Negative photosensitive resin composition, dry film, cured product, and electronic component

Abstract

To provide a negative photosensitive resin composition which is excellent in resolution and gives a cured product excellent in flexibility.SOLUTION: The negative photosensitive resin composition contains (A) an alkali-soluble resin, (B) a photosensitizer, and (C) a crosslinking agent. The alkali-soluble resin (A) contains a polyamic acid having a repeating unit represented by the following formula (1), having an unsaturated carbon bond at a molecular chain terminal, and having a number average molecular weight of less than 20,000. The photosensitizer (B) contains an oxime-based photopolymerization initiator. The crosslinking agent (C) contains a polyfunctional primary thiol compound having a bi- or higher functional thiol group in one molecule.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a negative photosensitive resin composition, and more particularly to a negative photosensitive resin composition containing a polyamic acid as a photosensitive component, a dry film having a resin layer formed from the coated and dried product of the negative photosensitive resin composition, a cured product of the negative photosensitive resin composition or the resin layer, and an electronic component having the cured product. [Background technology]

[0002] Conventionally, photosensitive resin compositions primarily composed of polyamic acid or polyhydroxyamide, precursors of polyimide or polybenzoxazole, have been used as insulating materials for rewiring in semiconductor devices. These polyamic acid or polyhydroxyamide undergoes a cyclization reaction to form imide or benzoxazole rings when heated at high temperatures (over 350°C), resulting in a rigid structure that increases the intermolecular packing density, resulting in a cured film with excellent chemical resistance and thermal properties.

[0003] Meanwhile, a so-called chip-first fan-out wafer-level packaging method is known, in which rewiring is formed after the chip is encapsulated with an encapsulant primarily composed of epoxy resin or the like. The insulating material for the rewiring used in this method is required to be one that can be cured at a temperature of approximately 220°C, given the heat resistance of epoxy resins. Therefore, methods are being investigated that can produce cured products that satisfy the chemical resistance and heat resistance of a cured film even at relatively low temperatures. For example, various approaches have been proposed, such as adding a crosslinking agent such as an epoxy compound to a photosensitive resin composition containing polyamic acid or polyhydroxyamide (Patent Document 1).

[0004] Furthermore, from the viewpoints of fine patterning and flexibility, positive-type photosensitive resin compositions such as the resin composition described in Patent Document 1 are widely used as insulating materials for semiconductor elements. On the other hand, in recent years, interest has also been growing in negative-type photosensitive resin compositions that offer excellent adhesion, chemical resistance, film thickness, pattern shape, and the like, in order to adapt to the increasingly complex structures and manufacturing processes of semiconductor elements. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-111718 Summary of the Invention [Problem to be solved by the invention]

[0006] When a negative-type photosensitive resin composition is applied to an insulating material or the like used in a semiconductor element, it is necessary to realize fine patterning and flexibility equivalent to those of a positive-type photosensitive resin composition, in addition to conventional properties such as heat resistance, electrical properties, and mechanical properties.

[0007] Therefore, a primary object of the present invention is to provide a negative-type photosensitive resin composition that can provide a cured product having excellent resolution and flexibility. Another object of the present invention is to provide a dry film having a resin layer formed by applying and drying the negative-type photosensitive resin composition, a cured product of the negative-type photosensitive resin composition or the resin layer, and an electronic component having the cured product. [Means for solving the problem]

[0008] The present inventors have focused on negative-type photosensitive resin compositions using polyamic acid, a precursor of polyimide, which has excellent properties such as heat resistance and flexibility, and have conducted extensive research. As a result, they have discovered that photoradical polymerization of a polyamic acid having a specific molecular weight and an unsaturated carbon bond at the molecular chain end with a crosslinker having a specific thiol group using a specific photosensitizer improves resolution and produces a cured product with excellent flexibility. The present invention has been completed based on this discovery. The gist of the present invention is as follows.

[0009] [1] (A) an alkali-soluble resin; (B) a photosensitizer; (C) a crosslinking agent; A negative photosensitive resin composition comprising: The alkali-soluble resin (A) is represented by the following formula (1): [ka] (In general formula (1), X represents a tetravalent organic group, Y represents a divalent organic group, and n represents an integer.) and a polyamic acid having a number average molecular weight of less than 20,000, which has a repeating unit represented by the formula: the (B) photosensitizer contains an oxime-based photopolymerization initiator, the (C) crosslinking agent contains a polyfunctional primary thiol compound having two or more functional thiol groups in one molecule; A negative photosensitive resin composition comprising: [2] The negative photosensitive resin composition according to [1], wherein the polyamic acid is derived from a compound in which the unsaturated carbon bond at the terminal of the molecular chain has a norbornene structure. [3] The negative photosensitive resin composition according to [1] or [2], wherein the polyfunctional primary thiol compound has 2 to 6 thiol groups in one molecule. [4] The negative photosensitive resin composition according to any one of [1] to [3], wherein at least one organic group of X and Y in the formula (1) has an ether bond (—O—). [5] The negative photosensitive resin composition according to any one of [1] to [4], wherein the polyamic acid has a number average molecular weight of more than 4,000 and not more than 10,000. [6] A dry film comprising a base film and a resin layer provided on at least one side of the base film, A dry film, wherein the resin layer is a product obtained by applying and drying the negative photosensitive resin composition according to any one of [1] to [5]. [7] A cured product of the negative photosensitive resin composition according to any one of [1] to [5] or the resin layer of the dry film according to [6]. [8] An electronic component comprising the cured product according to [7]. [Effects of the Invention]

