forming performance, and the resist cured product after exposure has excellent chemical resistance. The negative photosensitive resin composition contains the following components (A) to (F). (A) novolac phenolic resin in which the molar ratio of structural unit (a1) derived from cresol, structural unit (a2) derived from benzaldehyde, and 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 of polymerizable unsaturated group-containing alkali-soluble resin and (meth) acrylic alkali-soluble resin / (C) polymerizable compound / (D) polymerization initiator / (E) coloring component / (F) organic solvent.

Description

Technical Field

[0001] This invention relates to a negative photosensitive resin composition, a hardened film, a resist film, a resist underlayer film, and a resist permanent film. Background Technology

[0002] Organic electroluminescence (EL) displays have attracted much attention as the next generation of flat panel displays. EL displays are self-emissive display devices that utilize electric fields based on organic compounds to emit light. They possess excellent characteristics such as wide viewing angles, high-speed image display, and the potential for further thinning and weight reduction. In recent years, with the increasing precision of EL displays, there has been a demand for further miniaturization of the light-emitting elements.

[0003] Organic EL displays (OLEDs) emit light using the energy from the recombination of electrons injected from the cathode and holes injected from the anode. Therefore, the presence of substances that create energy levels that hinder the recombination of electrons and holes leads to a decrease in the luminous efficiency of the light-emitting element and a reduction in the lifespan of the OLED display. Consequently, to separate the pixels of the light-emitting element, an insulating layer called a pixel separation layer, using a negative-type photosensitive resin composition, is typically formed between the transparent electrode on the light extraction side and the opposite metal electrode. Since this pixel separation layer is formed adjacent to the light-emitting element, the reduction in insulation, deformation, or deterioration caused by the light emission and heat generated by the pixel separation layer can contribute to the reduced lifespan of the OLED display.

[0004] On the other hand, in addition to insulation, the pixel segmentation layer is required to be blackened (highly opaque) in order to improve the visibility and contrast of the organic EL display, and a photosensitive resin composition containing a black pigment is used. Carbon black is commonly known as a black pigment, but carbon black has high conductivity, and there are concerns that its addition may reduce the insulation of the pixel segmentation layer, causing malfunctions in the display device.

[0005] Therefore, in order to improve the insulation of pixel segmentation layers using carbon black, a method of coating the surface of carbon black with epoxy resin has been proposed (e.g., Patent Document 1). However, although the negative photosensitive resin composition using carbon black described in Patent Document 1 has improved insulation, it is not suitable for forming fine patterns.

[0006] In addition, a photosensitive resin composition is being researched and developed, in which a (meth)acrylated epoxy resin, after a portion of the epoxy resin has been (meth)acrylated, and an alkali-soluble resin are used as the main components of the pixel dividing layer (for example, Patent Document 2). However, in the photosensitive resin composition described in Patent Document 2, although the insulation is improved, sufficient alkali solubility cannot be obtained, and the generation of residue becomes a problem.

[0007] In addition, a negative photosensitive resin composition in which epoxy groups and alkali-soluble groups are introduced into a (meth)acrylic resin backbone has been proposed (for example, Patent Document 3). However, in reality, even in the photosensitive resin composition described in Patent Document 3, the alkali solubility is still insufficient, and residue of the pattern after development can still be seen due to insufficient sensitivity.

[0008] As mentioned above, with the increasing sophistication of organic EL displays, there is a need to develop a negative photosensitive resin composition capable of forming finer pixel segmentation layer patterns without producing residue.

[0009] [Existing technical documents]

[0010] [Patent Document]

[0011] [Patent Document 1] Japanese Patent Application Publication No. 2001-207079

[0012] [Patent Document 2] Japanese Patent Application Publication No. 2023-97382

[0013] [Patent Document 3] Japanese Patent Application Publication No. 2022-38599 Summary of the Invention

[0014] [The problem the invention aims to solve]

[0015] The purpose of this invention is to provide a negative photosensitive resin composition, wherein the resist film before exposure has alkali solubility and excellent film-forming properties, and the resist hardened material after exposure has excellent chemical resistance.

[0016] [Technical means to solve the problem]

[0017] The present invention relates to a negative photosensitive resin composition containing the following components (A) to (F).

[0018] (A) A phenolic varnish-type phenolic resin with a molar ratio of (a1):(a2):(a3) of cresol-derived structural unit (a1):(a2):(a3) of 1.0:0.3–0.8:0.3–0.8.

[0019] (B) At least one alkali-soluble resin selected from alkali-soluble resins containing polymerizable unsaturated groups and (meth)acrylic acid-based alkali-soluble resins.

[0020] (C) Polymer compounds

[0021] (D) Polymerization initiator

[0022] (E) Coloring components

[0023] (F) Organic solvents

[0024] The present invention also relates to a hardened film obtained from the aforementioned negative photosensitive resin composition.

[0025] The present invention also relates to a resist film obtained from the aforementioned negative photosensitive resin composition.

[0026] The present invention also relates to a photoresist underlayer film obtained from the aforementioned negative photosensitive resin composition.

[0027] The present invention also relates to a permanent resist film obtained from the aforementioned negative photosensitive resin composition.

[0028] [The effects of the invention]

[0029] The present invention provides a negative photosensitive resin composition, wherein the resist film before exposure has alkali solubility and excellent film-forming properties, and the resist hardened material after exposure has excellent chemical resistance. Attached Figure Description

[0030] Figure 1 This is the GPC chart of the phenolic varnish-type phenolic resin obtained in Synthesis Example 1.

[0031] Figure 2 This is the GPC chart of the phenolic varnish-type phenolic resin obtained in Synthesis Example 2.

[0032] Figure 3 This is the GPC chart of the phenolic varnish-type phenolic resin obtained in Synthesis Example 3.

[0033] Figure 4 This is the GPC chart of the phenolic varnish-type phenolic resin obtained in Synthesis Example 4.

[0034] Figure 5 This is the GPC chart of the phenolic varnish-type phenolic resin obtained in Synthesis Example 5.

[0035] Figure 6 This is the GPC chart of the phenolic varnish-type phenolic resin obtained in Synthesis Example 6.

[0036] Figure 7 This is the GPC chart of the phenolic varnish-type phenolic resin obtained in Synthesis Example 7. Detailed Implementation

[0037] The following describes the form used to implement the invention.

[0038] Furthermore, in this specification, "x~y" is defined as a numerical range representing "above x and below y". The upper and lower limits of the numerical range can be combined arbitrarily.

[0039] Furthermore, combining two or more of the various forms of the present invention described below also constitutes a form of the present invention.

[0040] An embodiment of the negative photosensitive resin composition of the present invention contains the following components (A) to (F).

[0041] (A) A phenolic varnish-type phenolic resin with a molar ratio of (a1):(a2):(a3) of cresol-derived structural unit (a1):(a2):(a3) of 1.0:0.3–0.8:0.3–0.8.

[0042] (B) At least one alkali-soluble resin selected from alkali-soluble resins containing polymerizable unsaturated groups and (meth)acrylic acid-based alkali-soluble resins.

[0043] (C) Polymer compounds

[0044] (D) Polymerization initiator

[0045] (E) Coloring components

[0046] (F) Organic solvents

[0047] In this embodiment, by using the phenolic varnish-type phenolic resin described in (A), the occurrence of film-forming defects can be suppressed. Furthermore, a resist film with high alkali solubility in the unexposed areas can be obtained. Additionally, the chemical resistance of the hardened resist is improved.

[0048] The following describes the composition of the negative photosensitive resin composition.

[0049] ·Ingredients (A)

[0050] In the phenolic resin of the varnish type used as component (A), the molar ratio of structural units (a1) derived from cresol, structural units (a2) derived from benzaldehyde, and structural units (a3) ​​derived from hydroxybenzaldehyde [(a1):(a2):(a3)] is 1.0:0.3~0.8:0.3~0.8.

[0051] From the viewpoint of obtaining a chemically resistant hardened film that not only has high sensitivity but also hardens at low temperatures, the molar ratio of the structural units (a1) derived from cresol, (a2) derived from benzaldehyde, and (a3) ​​derived from hydroxybenzaldehyde in component (A) [(a1):(a2):(a3)] is preferably 1.0:0.5 to 0.7:0.3 to 0.5, more preferably 1.0:0.55 to 0.65:0.35 to 0.45.

[0052] Component (A) may also contain structural units other than those derived from cresol (a1), benzaldehyde (a2), and hydroxybenzaldehyde (a3). Structural units other than (a1) to (a3) ​​may be derived from phenols or aldehydes other than cresol, benzaldehyde, and hydroxybenzaldehyde.

[0053] Examples of phenols include: phenol, 2,3-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, etc.

[0054] Examples of 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.

[0055] From the viewpoint of obtaining a hardened film with high sensitivity, low temperature curing, and chemical resistance, the total content of the structural unit (a1), structural unit (a2), and structural unit (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.

[0056] The total content of the structural unit (a1), structural unit (a2), and structural unit (a3) ​​can also be substantially 100% by mass. Furthermore, "substantially 100% by mass" means that it inevitably includes structural units other than the structural unit (a1), structural unit (a2), and structural unit (a3).

[0057] The weight-average molecular weight of the phenolic varnish-type phenolic resin used as component (A) is preferably 1,000 or more, more preferably 1,500 or more. Furthermore, it is 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 provides high heat resistance, and is therefore preferred. Conversely, a weight-average molecular weight of 15,000 or less provides high sensitivity, and is therefore preferred. In this specification, the weight-average molecular weight is measured under the conditions described in the examples.