[0010] According to the present invention, it is possible to realize a negative photosensitive resin composition that can give a cured product that is excellent in both resolution and flexibility.

[0011] [Negative-type photosensitive resin composition] The negative-type photosensitive resin composition according to the present invention contains, as essential components, (A) an alkali-soluble resin, (B) a photosensitizer, and (C) a crosslinker. By using, as the (A) alkali-soluble resin, a polyamic acid having a specific molecular weight (a number-average molecular weight of less than 20,000) and having an unsaturated carbon bond at at least one molecular chain terminal, as the (B) alkali-soluble resin, an oxime-based photopolymerization initiator, and as the (C) crosslinker, a polyfunctional primary thiol compound, it is possible to improve resolution while imparting flexibility to the resulting cured product. While the reason for this is unclear, it is believed to be as follows. The photosensitive resin composition of the present invention is a negative-tone photosensitive resin composition that generates radical active species upon exposure, which then induces a thiol-ene reaction between the terminal unsaturated carbon bonds of the polyamic acid and the thiol groups of the crosslinking agent, dissolving the unexposed areas in a developer to form a pattern. Furthermore, the use of a polyfunctional primary thiol compound as the crosslinking agent suppresses steric hindrance at the crosslinked sites, imparting excellent flexibility to the resulting cured product. However, the primary thiol groups contained in the crosslinking agent are inhibited by oxygen, making it difficult to promote crosslinking reactions and achieve sufficient development resistance after exposure. Therefore, the use of an oxime-based photopolymerization initiator and a polyamic acid with a relatively low molecular weight in the present invention is believed to enable both excellent resolution and flexibility as a cured product, even when a polyfunctional primary thiol compound is used as the crosslinking agent. The components of the negative-tone photosensitive resin composition of the present invention are described in detail below.

[0012] <(A) Alkali-soluble resin> The negative-type photosensitive resin composition according to the present invention contains, as a resin component, a polyamic acid having a repeating unit represented by the following formula (1), an unsaturated carbon bond at at least one molecular chain terminal, and a number-average molecular weight of less than 20,000. The polyamic acid is a polyimide precursor, and upon heating, the amic acid in the structure undergoes dehydration ring closure to form an imide ring. The polyamic acid may also be a polybenzoxazole precursor. [ka] (In general formula (1), X represents a tetravalent organic group, Y represents a divalent organic group, and n represents an integer.)

[0013] The polyamic acid represented by the formula (1) can be obtained by reacting a carboxylic acid anhydride component with an amine component and / or an isocyanate component by a standard method. That is, it can be obtained by reacting a carboxylic acid anhydride having an X skeleton with an amine component and / or an isocyanate component having a Y skeleton. Imidization can be carried out by thermal imidization, chemical imidization, or a combination of these methods.

[0014] Examples of the carboxylic acid anhydride component include tetracarboxylic acid anhydrides and tricarboxylic acid anhydrides, but are not limited to these acid anhydrides, and any compound having an acid anhydride group and a carboxyl group that react with an amino group or an isocyanate group, including derivatives thereof, can be used. Furthermore, these carboxylic acid anhydride components may be used alone or in combination of two or more.

[0015] Examples of tetracarboxylic acid anhydrides include pyromellitic dianhydride, 3-fluoropyromellitic dianhydride, 3,6-difluoropyromellitic dianhydride, 3,6-bis(trifluoromethyl)pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,2'-difluoro-3,3',4,4'-biphenyltetracarboxylic dianhydride, and 5,5'-difluoro-3,3',4,4'-biphenyltetracarboxylic dianhydride. Acid dianhydrides, 6,6'-difluoro-3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',5,5',6,6'-hexafluoro-3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2'-bis(trifluoromethyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride, 5,5'-bis(trifluoromethyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride, 6,6'-bis(trifluoromethyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',5,5'-tetrafluoro- hexakis(trifluoromethyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',6,6'-tetrakis(trifluoromethyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride, 5,5',6,6'-tetrakis(trifluoromethyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride, and 2,2',5,5',6,6'-hexakis(trifluoromethyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3',4,4 "-terphenyltetracarboxylic dianhydride, 3,3'",4,4'"-quaterphenyltetracarboxylic dianhydride, 3,3"",4,4""-quinquephenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethynylidene-4,4'-diphthalic dianhydride, 2,2-propylidene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-Diphthalic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, difluoromethylene-4,4'-diphthalic dianhydride, 1,1,2,2-tetrafluoro-1,2-ethylene-4,4'-diphthalic dianhydride, 1,1,2,2,3,3-hexafluoro-1,3-trimethylene-4,4'-diphthalic dianhydride, 1,1,2,2,3,3,4,4-octafluoro-1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,1,2,2,3,3,4,4,5,5-de Fluoro-1,5-pentamethylene-4,4'-diphthalic dianhydride, thio-4,4'-diphthalic dianhydride, sulfonyl-4,4'-diphthalic dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethylsiloxane dianhydride, 1,3-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,3 -Bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, bis[3-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis(3,4-dicarboxyphenoxy)dimethylsilane dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)-1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-Anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4'-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic) dianhydride, methyl Ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethynylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2 -dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 3,3'-difluorooxy-4,4'-diphthalic dianhydride, 5,5'-difluorooxy-4,4'-diphthalic dianhydride, 6,6'-difluorooxy-4,4'-diphthalic dianhydride, 3,3',5,5',6,6'-hexafluorooxy-4,4'-diphthalic dianhydride, 3,3'-bis(trifluoromethyl)oxy-4,4'-diphthalic dianhydride Aqueous, 5,5'-bis(trifluoromethyl)oxy-4,4'-diphthalic dianhydride, 6,6'-bis(trifluoromethyl)oxy-4,4'-diphthalic dianhydride, 3,3',5,5'-tetrakis(trifluoromethyl)oxy-4,4'-diphthalic dianhydride, 3,3',6,6'-tetrakis(trifluoromethyl)oxy-4,4'-diphthalic dianhydride, 5,5',6,6'-tetrakis(trifluoromethyl)oxy-4,4'-diphthalic dianhydride, 3,3',5,5',6,6'-hexakis(trifluoromethyl)oxy-4,4'-Diphthalic dianhydride, 3,3'-difluorosulfonyl-4,4'-diphthalic dianhydride, 5,5'-difluorosulfonyl-4,4'-diphthalic dianhydride, 6,6'-difluorosulfonyl-4,4'-diphthalic dianhydride, 3,3',5,5',6,6'-hexafluorosulfonyl-4,4'-diphthalic dianhydride, 3,3'-bis(trifluoromethyl)sulfonyl-4,4'-diphthalic dianhydride, 5,5'-bis(trifluoromethyl)sulfonyl-4,4'-diphthalic dianhydride, 6,6'-bis(trifluoromethyl)sulfonyl 3,3',5,5'-Tetrakis(trifluoromethyl)sulfonyl-4,4'-diphthalic dianhydride, 3,3',6,6'-Tetrakis(trifluoromethyl)sulfonyl-4,4'-diphthalic dianhydride, 5,5',6,6'-Tetrakis(trifluoromethyl)sulfonyl-4,4'-diphthalic dianhydride, 3,3',5,5',6,6'-Hexakis(trifluoromethyl)sulfonyl-4,4'-diphthalic dianhydride, 3,3'-Difluoro-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride Aqueous, 5,5'-difluoro-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 6,6'-difluoro-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 3,3',5,5',6,6'-hexafluoro-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 3,3'-bis(trifluoromethyl)-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 5,5'-bis(trifluoromethyl)-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 6,6' -Difluoro-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 3,3',5,5'-tetrakis(trifluoromethyl)-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 3,3',6,6'-tetrakis(trifluoromethyl)-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 5,5',6,6'-tetrakis(trifluoromethyl)-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 3,3',5,5',6,6'-hexakis(trifluoromethyl)-2,2-Perfluoropropylidene-4,4'-diphthalic dianhydride, 9-phenyl-9-(trifluoromethyl)xanthene-2,3,6,7-tetracarboxylic dianhydride, 9,9-bis(trifluoromethyl)xanthene-2,3,6,7-tetracarboxylic dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 9,9-bis[4-(3,4-dicarboxy)phenyl]fluorene dianhydride, 9,9-bis[4-(2,3-dicarboxy)phenyl]fluorene dianhydride, ethylene glycol bistrimellitate dianhydride, 1,2-(ethylene)bis(trimellitate anhydride), 1,3-(trimethylene)bis(trimellitate) bis(trimellitate anhydride), 1,4-(tetramethylene)bis(trimellitate anhydride), 1,5-(pentamethylene)bis(trimellitate anhydride), 1,6-(hexamethylene)bis(trimellitate anhydride), 1,7-(heptamethylene)bis(trimellitate anhydride), 1,8-(octamethylene)bis(trimellitate anhydride), 1,9-(nonamethylene)bis(trimellitate anhydride), 1,10-(decamethylene)bis(trimellitate anhydride), 1,12-(dodecamethylene)bis(trimellitate anhydride), 1,16-(hexadecamethylene)bis(trimellitate anhydride), 1,18-(octadecamethylene)bis(trimellitate anhydride), and the like.