[0058] Component (A) is obtained by polycondensation of cresol, benzaldehyde and hydroxybenzaldehyde in an organic solvent using an acid catalyst in a molar ratio (cresol:benzaldehyde:hydroxybenzaldehyde) of 1.0:0.3 to 0.8:0.3 to 0.8.

[0059] Cresol is preferably m-cresol. Additionally, hydroxybenzaldehyde is preferably salicylaldehyde.

[0060] From the viewpoint of obtaining a hardened film with chemical resistance through low-temperature curing and high sensitivity, the molar ratio of cresol, benzaldehyde and hydroxybenzaldehyde in the reaction solvent (cresol:benzaldehyde:hydroxybenzaldehyde) is preferably 1.0:0.5 to 0.7:0.3 to 0.5, more preferably in the range of 1.0:0.55 to 0.65:0.35 to 0.45.

[0061] The molar ratio of benzaldehyde is preferably less than that of hydroxybenzaldehyde. That is, it is preferable that the molar ratio of benzaldehyde < that of hydroxybenzaldehyde.

[0062] When cresol, benzaldehyde and hydroxybenzaldehyde are condensed in an organic solvent to obtain a phenolic varnish-type phenolic resin as component (A), as described above, phenols and aldehydes other than cresol, benzaldehyde and hydroxybenzaldehyde may also be included in the organic solvent.

[0063] From the viewpoint of obtaining a hardened film with chemical resistance through not only high sensitivity but also low-temperature curing, the ratio of the total mass of cresol, benzaldehyde, and hydroxybenzaldehyde in the reaction solvent to the total mass of all starting materials that can be structural units of component (A) is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably substantially 100% by mass.

[0064] Examples of reaction solvents used in the manufacture 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, etc. Preferably, these are selected from one or more of ethanol, 1-propanol, and 2-propanol, and more preferably ethanol.

[0065] 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, relative to 100 parts by mass of the raw material used to derive the structural unit of constituent (A). Furthermore, it is preferably 500 parts by mass or less, more preferably 300 parts by mass or less.

[0066] Examples of acid catalysts used in manufacturing 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 these, inorganic acids and p-toluenesulfonic acid are preferred, and p-toluenesulfonic acid is more preferred, in order to further promote the reaction.

[0067] There is no particular limitation on the amount of acid catalyst added, but it is preferably 5 parts by mass or more, more preferably 20 parts by mass or more, relative to 100 parts by mass of the raw material used to derive the structural unit of component (A). Furthermore, it is preferably 150 parts by mass or less, more preferably 100 parts by mass or less.

[0068] In order to efficiently increase the molecular weight while promoting the reaction, the reaction temperature for polycondensing the raw material of component (A) is preferably 30°C or higher, more preferably 40°C or higher. Furthermore, it is preferably 100°C or lower, more preferably 80°C or lower.

[0069] The reaction time is preferably 4 hours or more, more preferably 12 hours or more. Furthermore, it is preferably 32 hours or less, more preferably 24 hours or less.

[0070] Component (A) is preferably formulated at 1.0% to 40% by mass, more preferably 5% to 40% by mass, in the solid components of the negative photosensitive resin composition.

[0071] • Ingredient (B)

[0072] The alkali-soluble resin (B-1) containing polymerizable unsaturated groups and the (meth)acrylic alkali-soluble resin (B-2) as component (B) can improve the alkali solubility of the unexposed part.

[0073] As a base-soluble resin containing polymerizable unsaturated groups (B-1), resins having both polymerizable unsaturated groups and acidic groups within the molecule can be used. For example, an epoxy (meth)acrylate acid adduct is preferred, which is obtained by reacting a compound having two or more epoxy groups with (meth)acrylate ("(meth)acrylate" refers to acrylic acid and / or methacrylic acid) to obtain an epoxy (meth)acrylate compound with hydroxyl groups, and one or more carboxylic acid compounds selected from dicarboxylic acids, tricarboxylic acids, monoanhydrides of tricarboxylic acids, tetracarboxylic acids, and dianhydrides of tetracarboxylic acids.

[0074] Examples of compounds having two or more epoxy groups that have been derived into epoxy (meth)acrylate acid adducts include bisphenol type epoxy compounds and phenolic varnish type epoxy compounds. Specifically, bisphenol type epoxy compounds represented by the following general formula (I) are preferred.

[0075] [Chemistry 1]

[0076]

[0077] In the formula, R1, R2, R3, and R4 independently represent a hydrogen atom, an alkyl group with 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-, fluorene-9,9-diyl, or a straight bond. l is an integer from 0 to 10.

[0078] R1 to R4 are preferably hydrogen atoms. Additionally, A is preferably fluorene-9,9-diaryl. Furthermore, since l typically exists in multiple values, the average value is 0 to 10 (not limited to integers), but the preferred average value of l is 0 to 3. The following explanation will use the case where l = 0 as an example.

[0079] Bisphenolic epoxy compounds are epoxy compounds with two glycidyl ether groups obtained by reacting bisphenols with epichlorohydrin. During the reaction, oligomerization of diglycidyl ether compounds usually occurs, thus containing epoxy compounds with more than two bisphenol skeletons.

[0080] Examples of bisphenols used in the aforementioned reaction include: bis(4-hydroxyphenyl)one, bis(4-hydroxy-3,5-dimethylphenyl)one, bis(4-hydroxy-3,5-dichlorophenyl)one, 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)sulfone, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dichloro ... 2,2-bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxyphenyl)dimethylsilane, bis(4-hydroxy-3,5-dimethylphenyl)dimethylsilane, bis(4-hydroxy-3,5-dichlorophenyl)dimethylsilane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxyphenyl)propane, (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 Fiberyl 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'-biphenyl, 3,3'-biphenyl, etc. Among these, bisphenols containing fluorene-9,9-diyl groups are preferred.

[0081] Examples of monoanhydrides of dicarboxylic or tricarboxylic acids that react with epoxy (meth)acrylates include: monoanhydrides of chain-type hydrocarbon dicarboxylic or tricarboxylic acids, alicyclic dicarboxylic or tricarboxylic acids, and aromatic dicarboxylic or tricarboxylic acids.

[0082] Examples of acid monoanhydrides that are chain-type dicarboxylic or tricarboxylic acids include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citric acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, octanoic acid, and diethylene glycol. They can also be acid monoanhydrides of dicarboxylic or tricarboxylic acids to which any substituent has been introduced.

[0083] In addition, acid monoanhydrides that are alicyclic dicarboxylic acids or tricarboxylic acids include, for example, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylmethylenetetrahydrophthalic acid, chloramphenic acid, hexahydrotriphenylamine, norbornanedicarboxylic acid, etc. They can also be acid monoanhydrides to which dicarboxylic acids or tricarboxylic acids with any substituents have been introduced.

[0084] Furthermore, the acid monohydric anhydrides that are aromatic dicarboxylic acids or tricarboxylic acids include, for example, phthalic acid, isophthalic acid, trimellitic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, etc. They can also be acid monohydric anhydrides to which dicarboxylic acids or tricarboxylic acids with any substituents have been introduced.

[0085] In addition, examples of dianhydrides of tetracarboxylic acids that react with epoxy (meth)acrylates include: dianhydrides of chain-type tetracarboxylic acids, alicyclic tetracarboxylic acids, or aromatic tetracarboxylic acids.

[0086] Examples of acid dianhydrides that are chain-type tetracarboxylic acids include butanetetracarboxylic acid, pentanetetracarboxylic acid, and hexanetetracarboxylic acid. They can also be acid dianhydrides of tetracarboxylic acids to which any substituent has been introduced.

[0087] In addition, dianhydrides that are alicyclic tetracarboxylic acids include, for example, dianhydrides of cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid, etc. They can also be dianhydrides of tetracarboxylic acids to which any substituent has been introduced.

[0088] Furthermore, examples of dianhydrides that are aromatic tetracarboxylic acids include 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. Dianhydrides of tetracarboxylic acids with any substituents may also be used.

[0089] As one embodiment, the carboxylic acid compound reacting with the epoxy (meth)acrylate is preferably an anhydride of (a) a dicarboxylic acid or a tricarboxylic acid and an anhydride of (b) a tetracarboxylic acid.

[0090] The molar ratio (a) / (b) of the anhydride of (a) dicarboxylic acid or tricarboxylic acid and the dianhydride of (b) tetracarboxylic acid that react with epoxy (meth)acrylate is preferably 0.01 to 10.0, more preferably 0.02 or more but less than 3.0. If the molar ratio (a) / (b) is within the range described above, it is easy to obtain the optimal molecular weight for preparing a photosensitive resin composition with good photopatterning properties, and in addition, it has high alkali solubility.

[0091] Epoxy (meth)acrylate acid adducts can be manufactured, for example, using the methods described in Japanese Patent Application Publication No. 8-278629 and Japanese Patent Application Publication No. 2008-9401. First, as a method for reacting (meth)acrylate with an epoxy compound, one method is as follows: equimolar amounts of (meth)acrylate, as well as the epoxy groups of the epoxy compound, are added to a solvent, and the reaction is carried out under heating and stirring at 90°C to 120°C while air is blown in the presence of a catalyst (triethylbenzylammonium chloride, 2,6-diisobutylphenol, etc.). Second, as a method for reacting an anhydride with the hydroxyl groups of the epoxy acrylate compound as a reaction product, one method is as follows: A predetermined amount of the epoxy acrylate compound, a dianhydride, and a monohydric anhydride are added to a solvent, and the reaction is carried out under heating and stirring at 90°C to 130°C in the presence of a catalyst (tetraethylammonium bromide, triphenylphosphine, etc.). The epoxy acrylate acid adducts obtained using these methods have a skeleton of general formula (II).

[0092] [Chemistry 2]

[0093]

[0094] In formula (II), R1, R2, R3, and R4 independently represent a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, a halogen atom, or a phenyl group, respectively; A represents -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, fluorene-9,9-diyl, or a straight bond; X represents a tetravalent carboxylic acid residue; Y1 and Y2 independently represent a hydrogen atom or -OC-Z-(COOH), respectively. k (Where Z represents a divalent or trivalent carboxylic acid residue, k represents a number from 1 to 2); j represents an integer from 1 to 20; R5 represents a hydrogen atom or a methyl group.)

[0095] Other examples of component (B-1) include resins containing both (meth)acrylic acid groups and carboxyl groups in copolymers such as (meth)acrylic acid and (meth)acrylates. For example, an alkali-soluble resin containing polymerizable unsaturated groups is obtained by: as a first step, copolymerizing (meth)acrylates containing glycidyl (meth)acrylic acid in a solvent to obtain a copolymer; as a second step, reacting (meth)acrylic acid with the obtained copolymer; and in a third step, reacting an anhydride of a dicarboxylic acid or tricarboxylic acid.

[0096] Another example of component (B-1) is a carbamate compound obtained by reacting a polyol compound having an ethylene unsaturated bond in its molecule as the first component, a diol compound having a carboxyl group in its molecule as the second component, and a diisocyanate compound as the third component. As a resin for the system, reference can be made to the resin shown in Japanese Patent Application Publication No. 2017-76071.

[0097] The weight-average molecular weight (Mw) of component (B-1) is preferably between 2,000 and 10,000, more preferably between 3,000 and 7,000. If the Mw is less than 2,000, the adhesion of the pattern during development cannot be maintained, and pattern peeling is likely to occur. In addition, if the Mw exceeds 10,000, development residue or residual film in unexposed areas is likely to remain. Furthermore, component (B-1) is preferably in the range of 30 mg KOH / g to 200 mg KOH / g. The reason is that if the value is less than 30 mg KOH / g, there may be situations where alkaline development cannot be performed smoothly or special development conditions such as strong alkali are required. In addition, if it exceeds 200 mg KOH / g, the penetration of the alkaline developer becomes too fast, which can easily cause peeling development.

[0098] Component (B-1) may be used alone or as a mixture of two or more.

[0099] As an alkali-soluble resin (B-2) based on (meth)acrylic acid, examples include alkali-soluble resins containing repeating units represented by at least one of general formulas (III) and (IV) below, and repeating units represented by at least one of general formulas (V) and (VI) below.

[0100] [Chemistry 3]

[0101]

[0102] In equation (III), R 1 R represents a hydrogen atom or a methyl group. 2 R represents a single bond or an alkylene group having 1 to 5 carbon atoms, or an alkylene ether group having 1 to 5 carbon atoms and 1 oxygen atom. 3 This indicates an alkyl, alkoxy, or acyl group having 1 to 5 carbon atoms. l represents an integer from 0 to 4, and m represents an integer from 1 to 4. When two or more R groups are present... 3 In this case, these R 3 They can be different from each other, or they can be the same.

[0103] In equation (IV), R 4 R represents a hydrogen atom or a methyl group. 5 This indicates an alkyl, alkoxy, or acyl group having 1 to 5 carbon atoms. n represents an integer from 0 to 4, and o represents an integer from 1 to 4. When there are two or more R groups...5 In this case, these R 5 They can be different from each other, or they can be the same.

[0104] [Chemistry 4]

[0105]

[0106] In equation (V), R 6 R represents a hydrogen atom or a methyl group. 7 Represents a single bond or an alkylene group having 1 to 5 carbon atoms, or an alkylene ether group having 1 to 5 carbon atoms and 1 oxygen atom. R 8 This indicates an alkyl group with 1 to 5 carbon atoms. p represents an integer from 1 to 5, and q represents an integer from 0 to 5. When there are two or more R groups... 8 In this case, these R 8 They can be different from each other, or they can be the same.

[0107] In equation (VI), R 9 R represents a hydrogen atom or a methyl group. 10 It represents a single bond or an alkylene group having 1 to 5 carbon atoms, or an alkylene ether group having 1 to 5 carbon atoms and 1 oxygen atom.

[0108] (Meth)acrylic acid base-soluble resin (B-2) can be obtained by copolymerizing monomers constituting repeating units represented by general formula (III) and / or general formula (IV) with monomers constituting repeating units represented by general formula (V) and / or general formula (VI). As a method of copolymerization, the method described in Japanese Patent Application Publication No. 5-19467 can be cited as an example.

[0109] Monomers constituting the repeating unit represented by general formula (III) include, specifically: 4-hydroxyphenyl methacrylate (hereinafter PQMA), methyl methacrylate (4-hydroxyphenyl), ethyl methacrylate ((4-hydroxyphenyl)ethyl methacrylate) (hereinafter PEMA), propyl methacrylate (4-hydroxyphenyl), etc.

[0110] Specifically, 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)propene, 1-(3-hydroxyphenyl)propene, 1-(4-hydroxyphenyl)propene, etc.

[0111] By using (meth)acrylic base-soluble resin (B-2) containing repeating units represented by general formula (III) and / or general formula (IV), it exhibits the effect of inhibiting free radical chain reactions, reducing the mask bias of the negative photosensitive resin composition, and enabling the formation of patterns as designed.

[0112] (Meth)acrylic acid-based alkali-soluble resin (B-2) preferably has a repeating unit represented by general formula (III). Furthermore, R in general formula (III) is more preferably preferred. 2 It is a single key.

[0113] Examples of monomers constituting the repeating unit represented by general formula (V) include: glycidyl acrylate, glycidyl methacrylate (GMA), 4-hydroxybutyl acrylate glycidyl ether (4HBAGE), methyl acrylate (3-ethyloxetane-3-yl), methyl acrylate (3-methyloxetane-3-yl), methyl methacrylate (3-ethyloxetane-3-yl), methyl methacrylate (3-methyloxetane-3-yl), tetrahydrofurfuryl acrylate, tetrahydro-2H-pyran-2-yl acrylate, etc. Glycidyl methacrylate is preferred.

[0114] Examples of monomers constituting the repeating unit represented by general formula (VI) include: methyl 3,4-epoxycyclohexyl methacrylate, methyl 3,4-epoxycyclohexyl acrylate, ethyl 3,4-epoxycyclohexyl methacrylate, and ethyl 3,4-epoxycyclohexyl acrylate. Among these, methyl 3,4-epoxycyclohexyl methacrylate is preferred.

[0115] By using a (meth)acrylic base-soluble resin (B-2) containing repeating units represented by general formula (V) and / or general formula (VI), and increasing the crosslinking density during the process of heat curing the negative photosensitive resin composition after patterning, an organic EL display device with excellent long-term reliability can be obtained.

[0116] When the sum of the molar ratios of repeating units represented by general formula (III) and general formula (IV) relative to 100 mol% of the total repeating units of the (meth)acrylic base-soluble resin (B-2) is set as M1 and M2 respectively, M1 is preferably 30 mol% or more and less than 70 mol%. By setting M1 to the range described above, both mask deviation reduction and high sensitivity of the negative photosensitive resin composition can be achieved simultaneously.

[0117] Furthermore, from the viewpoint of ensuring the storage stability of the negative photosensitive resin composition and minimizing mask deviation, the M1 / M2 ratio is preferably 0.4 or higher, and more preferably 0.6 or higher. On the other hand, from the viewpoint of ensuring the long-term reliability of the organic EL display device, the M1 / M2 ratio is preferably 1.5 or lower.

[0118] (Meth)acrylic acid-based alkali-soluble resin (B-2) can be copolymerized with any (meth)acrylic acid monomer as a monomer as needed. Specifically, it may also include: acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, phthalic acid, phthalic anhydride, crotonic acid, 2-carboxyethyl acrylate oligomer, 2-carboxyethyl methacrylate oligomer, etc., monomers with carboxyl groups; methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, methacrylic acid Isobutyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, and other acrylates or methacrylates or their (fluoro)alkyl ester monoisomeric forms; 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, 9-vinylcarbazole, and other unsaturated monoisomeric forms with aromatic rings.

[0119] Component (B) is preferably (meth)acrylic acid-based alkali-soluble resin (B-2).

[0120] Component (B) is preferably formulated at 1.0% to 40% by mass, more preferably 5% to 40% by mass, in the solid components of the negative photosensitive resin composition.

[0121] When using an alkali-soluble resin (B-1) containing polymerizable unsaturated groups, it is preferable to further formulate a partially (meth)acrylated epoxy resin (B-1-1) in which a portion of the epoxy resin is (meth)acrylated.

[0122] Resin (B-1-1) is a partially (meth)acrylated epoxy resin obtained by reacting an epoxy resin (also called an epoxy compound; the same applies below) as a raw material with acrylic acid and / or methacrylic acid, thereby (meth)acrylating a portion of the epoxy groups of the raw material epoxy resin.