[0016] Among the above-mentioned tetracarboxylic acid anhydrides, from the viewpoint of flexibility of the cured product, those having an ether bond (—O—) in the molecule, such as 4,4′-oxydiphthalic anhydride (ODPA), 4,4′-(4,4′-isopropylidenediphenoxy)diphthalic dianhydride (BPADA), and 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), are preferred.

[0017] Examples of tricarboxylic acid anhydrides include trimellitic anhydride and nuclear-hydrogenated trimellitic anhydride.

[0018] The amine component may be, but is not limited to, a diamine such as an aliphatic diamine or an aromatic diamine, or a polyamine such as an aliphatic polyetheramine, and may be used alone or in combination.

[0019] Examples of diamines include diamines with one benzene nucleus such as p-phenylenediamine (PPD), 1,3-diaminobenzene, 2,4-toluenediamine, 2,5-toluenediamine, and 2,6-toluenediamine; diaminodiphenyl ethers such as 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, and 3,4'-diaminodiphenyl ether; 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl; '-Bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis(4-aminophenyl)sulfide, 4,4'-diaminobenzanilide, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine (o-tolidine), 2,2'-dimethylbenzidine (m-tolidine), 3,3'-dimethoxybenzidine, 2,2'-dimethoxybenzidine, 3,3'-diaminodiphenyl ether, 3 ,4'-Diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, 3,3'-diamino-4,4'-dichlorobenzophenone, 3,3'-diamino-4,4'-dimethoxybenzophenone, 3,3'-diaminodiphenyl meth , 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 3,3'-diaminodiphenyl sulfoxide, 3,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfoxide, 3,3'-dicarboxy-4,Diamines with two benzene nuclei such as 4'-diaminodiphenylmethane, 1,3-bis(3-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(3-aminophenyl)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)-4-trifluoromethylbenzene, 3,3'-diamino-4-(4-phenyl)phenoxybenzophenone, 3,3'-diamino-4,4'-di(4-phenylphenoxy)benzophenone, 1,3-bis(3-aminophenylsulfide)benzene, Diamines with three benzene nuclei such as 1,3-bis(4-aminophenylsulfide)benzene, 1,4-bis(4-aminophenylsulfide)benzene, 1,3-bis(3-aminophenylsulfone)benzene, 1,3-bis(4-aminophenylsulfone)benzene, 1,4-bis(4-aminophenylsulfone)benzene, 1,3-bis[2-(4-aminophenyl)isopropyl]benzene, 1,4-bis[2-(3-aminophenyl)isopropyl]benzene, 1,4-bis[2-(4-aminophenyl)isopropyl]benzene, 3,3'-bis(3-aminophenoxy)biphenyl, 3,3'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[3-(3-aminophenoxy)phenyl]ether, bis[3-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]ether, bis[3-(3-aminophenoxy)phenyl]ketone, bis[3-(4-aminophenoxy)phenyl]ketone, bis[4-(3-aminophenoxy)phenyl]ketone, bis[4-(4-aminophenoxy)phenyl]ketone, bis[3-(3-aminophenoxy)phenyl]ketone bis[3-(4-aminophenoxy)phenyl]sulfide, bis[4-(3-aminophenoxy)phenyl]sulfide, bis[4-(4-aminophenoxy)phenyl]sulfide, bis[3-(3-aminophenoxy)phenyl]sulfone, bis[3-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[3-(3-aminophenoxy)phenyl]methane, bis[3-(4-aminophen 2,2-bis[3-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[3 aromatic diamines such as diamines with four benzene nuclei, such as 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,Examples of the aliphatic diamines include 8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, and 1,2-diaminocyclohexane. Examples of the aliphatic polyetheramines include ethylene glycol and / or propylene glycol-based polyamines. Amines having a carboxyl group can also be used, as shown below.

[0020] Among the above diamines, from the viewpoint of flexibility of the cured product, those having an ether bond (—O—) in the molecule, such as 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis(4-aminophenoxy)benzene (TPE-R), and 4,4′-diaminodiphenyl ether, are preferred.

[0021] Examples of amines having a carboxyl group include diaminobenzoic acids such as 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, and 3,4-diaminobenzoic acid, aminophenoxybenzoic acids such as 3,5-bis(3-aminophenoxy)benzoic acid and 3,5-bis(4-aminophenoxy)benzoic acid, 3,3'-diamino-4,4'-dicarboxybiphenyl, 4,4'-diamino-3,3'-dicarboxybiphenyl, 4,4'-diamino-2,2'-dicarboxybiphenyl, and 4,4'-diamino-2,2',5,5'-tetracarboxybiphenyl. Carboxybiphenyl compounds such as carboxybiphenyl, 3,3'-diamino-4,4'-dicarboxydiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 2,2-bis[3-amino-4-carboxyphenyl]propane, 2,2-bis[4-amino-3-carboxyphenyl]propane, 2,2-bis[3-amino-4-carboxyphenyl]hexafluoropropane, 4,4'-diamino-2,2',5,5'-tetracarboxydiphenylmethane and other carboxydiphenylmethane compounds carboxydiphenylalkanes such as 3,3'-diamino-4,4'-dicarboxydiphenyl ether, 4,4'-diamino-3,3'-dicarboxydiphenyl ether, 4,4'-diamino-2,2'-dicarboxydiphenyl ether, 4,4'-diamino-2,2',5,5'-tetracarboxydiphenyl ether, carboxydiphenyl ether compounds such as 3,3'-diamino-4,4'-dicarboxydiphenyl sulfone, 4,4'-diamino-3,3'-dicarboxydiphenyl sulfone, 4 Examples of suitable aryl groups include diphenyl sulfone compounds such as 4,4'-diamino-2,2'-dicarboxydiphenyl sulfone and 4,4'-diamino-2,2',5,5'-tetracarboxydiphenyl sulfone, bis[(carboxyphenyl)phenyl]alkane compounds such as 2,2-bis[4-(4-amino-3-carboxyphenoxy)phenyl]propane, and bis[(carboxyphenoxy)phenyl]sulfone compounds such as 2,2-bis[4-(4-amino-3-carboxyphenoxy)phenyl]sulfone.

[0022] The isocyanate component may be, but is not limited to, aromatic diisocyanates and their isomers and polymers, aliphatic diisocyanates, alicyclic diisocyanates and their isomers, or other general-purpose diisocyanates. These isocyanate components may be used alone or in combination.

[0023] Examples of diisocyanates include aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, biphenyl diisocyanate, diphenyl sulfone diisocyanate, and diphenyl ether diisocyanate, as well as their isomers and polymers; aliphatic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and xylylene diisocyanate; alicyclic diisocyanates and isomers obtained by hydrogenating the above-mentioned aromatic diisocyanates; and other general-purpose diisocyanates.

[0024] The polyamic acid represented by formula (1) may have an amide bond. This may be an amide bond obtained by reacting an isocyanate with a carboxylic acid, or may be formed by other reactions. It may also have bonds formed by other addition and condensation reactions.

[0025] For the synthesis of polyamic acid, known and commonly used alkali-soluble polymers, oligomers, and monomers having a carboxyl group and / or an acid anhydride group may be used. For example, the polyamic acid may be a resin obtained by reacting these known and commonly used alkali-soluble resins, either alone or in combination with the above-mentioned carboxylic acid anhydride component, with the above-mentioned amines / isocyanates.

[0026] The polyamic acid obtained as described above has at least one molecular chain end blocked with a compound having an unsaturated carbon bond. In the negative-tone photosensitive resin composition of the present invention, radical active species are generated from the oxime-based photopolymerization initiator upon light irradiation, and a crosslinking reaction proceeds through a thiol-ene reaction between the unsaturated carbon bond of the polyamic acid and the primary thiol group of the polyfunctional primary thiol compound, which serves as the crosslinking agent, thereby rendering the composition insoluble in a developer. Furthermore, because the molecular chain ends of the polyamic acid are blocked, the molecular weight does not increase more than necessary during synthesis or storage, and the unexposed areas of the negative-tone photosensitive resin composition exhibit excellent developability and improved storage stability.

[0027] From the viewpoints of resolution and storage stability, the unsaturated carbon bond at the molecular chain terminal of the polyamic acid is preferably derived from a compound having a norbornene structure. For example, when synthesizing the polyamic acid, an unsaturated carbon bond having a norbornene structure can be introduced at the molecular chain terminal of the polyamic acid by adding himic anhydride (5-norbornene-2,3-dicarboxylic anhydride) or methylnadic anhydride (methyl-5-norbornene-2,3-dicarboxylic anhydride) together with the above-mentioned carboxylic anhydride component, amine component and / or isocyanate component.