[0123] Thus, the resin (B-1-1) contains epoxy and (meth)acrylic acid groups in one molecule, thereby exhibiting both thermosetting and UV-curing properties. Therefore, during thermosetting, it can exist between components with vinyl unsaturated groups and light-blocking materials (coloring components) such as carbon black, which can be expected to suppress shrinkage during thermosetting. Consequently, suppression of contact between the light-blocking materials can be expected.

[0124] The relationship regarding the amount of (meth)acrylates can be determined based on the number (moles) of epoxy groups in the raw epoxy resin, and can be calculated according to its relationship with the number (moles) of (meth)acrylic acid groups after (meth)acrylation. More simply, it can be determined based on the input ratio of each raw material, based on the number (moles) of epoxy groups in the raw epoxy resin and the number (moles) of functional groups in the reacting (meth)acrylic acid. 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 (meth)acrylates in the raw epoxy groups can also be expressed as the modification rate [% (mol%)]. Regarding the modification rate of resin (B-1-1), it can be widely set without particular limitation according to its relationship with other components of the composition or its intended use. The preferred lower limit of the modification rate is 10%, a more preferred lower limit is 20%, a further preferred lower limit is 30%, a further more preferred lower limit is 40%, and the most preferred lower limit is 50%. On the other hand, the preferred upper limit for the modification rate is 90%, a more preferred upper limit is 80%, a further preferred upper limit is 70%, a further more preferred upper limit is 60%, and the most preferred upper limit is 50%. As the resin (B-1-1), multiple components with different modification rates can also be mixed and used. When multiple components with different modification rates are mixed and used, it is preferable that the modification rate range is satisfied as an average value.

[0125] In addition, the resin (B-1-1) can be synthesized according to known methods described in Japanese Patent Application Publication No. 2019-52273, etc.

[0126] Furthermore, substances with unmodified epoxy groups or substances with completely modified epoxy groups in the raw epoxy resin are not included in the definition of resin (B-1-1) as separate components, but these components may also be included in the negative photosensitive resin composition of this embodiment. As a mixture that also includes these components, a resin (B-1-1) having the aforementioned modification rate and other properties may also be specified.

[0127] As a resin (B-1-1), compounds represented by the following general formulas (1) to (5) can be listed.

[0128] [Chemistry 5]

[0129]

[0130] In formula (1), Cy is an aromatic hydrocarbon group with 6 to 12 carbon atoms or an alicyclic hydrocarbon group with 3 to 12 carbon atoms, Y is a divalent hydrocarbon group with 1 to 20 carbon atoms, and R 11 R is an independent hydrocarbon group having 1 to 10 carbon atoms. 12 Independently represent the bases represented by the following formulas (*) and / or (**), including at least one of each formula (*) and (**). R 17 It can be a hydrogen atom or a methyl group.

[0131] a, m, and n represent the number of repetitions independently, where a is 1 or more, m is 1 or 2, and n is 0 to 7.

[0132] [Chemistry 6]

[0133]

[0134] 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 in which a portion thereof is substituted by an alkyl or halogen atom having 1 to 6 carbon atoms, and more preferably a benzene ring, a naphthalene ring, or a biphenyl ring.

[0135] Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably -R. 18 - represents the basis, φ-R 18 -Cy2-R 18 -φ (φ represents the bond). R 18 Preferably, the group is selected from methylene, ethylene, and propylene. Cy2 is preferably selected from phenylene, naphthyl, biphenyl dimethyl, dicyclopentanediyl, dicyclopentenyl, and dicyclopentenyl, as well as groups formed by combinations thereof.

[0136] R 11 The substituents of Cy are independently hydrocarbon groups having 1 to 10 carbon atoms, preferably R. 11 It is a methyl group.

[0137] R 12Independently representing the epoxy group represented by formula (*) and / or the group formed by (meth)acrylating an epoxy group as represented by formula (**). As described above, the partially (meth)acrylated epoxy resin (B-1-1) is a substance obtained by (meth)acrylating a portion of a raw epoxy resin, and therefore contains at least one of each of these groups of formula (*) and formula (**) in one molecule.

[0138] a, m, and n each independently represent the number of repetitions. 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.

[0139] As specific examples of compounds represented by general formula (1), compounds represented by general formulas (1-1) to (1-3) can be listed below.

[0140] [Chemistry 7]

[0141]

[0142] In general formulas (1-1) and (1-2), a1 and b independently represent the number of repetitions. a is usually 0 to 45, but preferably 1 to 40. b is usually 0 to 45, but preferably 1 to 40. a1+b is 1 or more, and the bond order of a1 and b can be random.

[0143] In addition, q in general formula (1-3) is also a repetition number, and q is usually 1 or more.

[0144] [Chemistry 8]

[0145]

[0146] In equation (2), R 14 This represents the residues of an organic compound having d active hydrogen groups. Similar to formula (1), R 12 Each expression (*) and / or expression (**) is represented independently, and each expression (*) and expression (**) is contained at least once within a molecule. d is an integer from 1 to 100. c are each an independent integer from 0 to 100, and the sum of the cs is 2 to 100.

[0147] In general formula (2), R 14 R represents the residues of an organic compound having d active hydrogen groups. 12Similar to the above, this refers to the epoxy group represented by formula (*) and / or the epoxy group represented by formula (**) after being (meth)acrylated. As with general formula (1), a portion of the epoxy groups in the raw epoxy resin of general formula (2), i.e., formula (*), are (meth)acrylated, thereby obtaining a resin associated with general formula (2). Therefore, in general formula (2), at least one of each of the groups of formula (*) and formula (**) is also included in a molecule.

[0148] c and d represent the number of repetitions independently. d is an integer from 1 to 100, preferably an integer from 2 to 10, and more preferably an integer from 3 to 6.

[0149] Furthermore, each of the values ​​of c is an integer from 0 to 100. It is preferable to be an integer from 2 to 10, and more preferably an integer from 3 to 6. In addition, from the viewpoint of the degree of crosslinking or solubility after hardening, the sum of each of c is 2 to 100, preferably 3 to 30, and more preferably 4 to 20.

[0150] Furthermore, regarding the R mentioned above 14 The residues of [specific compound name], as precursors of which are organic compounds having active hydrogen groups, can be listed as: alcohols, phenols, carboxylic acids, amines, thiols, and other known compounds described in Japanese Patent No. 5744528. As for compounds having the aforementioned R [specific compound name] residues, examples include: alcohols, phenols, carboxylic acids, amines, thiols, etc. 14 Commercially available raw material epoxy compounds, such as Daicel Inc.’s EHPE3150 [a 1,2-epoxy-4-(2-epoxyethylene)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol], are examples, but are not limited to these.

[0151] [Chemistry 9]

[0152]

[0153] In equation (3), f, g, h, and i are each independently 0 or 1, and f + g + h + i = 1 to 3. 13 Independently represent the following formulas (***) and / or (****), including at least one of each: formula (***) and formula (****). R 17 It can be a hydrogen atom or a methyl group.

[0154] [Chemistry 10]

[0155]

[0156] Regarding the compounds represented by general formula (3), since R is a separate independent R 13The group, having a 3,4-epoxycyclohexyl group as represented by the following formula (***), and having a portion of it having an epoxycyclohexyl group as represented by formula (****) after being (meth)acrylated, thus comprising at least one of these groups of formula (***) and formula (****).

[0157] Commercially available epoxy compounds that serve as raw materials for compounds of general formula (3) include, for example, Daicel Inc.’s EPOLEAD GT401 [butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone], but are not limited to these.

[0158] R 13 -WR 13 (4)

[0159] In formula (4), W represents a single bond or a divalent organic group with 1 to 20 carbon atoms that may contain heteroelements. Similar to the general formula (3), R... 13 Independently represent formula (***) and / or formula (****), including at least one of each of formula (***) and formula (****).

[0160] As a specific W, it may also include a divalent hydrocarbon group, a divalent group having a carboxyl group at one or both ends of the hydrocarbon group, and may also have an ether bond or an ester bond internally. More specifically, the substances represented by formulas (14) to (20) described in Japanese Patent Application Publication No. 2020-166254 can be used as raw materials. Regarding the compound represented by general formula (4), it is also because R is 13 The group, having a 3,4-epoxycyclohexyl group represented by formula (***), also has a portion having an epoxycyclohexyl group (meth)acrylated as represented by formula (****), thus comprising at least one of each of these groups of formula (***) and formula (****). That is, in general formula (4), each of the groups of formula (***) and formula (****) is included. Commercially available epoxy compounds that are raw materials for compounds of general formula (4) include, for example, Celloxide 2021P [3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate] from Daicel Inc., but are not limited thereto.

[0161] [Chemistry 11]

[0162]

[0163] In equation (5), Z represents -CO-, -SO2-, -C(CF3)2-, -Si(CF3)2-, -CH2-, -C(CF3)2-, -O-, 9,9-fluorene group, or is absent. R12 Independently represent the following formulas (*) and / or (**), including at least one of each. R 17 It can be a hydrogen atom or a methyl group. R 15 and R 16 Each can be independently represented by a hydrogen atom or an alkyl or halogen atom having 1 to 5 carbon atoms.

[0164] p represents the number of repetitions, which is an integer from 0 to 10.

[0165] [Chemistry 12]

[0166]

[0167] In general formula (5), Z represents -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CF3)2-, -O-, 9,9-fluorenyl or not present, preferably -CH2-, 9,9-fluorenyl.