[0028] The polyamic acid preferably has an acid value of 20 to 200 mgKOH / g, more preferably 60 to 150 mgKOH / g. By setting the acid value of the polyamic acid within the above range, a good balance is achieved between the developability of the unexposed areas and the development resistance of the exposed areas, thereby further improving the resolution.

[0029] The negative-type photosensitive resin composition of the present invention uses a polyamic acid having a number-average molecular weight of less than 20,000 to achieve excellent development resistance by promoting reactivity with a polyfunctional primary thiol compound in exposed areas, while also achieving excellent developability in unexposed areas. Furthermore, in consideration of resolution and cured coating film properties, the number-average molecular weight of the polyamic acid is preferably more than 4,000 and not more than 10,000.

[0030] <(B) Photosensitizer> The negative-type photosensitive resin composition of the present invention contains an oxime-based photopolymerization initiator as a photosensitizer. The oxime-based photopolymerization initiator is an oxime ester-based photopolymerization initiator, and is preferably an oxime ester-based photopolymerization initiator containing a structural moiety represented by the following general formula (I), and more preferably an oxime ester-based photopolymerization initiator having a carbazole structure. A dimeric oxime ester-based photopolymerization initiator may be used as the oxime ester-based photopolymerization initiator having a carbazole structure.

[0031] [ka]

[0032] In general formula (2), R 1 represents a hydrogen atom, a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group, or a benzoyl group. 2 represents a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group, or a benzoyl group.

[0033] R 1 and R 2 The phenyl group represented by the following formula may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a phenyl group, and a halogen atom.

[0034] R 1 and R 2 The alkyl group represented by the formula (I) is preferably an alkyl group having 1 to 20 carbon atoms, which may contain one or more oxygen atoms in the alkyl chain, and may be substituted with one or more hydroxyl groups.

[0035] R 1 and R 2 The cycloalkyl group represented by the following formula is preferably a cycloalkyl group having 5 to 8 carbon atoms.

[0036] R 1 and R 2The alkanoyl group represented by the formula: is preferably an alkanoyl group having 2 to 20 carbon atoms.

[0037] R 1 and R 2 The benzoyl group represented by the following formula may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a phenyl group, and the like.

[0038] Examples of the oxime ester photopolymerization initiator containing the structural moiety represented by general formula (2) include 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)], compounds represented by the following formula (2-1), 2-(acetyloxyiminomethyl)thioxanthen-9-one, and oxime ester compounds having a carbazole skeleton, such as ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), and compounds represented by the following general formula (2-2).

[0039] [ka]

[0040] In general formula (2-2), R 11 is R in general formula (2) 1 is synonymous with R 12 and R 14 are each independently R in general formula (2). 2 It is synonymous with R. 13 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms (when the alkyl group constituting the alkoxyl group has 2 or more carbon atoms, the alkyl group may be substituted with one or more hydroxyl groups and may have one or more oxygen atoms in the middle of the alkyl chain), or a phenoxycarbonyl group.

[0041] Such oxime ester photopolymerization initiators are preferred because they have superior photosensitivity compared to other photopolymerization initiators (radical generators), and when the negative-type photosensitive resin composition of the present invention is exposed to light, they induce a thiol-ene reaction between the unsaturated carbon bond of the polyamic acid and the primary thiol group, thereby achieving excellent resolution. The oxime ester photopolymerization initiator may also be a dimer.

[0042] The dimeric oxime ester photopolymerization initiator is more preferably a compound represented by the following general formula (2-3). [ka]

[0043] In general formula (2-3), R 16 represents a hydrogen atom, an alkyl group, an alkoxy group, a phenyl group, or a naphthyl group. 14 , R 15 each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen group, a phenyl group, a naphthyl group, an anthryl group, a pyridyl group, a benzofuryl group, or a benzothienyl group. Ar represents a single bond, or an alkylene group having 1 to 10 carbon atoms, a vinylene group, a phenylene group, a biphenylene group, a pyridylene group, a naphthylene group, an anthrylene group, a thienylene group, a furylene group, a 2,5-pyrrole-diyl group, a 4,4'-stilbene-diyl group, or a 4,2'-styrene-diyl group. n represents an integer of 0 to 1.

[0044] In general formula (2-3), R 16 The alkyl group represented by the formula is preferably an alkyl group having 1 to 17 carbon atoms. 16 The alkoxy group represented by the formula is preferably an alkoxy group having 1 to 8 carbon atoms. 16 The phenyl group represented by the formula (R) may have a substituent, and examples of the substituent include an alkyl group (preferably having 1 to 17 carbon atoms), an alkoxy group (preferably having 1 to 8 carbon atoms), an amino group, an alkylamino group (preferably having 1 to 8 carbon atoms in the alkyl group), or a dialkylamino group (preferably having 1 to 8 carbon atoms in the alkyl group).16 The naphthyl group represented by the formula (I) may have a substituent, and the substituent may be R 16 Examples of the substituents include the same as those that can be possessed by the phenyl group represented by the following formula:

[0045] In general formula (2-3), R 14 , R 15 The alkyl group represented by the formula is preferably an alkyl group having 1 to 17 carbon atoms. 14 , R 15 The alkoxy group represented by the formula is preferably an alkoxy group having 1 to 8 carbon atoms. 14 , R 15 The phenyl group represented by the formula (R) may have a substituent, and examples of the substituent include an alkyl group (preferably having 1 to 17 carbon atoms), an alkoxy group (preferably having 1 to 8 carbon atoms), an amino group, an alkylamino group (preferably having 1 to 8 carbon atoms in the alkyl group), or a dialkylamino group (preferably having 1 to 8 carbon atoms in the alkyl group). 14 , R 15 The naphthyl group represented by the formula (I) may have a substituent, and the substituent may be R 14 , R 15 Examples of the substituents include the same as those that can be possessed by the phenyl group represented by the following formula:

[0046] Furthermore, in the general formula (2-3), R 14 , R 16 are each independently a methyl group or an ethyl group, R22 is methyl or phenyl, Ar is a single bond, a phenylene group, a naphthylene group or a thienylene group, and n is preferably 0.

[0047] As the compound represented by general formula (I-3), the following compounds are more preferred. [ka]

[0048] Commercially available oxime ester photopolymerization initiators include CGI-325 manufactured by BASF Japan, Irgacure OXE01 (1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)]), Irgacure OXE02 (ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime)), N-1919 and NCI-831 manufactured by ADEKA, TR-PBG-304 manufactured by Changzhou Strong Electronic New Materials Co., Ltd., and TOE-04-A3 manufactured by Nippon Chemical Industry Co., Ltd.

[0049] The content of the oxime ester photopolymerization initiator is not particularly limited, but may be, for example, 1 to 20 parts by mass relative to 100 parts by mass of the alkali-soluble resin.

[0050] The negative-type photosensitive resin composition of the present invention may contain another photopolymerization initiator as the photosensitizer (B). Examples of the other photopolymerization initiator include known and commonly used compounds such as benzophenones, acetophenones, aminoacetophenones, benzoin ethers, benzil ketals, acylphosphine oxides, oxime ethers, and titanocenes.

[0051] <(C) Crosslinking Agent> The negative photosensitive resin composition of the present invention contains, as a crosslinking agent (C), a polyfunctional primary thiol compound having two or more functional thiol groups in one molecule, as represented by the following general formula (3). [ka]

[0052] X represents an aliphatic group having 1 to 40 carbon atoms, an aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, or a heterocyclic ring-containing group having 2 to 35 carbon atoms, each having the same valence as m, and m represents an integer of 2 to 10. In the present invention, from the viewpoints of the resolution of the negative photosensitive resin composition and the flexibility of the cured product, m is preferably 2 to 6, and more preferably 4 to 6.

[0053] The above X is used as a linking group that bonds m -SH groups. The aliphatic group having 1 to 40 carbon atoms, the aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, and the heterocyclic group having 2 to 35 carbon atoms, which have a valence equal to m and are represented by X, are groups having a structure in which m-1 hydrogen atoms have been removed from a monovalent aliphatic group having 1 to 40 carbon atoms, a monovalent aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, and a monovalent heterocyclic group having 2 to 35 carbon atoms, respectively.

[0054] One or more methylene groups in the aliphatic group, aromatic hydrocarbon ring-containing group, and heterocyclic ring-containing group for X in general formula (3) may be replaced by a group selected from -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -O-CO-NH-, -NR'-, -SS-, or -SO2-, or may be replaced by a group consisting of a combination of these groups, provided that the oxygen atoms are not adjacent to each other.

[0055] Examples of the divalent aliphatic group having 1 to 40 carbon atoms and represented by X in general formula (3) include groups having a structure in which one hydrogen atom has been removed from a monovalent aliphatic group having 1 to 40 carbon atoms, such as alkylenes such as methylene, ethylene, propylene, butylene, and butyldiyl; groups in which the methylene chain of the alkylene is replaced with -O-, -S-, -CO-O-, or -O-CO-; groups containing residues of polyols such as ethanediol, propanediol, butanediol, pentanediol, and hexanediol; residues of dithiols such as ethanedithiol, propanedithiol, butanedithiol, pentanedithiol, and hexanedithiol; and groups in which these groups are substituted with the substituents described below.