[0168] R 12 This refers to the epoxy group represented by formula (*) and / or the group formed by (meth)acrylating an epoxy group as represented by formula (**). Therefore, with respect to general formula (5), it also includes one of each of these groups of formula (*) and formula (**).

[0169] R 15 and R 16 Each of the following can be independently represented: a hydrogen atom or an alkyl or halogen atom having 1 to 5 carbon atoms, preferably a hydrogen atom or a methyl atom.

[0170] p represents the repetition number, which is an integer from 0 to 10, preferably from 0 to 8.

[0171] The synthesis endpoint of partially (meth)acrylated epoxy resin (B-1-1) can be confirmed by measuring acid value, etc.

[0172] Regarding the partially (meth)acrylated epoxy resin (B-1-1), it is preferable to use an epoxy resin with a weight average molecular weight of 200 to 20,000, more preferably 250 to 15,000.

[0173] Regarding the amount of partially (meth)acrylated epoxy resin (B-1-1), it is preferred to contain 0.2% to 60% by mass in the solid components of the negative photosensitive resin composition, more preferably 0.2% to 55% by mass, and even more preferably 0.3% to 50% by mass.

[0174] Furthermore, regarding the amount of partially (meth)acrylated epoxy resin (B-1-1), it is preferably 0.8 to 1000 parts by mass relative to 100 parts by mass of the alkali-soluble resin (B-1) containing polymerizable unsaturated groups, or to 100 parts by mass of the total of (B-1) and component (C) (polymeric compound) described later; more preferably, it is 0.9 to 900 parts by mass; and even more preferably, it is 1.5 to 800 parts by mass. By setting the amount by mass relative to component (B-1) or the total of component (B-1) and component (C), sufficient photocurability can be obtained, and good patterning characteristics can be acquired, which is therefore preferred.

[0175] Furthermore, the partially (meth)acrylated epoxy resin (B-1-1) is preferably formulated in an amount of 0.5 to 180 parts by weight relative to 100 parts by weight of the coloring component (E) described later, more preferably 1.0 to 160 parts by weight, and even more preferably 1.0 to 140 parts by weight. By appropriately adjusting the amount relative to component (E) in this way, good affinity with component (E) can be maintained while achieving a balance between sufficient light-blocking properties and electrical resistance.

[0176] Resin (B-1-1) can be used alone, or a mixture of two or more can be used.

[0177] For information on alkali-soluble resins (B-1) containing polymerizable unsaturated groups and partially (meth)acrylic epoxy resins (B-1-1), please refer to Japanese Patent Application Publication No. 2023-97382.

[0178] • Ingredient (C)

[0179] The polymeric compound as component (C) can crosslink the molecules of component (B) with each other. Examples of component (C) include: 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyhexyl methacrylate, and other methacrylates containing hydroxyl groups; or ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri ... 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, or dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, phosphazene epoxy-modified hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, etc. (meth)acrylates, dendritic polymers having (meth)acryloyl groups, etc. One polymerizable compound may be used; additionally, two or more may be used in combination. Examples of dendritic polymers having (meth)acryloyl groups include known dendritic polymers obtained by adding a thiol group from a polyhydric mercapto compound to a portion of the carbon-carbon double bond in the (meth)acryloyl group of a polyfunctional (meth)acrylate compound.

[0180] Polymerizable compounds are more preferably composed of components having two or more vinyl unsaturated bonds. Furthermore, the acrylic equivalent obtained by dividing the molecular weight of the monomer by the number of (meth)acryloyl groups in one molecule is 50 to 300.

[0181] Component (C) is preferably formulated into the solid components of the negative photosensitive resin composition at 1.0% to 40% by mass, more preferably 5% to 40% by mass.

[0182] • Ingredient (D)

[0183] The polymerization initiator, as component (D), refers to a compound that generates free radicals through bond breaking and / or reaction caused by exposure. By containing a polymerization initiator, the exposed portion of the film in the negative photosensitive resin composition becomes insoluble relative to the alkaline developer, thereby forming a negative pattern. Furthermore, it promotes the curing of the exposed portion, thus increasing sensitivity.

[0184] There are no particular limitations on the polymerization initiator; known photopolymerization initiators can be used. Examples include: acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminoacetophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, benzyl dimethyl ketal, and other acetophenone derivatives; benzophenone, 2-chlorobenzophenone, p,p'-bis(dimethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone (Mischel ketone), 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4,4'-diethylaminobenzophenone, and other benzophenone derivatives; benzoin, benzoyl, benzoyl benzoate, etc. Benzyl ethers, such as benzoin isopropyl ether and benzoin isobutyl ether; biimidazole compounds such as 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, 2,4,5-triarylbiimidazole, and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2-biimidazole; 2-trichloromethyl-5-styryl-1,3- 4-Oxadiazole, 2-trichloromethyl-5-(p-cyanostylenyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-methoxystylenyl)-1,3,4-oxadiazole and other halomethyldiazole compounds; 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 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-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-1 ... Halomethyl-triazine compounds include (-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)-1,3,5-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-benzoyl oxime), 1-(4-phenylthiophenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylthiophenyl)butane-1,2-dione-2-oxime-O-acetate, 1-(4-methylthiophenyl)butane-1-ketooxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-dicycloheptyl-1-ketooxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-adamantylmethane-1-ketooxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-adamantylmethane-1-ketooxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-adamantylmethane-1-ketooxime-O-benzoate, [9-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-adamantylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-tetrahydrofuranylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-tetrahydrofuranylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-thiophenylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-thiophenylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6- (2-Methylbenzoyl)-9H-carbazole-3-yl]-morpholinylmethane-1-ketooxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-morpholinylmethane-1-ketooxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethane-1-ketooxime-O-dicycloheptane carboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethane-1-ketooxime-O-tricyclodecane carboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethane-1-ketooxime-O-tricyclodecane carboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethane-1-ketooxime-O-adamantane carboxylate, 1-[4-(benzene) [7-(2-methylbenzoyl)-1,2-dione]octane-1,2-dione = 2-O-benzoyl oxime, 1-[9-ethyl-6-(2-methylbenzoyl)carbazole-3-yl]acetone-O-acetyl oxime, (2-methylphenyl)(7-nitro-9,9-dipropyl-9H-fluoren-2-yl)-acetyl oxime, acetone, 1-[7-(2-methylbenzoyl)-9, [9-Dipropyl-9H-fluoren-2-yl]-1-(O-acetyl oxime), acetone, 1-(9,9-dibutyl-7-nitro-9H-fluoren-2-yl)-1-O-acetyl oxime, acetone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime), and other O-acyl oxime compounds;Sulfur compounds such as thioxanthones, 2-chlorothioxanthones, 2,4-dimethylthioxanthones, 2,4-diethylthioxanthones, 2-methylthioxanthones, 2-isopropylthioxanthones, 4-isopropylthioxanthones, 2,4-dichlorothioxanthones, and 1-chloro-4-propoxythioxanthones; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone; organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, and cumene peroxide; and compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole. Thiol compounds such as β-mercaptoesters, 2-ethylhexyl-3-mercaptoester propionate, n-octyl-3-mercaptoester propionate, methoxybutyl-3-mercaptoester propionate, stearyl-3-mercaptoester propionate, trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetra(3-mercaptobutyrate), pentaerythritol tetra(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), 3,3'-thiodipropionic acid, dithiodipropionic acid, and lauryl thiopropionic acid are used. Among these, O-acyl oxime compounds are preferred for easily obtaining highly sensitive photosensitive resin compositions. Additionally, two or more polymerization initiators may be used. Furthermore, in this application, the term "polymerization initiator" may include the meaning of a sensitizer.

[0185] Furthermore, it does not function as a polymerization initiator or sensitizer on its own, but by combining it with the aforementioned compounds, compounds that can enhance the ability of polymerization initiators or sensitizers can be added. Examples of such compounds include amine compounds that are effective when used in combination with benzophenone. Examples of such 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, 4,4'-bis(ethylmethylamino)benzophenone, etc.

[0186] The amount of component (D) is preferably 2 to 40 parts by mass relative to the total of 100 parts by mass of components (A), (B) and (C) as resin components, and more preferably 3 to 30 parts by mass.

[0187] • Ingredient (E)

[0188] As component (E), i.e., coloring component, known coloring components may be used without limitation. Component (E) is preferably an organic pigment or an inorganic pigment, more preferably a light-shielding material containing an organic black pigment, a mixed organic pigment, or an inorganic black pigment.

[0189] Examples of black organic pigments include perylene black, aniline black, cyanine black, and lactam black. Examples of mixed organic pigments include pigments that are pseudo-blackened by mixing two or more pigments selected from red, blue, green, purple, yellow, cyanine, and magenta. Examples of inorganic black pigments include carbon black, chromium oxide, iron oxide, and titanium black. These coloring components can be used individually or in combination of two or more. The appropriate component can be selected based on the intended use of the photosensitive resin composition. Among these coloring components, carbon black is more preferred from the viewpoints of opacity, surface smoothness, dispersion stability, and affinity with the resin. On the other hand, titanium black is suitable for applications where resistivity and opacity are important, and lactam black is suitable for applications where infrared transmittance and low dielectric properties are important.

[0190] As carbon black, untreated or oxidized carbon black is preferred. Here, "untreated" means that no special surface treatment such as oxidation or resin coating has been performed. "Oxidation" refers to treating the surface of the carbon black with an oxidizing agent before the dispersion process. Because this untreated or oxidized carbon black has a large number of acidic functional groups on its surface, it reacts with the epoxy groups of the partially (meth)acrylic epoxy resin (B-1-1) during thermosetting to obtain the hardened film, thereby allowing a large amount of resin (B-1-1) to be present near the carbon black, which is therefore preferred. Furthermore, if it is desired to use carbon black to further improve the resistivity of the hardened film, surface-coated carbon black that has been coated with dyes, pigments, resins, etc., can also be used.

[0191] The amount of component (E) can be arbitrarily determined, for example, in a way that achieves the desired opacity. For example, it is preferably 30% to 70% by mass, more preferably 40% to 60% by mass, relative to the solid content in the photosensitive resin composition.

[0192] Component (E) is preferably prepared by pre-dispersing it in a solvent with a dispersant to form a coloring dispersion, and then formulated into the photosensitive resin composition. Here, the dispersing solvent is part of the organic solvent described later in (F), and therefore any substance listed in component (F) can be used. For example, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, etc. are suitably used.

[0193] As the dispersant, various known dispersants, such as polymeric dispersants, can be used. Examples of dispersants include, without particular limitation, known compounds conventionally used for pigment dispersion (compounds commercially available under names such as dispersant, dispersing wetting agent, and dispersing accelerator), such as cationic polymeric dispersants, anionic polymeric dispersants, nonionic polymeric dispersants, and pigment derivative-type dispersants (dispersing aids). Cationic polymeric dispersants are particularly suitable, having cationic functional groups such as imidazole, pyrrole, pyridinyl, primary amino, secondary amino, or tertiary amino groups as adsorption sites for pigments, and having an amine value of 1 mg KOH / g to 100 mg KOH / g and a number average molecular weight in the range of 1,000 to 100,000. Regarding the amount of the dispersant, it is preferably 1% to 30% by mass relative to the (E) coloring component.

[0194] ·Ingredients(F)

[0195] As a component (F), namely organic solvents, examples include: methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy-2-butanone, diacetone alcohol, and other alcohols; terpenes such as α-terpineol or β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, 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... Diol ethers such as monomethyl ether of alcohol, monoethyl ether of propylene glycol, monomethyl ether of dipropylene glycol, monoethyl ether of dipropylene glycol, monomethyl ether of triethylene glycol, and monoethyl ether of triethylene glycol; esters such as ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, 3-methoxy-3-methyl-1-butyl acetate, cellolytic acetate, ethyl cellolytic acetate, butyl cellolytic acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. By using these esters to dissolve, disperse, and mix components (A) to (E), a homogeneous solution composition can be prepared.

[0196] Regarding the amount of organic solvent in the negative photosensitive resin composition, for obtaining a uniform coating by a coating method such as spin coating, the concentration of the solid component in the composition is preferably 5% by mass or more. Furthermore, it is preferably 65% ​​by mass or less.

[0197] Other ingredients

[0198] In this embodiment of the negative photosensitive resin composition, additives such as epoxy resin (not the resin described in B-1-1)), thermal polymerization inhibitors, antioxidants, plasticizers, fillers, leveling agents, defoamers, coupling agents, surfactants, and viscosity modifiers may be formulated as needed. Known epoxy resins can be used as the epoxy resin. Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, and hindered phenolic compounds. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. Examples of fillers include glass fiber, silica, mica, and alumina. Examples of defoamers or leveling agents include silicone-based, fluorine-based, and acrylic-based compounds. In addition, examples of surfactants include: anionic surfactants such as ammonium lauryl sulfate and triethanolamine polyoxyethylene alkyl ether 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 with polydimethylsiloxane as the main skeleton; and fluorinated surfactants. Examples of coupling agents include: silane coupling agents such as 3-(glycidoxy)propyltrimethoxysilane, 3-isocyanopropyltriethoxysilane, and 3-ureopropyltriethoxysilane.

[0199] The negative photosensitive resin composition of this embodiment can be prepared by stirring and mixing the components (A) to (F) and various additives as needed using conventional methods to form a homogeneous liquid.

[0200] When preparing solid substances such as fillers and pigments into this composition, it is preferable to use a dispersing device such as a solvent, homogenizer, or three-roll mill for dispersion and mixing. Alternatively, to remove coarse particles or impurities, the composition can be filtered using a mesh filter, membrane filter, or similar device.

[0201] The negative photosensitive resin composition of this embodiment can be suitably used for applications such as resist films, resist underlayer films, and resist permanent films.

[0202] The negative photosensitive resin composition of the present invention can be formed into a resist film, a resist underlayer film, and a resist permanent film, etc. (hereinafter, the resist film, resist underlayer film, and resist permanent film are sometimes collectively referred to as resist film, etc.) by using the same method as conventional negative photosensitive resin compositions.

[0203] Specifically, by coating the negative photosensitive resin composition of the present invention onto the object to be photolithographically lithographically applied and pre-baking it, a film of the photosensitive resin composition with the solvent removed (photosensitive film) can be obtained.

[0204] Examples of coating methods include spin coating, roller coating, flow coating, dip coating, spray coating, and blade coating. Pre-baking, for example, only requires heating at a temperature of 60°C or higher and 150°C for 30 seconds to 600 seconds. Furthermore, the negative photosensitive resin composition of the present invention can be suitably applied to glass substrates, silicon substrates, aluminum substrates, silicon carbide substrates, silicon nitride substrates, gallium nitride substrates, transparent conductive films, copper substrates, copper-plated substrates, etc.

[0205] By exposing the photosensitive film, the solubility of the exposed portion relative to the 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 gamma rays (wavelength 436 nm) and i-rays (wavelength 365 nm) from a high-pressure mercury lamp are suitable. After exposure, a heat treatment at approximately 100°C to 150°C may also be performed.

[0206] The photosensitive film obtained from the negative photosensitive resin composition of the present invention can be patterned at high resolution due to the large difference in alkali solubility between the exposed and unexposed portions. Therefore, it can be suitably used in resist films and the like. Furthermore, in this application, resist films and the like include both photosensitive films before exposure and non-photosensitive films after exposure.

[0207] Alkaline developing solutions used in post-exposure development include: inorganic alkaline substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and 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; alkaline amines such as dimethylethanolamine and triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; and alkaline aqueous solutions of cyclic amines such as pyrrole and piperidine.

[0208] Alcohols, surfactants, etc., may be added to the alkaline developer as needed. The alkalinity 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 commonly used.

[0209] When the negative photosensitive resin composition of the present invention is used for the application of a photoresist underlayer film (bottom anti-reflection coating (BARC) film), the negative photosensitive resin composition of the present invention can be used directly as a photoresist underlayer film composition. In addition, other resin components, surfactants, dyes, fillers, crosslinking agents, solubilizers and other additives may be added as needed.

[0210] Other resin components include, for example, various phenolic varnish resins, addition polymers of alicyclic dienes such as dicyclopentadiene and phenolic compounds, modified phenolic varnish resins of compounds containing phenolic hydroxyl groups and aromatic compounds containing alkoxy groups, phenol aralkyl resins (Xylock resins), naphthol aralkyl resins, trimethylolmethane resins, tetrahydroxyphenylethane resins, biphenyl-modified phenolic resins, biphenyl-modified naphthol resins, aminotriazine-modified phenolic resins, and various vinyl polymers.

[0211] When using other resin components, the mixing ratio of the negative photosensitive resin composition of the present invention with other resins can be arbitrarily set according to the application. For example, the ratio of other resins to 0.5 to 100 parts by weight relative to 100 parts by weight of component (A) is preferred.

[0212] The composition for the photoresist underlayer film can be prepared by adjusting the components and mixing them using a mixer or the like. Furthermore, if the composition for the photoresist underlayer film contains fillers or pigments, it can be adjusted by dispersing or mixing using a dissolving apparatus such as a solvent, homogenizer, or three-roll mill.

[0213] To form a photoresist underlayer film from a photoresist underlayer film composition, one method is as follows: the photoresist underlayer film composition is coated onto an object to be photolithographically etched, such as a silicon substrate, dried at a temperature of 100°C to 200°C, and then hardened by heating at a temperature of 250°C to 400°C. Next, a photoresist pattern is formed on this underlayer film using conventional photolithography, and then dry etching is performed using a halogen-based plasma gas or the like, thereby forming a photoresist pattern using a multilayer photoresist method.

[0214] When using the negative photosensitive resin composition of the present invention for use as a permanent resist film, in addition to the components (A) to (F) of the present invention, other resins, surfactants, dyes, fillers, crosslinking agents, solubilizers, and other additives may be added as needed. Examples of other resins used herein include resins that are the same as those used in the composition for the lower layer of the resist film.

[0215] In photolithography methods using a resist permanent film composition, for example, other resin components and additive components are dissolved and dispersed in the negative photosensitive resin composition of the present invention, coated onto the object to be photolithographically applied, and pre-baked at a temperature of 60°C to 150°C. The coating method can be any of spin coating, roll coating, flow coating, dip coating, spray coating, or blade coating. Next, the target resist pattern is exposed through a predetermined mask, and the unexposed areas are dissolved using an alkaline developer, thereby forming the resist pattern.

[0216] For the photoresist permanent film of this embodiment, for example, for semiconductor devices, it is suitable for use as an encapsulation adhesive layer for solder resist, encapsulation material, underfill material, circuit element, etc., and as an adhesive layer for integrated circuit elements and circuit substrate. In addition, for thin-film displays represented by liquid crystal display (LCD) and organic light-emitting diode (OELD), it is suitable for use as a thin-film transistor protective film, liquid crystal color filter protective film, black matrix, spacer, etc.

[0217] [Example]

[0218] The present invention will be further illustrated in detail below with specific examples. Furthermore, the weight-average molecular weight (Mw) of the synthesized resin was determined under the conditions described below using gel permeation chromatography (GPC).

[0219] [GPC Measurement Conditions]

[0220] Measurement device: HLC-8220GPC manufactured by Tosoh Corporation.

[0221] Tube column: "Shodex KF802" manufactured by Showa Denko Co., Ltd.: 8.0mmφ×300mm

[0222] +Shodex KF802 manufactured by Showa Denko Co., Ltd.: 8.0mm φ × 300mm

[0223] +Shodex KF803 manufactured by Showa Denko Co., Ltd.: 8.0mm φ × 300mm

[0224] +Shodex KF804 manufactured by Showa Denko Co., Ltd.: 8.0mmφ×300mm

[0225] Column temperature: 40℃

[0226] Detector: Refractive Index (RI) (Differential refractometer)

[0227] Data processing: "GPC-8020 Model II Version 4.30" manufactured by Tosoh Corporation

[0228] Solvent: Tetrahydrofuran

[0229] Flow rate: 1.0 mL / min

[0230] Sample: Prepared by filtering a tetrahydrofuran solution, calculated as 0.5% by mass based on resin solids, using a microfilter.

[0231] Injection volume: 0.1 mL

[0232] Standard sample: the following monodisperse polystyrene

[0233] (Standard sample: monodisperse polystyrene)

[0234] The "A-500" manufactured by Tosoh Corporation

[0235] The "A-2500" manufactured by Tosoh Corporation

[0236] The "A-5000" manufactured by Tosoh Corporation

[0237] The F-1 fighter jet manufactured by Tosoh Corporation.

[0238] The F-2 manufactured by Tosoh Corporation

[0239] The F-4 manufactured by Tosoh Corporation

[0240] The F-10 manufactured by Tosoh Corporation

[0241] The F-20 manufactured by Tosoh Corporation

[0242] Synthesis Example 1 (Synthesis of Phenolic Resin (A-1) of Phenolic Varnish Type)

[0243] 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 p-toluenesulfonic acid were added to a 2000 mL four-necked flask equipped with a cooling tube and dissolved in 300 g of ethanol as the reaction solvent. The mixture was then heated to 80 °C using a covered 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 by separation. The solvent was removed from the residual resin solution by vacuum distillation, and the solution was then dried under vacuum to obtain 281 g of a light red phenolic varnish-type phenolic resin (A-1) powder.

[0244] The Mw of phenolic varnish-type phenolic resin (A-1) is 3,100. The GPC diagram of phenolic varnish-type phenolic resin (A-1) is shown below. Figure 1 .

[0245] Synthesis Example 2 (Synthesis of Phenolic Resin (A-2) of Phenolic Varnish Type)

[0246] The starting materials were set as follows: 164 g (1.52 mol) of m-cresol, 80 g (0.75 mol) of benzaldehyde, and 92 g (0.75 mol) of salicylaldehyde. Otherwise, 280 g of phenolic varnish-type phenolic resin powder (A-2) was obtained in the same manner as in Synthesis Example 1. The Mw of the phenolic varnish-type phenolic resin (A-2) was 2,370.

[0247] The GPC diagram of phenolic varnish-type phenolic resin (A-2) is shown in... Figure 2 .

[0248] Synthesis Example 3 (Synthesis of Phenolic Resin (A-3) of Phenolic Varnish Type)

[0249] The starting materials were set as follows: 164 g (1.52 mol) of m-cresol, 67 g (0.63 mol) of benzaldehyde, and 115 g (0.94 mol) of salicylaldehyde. Otherwise, 279 g of phenolic varnish-type phenolic resin powder (A-3) was obtained in the same manner as in Synthesis Example 1. The Mw of the phenolic varnish-type phenolic resin (A-3) was 2,700.

[0250] The GPC diagram of phenolic varnish-type phenolic resin (A-3) is shown in... Figure 3 .

[0251] Synthesis Example 4 (Synthesis of Phenolic Resin (A-4) of Phenolic Varnish Type)

[0252] The starting materials were set as follows: 164 g (1.52 mol) of m-cresol, 117 g (1.10 mol) of benzaldehyde, and 58 g (0.47 mol) of salicylaldehyde. Otherwise, 282 g of phenolic varnish-type phenolic resin powder (A-4) was obtained in the same manner as in Synthesis Example 1. The Mw of the phenolic varnish-type phenolic resin (A-4) was 2,900.

[0253] The GPC diagram of phenolic varnish-type phenolic resin (A-4) is shown in... Figure 4 .

[0254] Synthesis Example 5 (Synthesis of Phenolic Resin (A-5) of Phenolic Varnish Type)

[0255] The reaction solvent was set as 250g of ethanol, 30g of 1-propanol, and 15g of 2-propanol. Otherwise, 282g of phenolic varnish-type phenolic resin (A-5) powder was obtained in the same manner as in Synthesis Example 1. The Mw of phenolic varnish-type phenolic resin (A-5) was 3,200.

[0256] The GPC diagram of phenolic varnish-type phenolic resin (A-5) is shown in... Figure 5 .

[0257] Synthesis Example 6 (Synthesis of Phenolic Resin (A-6) for Phenolic Varnish Type)

[0258] 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 p-toluenesulfonic acid were added to a 2000 mL four-necked flask equipped with a cooling tube and dissolved in 300 g of methanol as the reaction solvent. The mixture was then heated under a covered heater and stirred at 65 °C 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 by separation. The solvent was removed from the residual resin solution by vacuum distillation, and the solution was then dried under vacuum to obtain 286 g of a light red phenolic varnish-type phenolic resin (A-6) powder. The Mw of the phenolic varnish-type phenolic resin (A-6) was 6,800.

[0259] The GPC diagram of phenolic varnish-type phenolic resin (A-6) is shown in... Figure 6 .

[0260] Synthesis Example 7 (Synthesis of Phenolic Resin (A-7) for Phenolic Varnish Type)

[0261] The starting materials were set as follows: 164 g (1.52 mol) of m-cresol, 102 g (0.96 mol) of benzaldehyde, and 86 g (0.70 mol) of salicylaldehyde. Otherwise, 283 g of phenolic varnish-type phenolic resin powder (A-7) was obtained in the same manner as in Synthesis Example 6. The Mw of the phenolic varnish-type phenolic resin (A-7) was 13,900.

[0262] The GPC diagram of phenolic varnish-type phenolic resin (A-7) is shown in... Figure 7 .

[0263] Comparative Synthesis Example 1 (Synthesis of Phenolic Resin (A-8) for Phenolic Varnish Type)

[0264] Under a dry nitrogen stream, 140 g (1.30 mol) of m-cresol, 76 g (0.7 mol) of p-cresol, 151 g (1.86 mol) of 37% formaldehyde aqueous solution (formaldehyde 1.86 mol), and 1 g (0.01 mol) of oxalic acid dihydrate were added to a 2000 mL three-necked flask equipped with a cooling tube and dissolved in 528 g of methyl isobutyl ketone (MIBK). The mixture was then heated using a covered heater, with the reaction solution refluxed and stirred for 4 hours to allow the reaction to proceed. After the reaction, water was added, and the mixture was separated and washed five times. The methyl isobutyl ketone was removed by vacuum distillation at 60 °C using an evaporator, followed by vacuum drying to obtain 212 g of a light red powder, phenolic varnish-type phenolic resin (A-8). The Mw of the phenolic varnish-type phenolic resin (A-8) was 3,600.

[0265] Synthesis Example 8 (Synthesis of Alkali-Soluble Resin (b-1) Containing Polymerizable Unsaturated Groups)

[0266] Referring to Synthesis Example 1 of Japanese Patent Application Publication No. 2023-97382, an alkali-soluble resin solution (b-1) containing polymerizable unsaturated groups (solid content concentration 50%) was obtained. Specifically, 114.4 g (0.23 mol) of the reaction product of 9,9-bis(4-hydroxyphenyl)fluorene and chloromethyl ethylene oxide, 33.2 g (0.46 mol) of acrylic acid, 157 g of propylene glycol monomethyl ether acetate (PGMEA), and 0.48 g of tetraethylammonium bromide were added to a 500 mL four-necked flask equipped with a reflux condenser, and the mixture was stirred under heating at 100°C to 105°C for 20 hours to allow the reaction to proceed. Subsequently, 35.3 g (0.12 mol) of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride and 18.3 g (0.12 mol) of 1,2,3,6-tetrahydrophthalic anhydride were added to the flask, and the mixture was heated and stirred at 120℃~125℃ for 6 hours to obtain a solution of alkali-soluble resin (b-1) containing polymerizable unsaturated groups.

[0267] Synthesis Example 9 (Synthesis of Partially Acrylated Epoxy Resin (b-1-1))

[0268] Referring to Synthesis Example 2 of Japanese Patent Application Publication No. 2023-97382, a partially acrylic epoxy resin solution (b-2) (solid content concentration 50%) was obtained. Specifically, the following phenolic varnish-type epoxy resin, i.e., in the structure represented by general formula (1) where Cy is a benzene ring and R... 12 All are groups of formula (*), Y is methylene, R 11 A phenolic varnish-type epoxy resin with methyl group, m=1, n=1, a≒6.8, Mw=1574, and epoxy equivalent=203g / eq was used as the raw material resin. To 282 parts by mass (1.389 equivalents) of the raw material resin, 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 parts by mass of hydroquinone monomethyl ether were added, along with 1 part by mass of phenolsulfonic acid. The mixture was reacted at 80℃~90℃ for 10 hours. Thus, the R of the raw material resin was obtained. 12 A portion of the functional groups (equivalent ratio 50%) are acryliced ​​in the partially acrylic epoxy resin (b-1-1).

[0269] Synthesis Example 10 (Synthesis of (meth)acrylic acid base-soluble resin (b-2))

[0270] Referring to Synthesis Example 1 of Japanese Patent Application Publication No. 2022-38599, a methacrylic resin (b-2) containing epoxy and hydroxyl groups (20% solids concentration) was obtained. Specifically, 33.40 g of 4-hydroxyphenyl methacrylate ("PQMA" manufactured by Showa Denko Co., Ltd.) 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 and Koko Pure Chemical Industries Co., Ltd.) as a polymerization initiator was completely dissolved in 15.0 g of PGMEA. The two solutions obtained were simultaneously added dropwise over 2 hours to 45.0 g of PGMEA heated to 85°C in a 300 mL three-necked flask under a nitrogen atmosphere. After the addition was completed, the mixture was allowed to react at 85°C for 3 hours, thereby obtaining a 20% by weight solution of a (meth)acrylic base-soluble resin (b-2) with a PQMA / GMA ratio of 80 / 20.

[0271] [Negative Photosensitive Resin Composition]

[0272] Example 1

[0273] 1.16 g of phenolic varnish-type phenolic resin powder (A-1) obtained in Synthesis Example 1, 2.32 g of alkali-soluble resin solution (b-1) containing polymerizable unsaturated groups, 0.06 g of partially acrylic epoxy resin solution (b-1-1), 1.57 g of polymerizable compound (C) (manufactured by Nippon Kayaku Co., Ltd.: dipentaerythritol hexaacrylate), 0.46 g of polymerization initiator (D) (manufactured by ADEKA Co., Ltd., NCI-831), 13.12 g of carbon black dispersion (E) (25% carbon black, 6% dispersant in propylene glycol monomethyl ether acetate (PGMEA) solvent), and 23.59 g of propylene glycol monomethyl ether acetate (PGMEA) (F) (manufactured by Kyowa Neochem Co., Ltd.; PMA-P) were mixed and dissolved to obtain a negative photosensitive resin composition.

[0274] Examples 2 to 7, Comparative Example 1

[0275] Using the phenolic varnish-type phenolic resin powder (A-2) to phenolic varnish-type phenolic resin powder (A-8) shown in Table 1 as component (A), the negative photosensitive resin composition was obtained in the same manner as in Example 1.

[0276] Example 8

[0277] A negative photosensitive resin composition was obtained by mixing and dissolving 1.18 g of phenolic varnish-type phenolic resin (A-1) powder, 5.9 g of (meth)acrylic acid base-soluble resin solution (b-2) synthesized in Synthesis Example 10, 1.76 g of polymerizable compound (C) (manufactured by Nippon Kayaku Co., Ltd.: dipentaerythritol hexaacrylate), 0.46 g of polymerization initiator (D) (manufactured by ADEKA (stock), NCI-831), 13.12 g of carbon black dispersion (E) (25% carbon black, 6% dispersant in propylene glycol monomethyl ether acetate (PGMEA) solvent), and 20.83 g of PGMEA (F) (manufactured by Kyowa Neochem Co., Ltd.; PMA-P).

[0278] Examples 9 to 14, Comparative Example 2

[0279] Using the phenolic varnish-type phenolic resin powder (A-2) to phenolic varnish-type phenolic resin powder (A-8) shown in Table 2 as component (A), the negative photosensitive resin composition was obtained in the same manner as in Example 8.

[0280] Comparative Example 3

[0281] Instead of phenolic varnish-type phenolic resin (A-1), 2.32 g of an alkali-soluble resin solution (b-1) containing polymerizable unsaturated groups synthesized in Synthesis Example 8 was used, and PGMEA(F) was set to 22.43 g. Otherwise, a negative photosensitive resin composition was obtained using the same method as in Example 1.

[0282] Comparative Example 4

[0283] Instead of phenolic varnish-type phenolic resin (A-1), 5.9 g of the (meth)acrylic base-soluble resin solution (b-2) synthesized in Synthesis Example 10 was used, and PGMEA(F) was set to 16.11 g. Otherwise, the negative photosensitive resin composition was obtained by the same method as in Example 8.

[0284] [evaluate]

[0285] The negative photosensitive resin compositions prepared in the examples and comparative examples were used to prepare resist films, and the film-forming properties, the alkali solubility of the resist film before exposure, and the chemical resistance of the resist film after exposure were evaluated.

[0286] (1) Film-forming properties

[0287] Using a rod coater (manufactured by Daiichi Rika Co., Ltd.: no. 02), a negative photosensitive resin composition was coated onto a 5-inch diameter silicon wafer to a thickness of approximately 5 μm. The coated film was then pre-baked at 100°C for 60 seconds. The resulting wafer surface was observed using an optical microscope to evaluate for the presence or absence of dross.

[0288] The case without scum is defined as good compatibility (○), and the case with scum is defined as insufficient compatibility (×). The evaluation results are shown in Tables 1 and 2.

[0289] (2) Alkali solubility

[0290] After applying the negative photosensitive resin composition to a silicon wafer with a thickness of approximately 5 μm using a bar coater, the coated film was pre-baked at 100°C for 60 seconds. The resulting wafer was then immersed in a 250 mL vat containing developer (2.38% tetramethylammonium hydroxide aqueous solution) for 10 seconds. The removed wafer was then rinsed with pure water for 10 seconds, and any residue (resist film) on the wafer was evaluated.

[0291] The condition with no residue is marked as good (○), and the condition with residue is marked as insufficient (×). The evaluation results are shown in Table 1 and Table 2.

[0292] (3) Chemical resistance of the hardened film

[0293] The negative photosensitive resin composition was coated onto a 5-inch diameter silicon wafer using a rod coater (manufactured by Daiichi Rika Co., Ltd.: no. 02) to a thickness of approximately 5 μm, and then dried at 100°C for 60 seconds. It was then irradiated with 200 mJ / cm² ultraviolet light using an ultraviolet (UV) irradiation device (manufactured by Sanyo Electric Co., Ltd.: UVE-1001SD). 2 The light is then applied, followed by baking at 230°C for 180 seconds to obtain a wafer with a hardened film.

[0294] After measuring the film thickness of the obtained wafers, they were split into two. One of the split wafers was immersed in 50% sulfuric acid solution (assuming plating solution) for 15 minutes, and the other was immersed in a 2.38% tetramethylammonium hydroxide (TMAH) solution for 15 minutes. After rinsing the wafers removed from the solutions with pure water, the film thickness was measured again.

[0295] Chemical resistance was evaluated using the change rate of film thickness before and after immersion in solvent. A change rate of less than 2% was designated as good (○), and a change rate of more than 2% was designated 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 polymerizable unsaturated groups synthesized in Synthesis Example 8, and (b-2) alkali-soluble resin is the (meth)acrylic acid-based alkali-soluble resin synthesized in Synthesis Example 10.

[0296] [Table 1]

[0297]

[0298]

[0299] In Table 1, the molar ratio of structural units of component (A) [(a1) / (a2) / (a3)] is the molar ratio of structural units (a1) derived from m-cresol, structural units (a2) derived from benzaldehyde, and structural units (a3) ​​derived from salicylaldehyde.

[0300] Tables 1 and 2 confirm that the resist film using the negative photosensitive resin composition of the present invention exhibits high film-forming properties. Furthermore, the resist film demonstrates high alkali solubility. Consequently, the resist-cured film exhibits excellent chemical resistance.

Claims

1. A negative photosensitive resin composition comprising the following components (A) to (F), (A) A phenolic varnish-type phenolic resin with a molar ratio (a1):(a2):(a3) of cresol-derived structural unit (a1):(a2):(a3) of 1.0:0.3~0.8:0.3~0.8; (B) At least one alkali-soluble resin among alkali-soluble resins containing polymerizable unsaturated groups and (meth)acrylic acid-based alkali-soluble resins. (C) Polymer compounds; (D) Polymerization initiator; (E) Coloring components; (F) Organic solvents.

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

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

4. The negative photosensitive resin composition according to claim 1 or 2, wherein, The total content of the structural units (a1) derived from cresol, (a2) derived from benzaldehyde, and (a3) ​​derived from hydroxybenzaldehyde in component (A) is 30% by mass or more.

5. The negative photosensitive resin composition according to claim 1 or 2, wherein, The weight average molecular weight of component (A) is above 1,000 and below 15,000.

6. A hardened film obtained from the negative photosensitive resin composition as described in claim 1 or 2.

7. A photoresist film obtained from the negative photosensitive resin composition as described in claim 1 or 2.

8. A photoresist underlayer film obtained from the negative photosensitive resin composition as described in claim 1 or 2.

9. A permanent resist film obtained from the negative photosensitive resin composition as described in claim 1 or 2.

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