[0056] Examples of the trivalent aliphatic group having 1 to 40 carbon atoms represented by X include groups having a structure in which two hydrogen atoms have been removed from a monovalent aliphatic group having 1 to 40 carbon atoms, such as alkylidines such as propylidine and 1,1,3-butylidine; groups containing a residue of a polyol such as trimethylolpropane; and groups in which these groups are substituted with the substituents described below.

[0057] Examples of the tetravalent aliphatic group having 1 to 40 carbon atoms represented by X include groups having a structure in which three hydrogen atoms have been removed from the above-mentioned monovalent aliphatic group having 1 to 40 carbon atoms, such as groups containing a residue of a polyol such as pentaerythritol and groups in which these groups are substituted with the substituents described below.

[0058] Examples of the hexavalent aliphatic group having 1 to 40 carbon atoms represented by X include groups having a structure in which five hydrogen atoms have been removed from a monovalent aliphatic group having 1 to 40 carbon atoms, such as groups containing a residue of a polyol such as dipentaerythritol and groups in which such groups are substituted with the substituents described below.

[0059] Examples of the divalent aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms and represented by X in general formula (3) include groups having a structure in which one hydrogen atom has been removed from a monovalent aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, such as arylene groups such as phenylene and naphthylene; residues of bifunctional phenols such as catechol and bisphenol; 2,4,8,10-tetraoxaspiro[5,5]undecane; and groups in which these groups are substituted with the substituents described below.

[0060] Examples of the trivalent aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms represented by X include groups having a structure in which two hydrogen atoms have been removed from a monovalent aromatic hydrocarbon ring-containing group having 6 to 35 carbon atoms, such as phenyl-1,3,5-trimethylene and groups in which such groups are substituted with the substituents described below.

[0061] Examples of the divalent heterocycle-containing group having 2 to 35 carbon atoms represented by X include groups having a structure in which one hydrogen atom has been removed from a monovalent heterocycle-containing group having 2 to 35 carbon atoms, such as groups having a pyridine ring, pyrimidine ring, piperidine ring, piperazine ring, triazine ring, furan ring, thiophene ring, indole ring, etc., and groups in which one or more hydrogen atoms of these groups have been substituted with a substituent described below.

[0062] Examples of the trivalent heterocyclic ring-containing group represented by X and having 2 to 35 carbon atoms include groups having a structure in which two hydrogen atoms have been removed from a monovalent heterocyclic ring-containing group having 2 to 35 carbon atoms, such as a group having an isocyanuric ring, a group having a triazine ring, and groups in which one or more hydrogen atoms of these groups have been substituted with a substituent described below.

[0063] Examples of the tetravalent heterocyclic ring-containing group represented by X and having 2 to 35 carbon atoms include groups having a structure in which three hydrogen atoms have been removed from a monovalent heterocyclic ring-containing group having 2 to 35 carbon atoms, such as a group having a glycoluril group and a group in which the hydrogen atoms of this group have been substituted with a substituent described below.

[0064] Each functional group in X, such as an aliphatic group, an aromatic hydrocarbon ring-containing group, or a heterocyclic ring-containing group, may have a substituent, and unless otherwise specified, is an unsubstituted functional group that does not have a substituent or a functional group that has a substituent.

[0065] The crosslinking agent (C) is preferably contained in an amount of 0.5 to 50 parts by mass, and more preferably 10 to 30 parts by mass, per 100 parts by mass of the alkali-soluble resin (A).

[0066] In addition to the primary thiol compounds described above, a secondary thiol compound may be used in combination as the (C) crosslinking agent, as long as the effects of the present invention are not impaired.

[0067] <Other ingredients> The negative-tone photosensitive resin composition of the present invention may contain compounds having (meth)acrylic groups, epoxy groups, oxetanyl groups, or the like that are reactive with the unsaturated carbon bonds or carboxyl groups of the polyamic acid to improve the development resistance of the exposed area and the physical properties of the cured film. Also, known plasticizers and thermal acid generators may be added to promote the imidization reaction of the polyamic acid. Known sensitizers may be added to improve photosensitivity. Known adhesion agents, such as silane coupling agents, may also be added to improve adhesion to the substrate. Furthermore, various organic or inorganic low-molecular-weight or high-molecular-weight compounds may be added to impart processing properties and various functionalities to the negative-tone photosensitive resin composition. For example, surfactants, leveling agents, fine particles, etc. may be used. Examples of fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, and inorganic fine particles such as silica, carbon, and layered silicates. The negative-tone photosensitive resin composition of the present invention may also contain various colorants, fibers, etc.

[0068] The negative-tone photosensitive resin composition of the present invention may contain a solvent for viscosity adjustment, etc. The solvent is not particularly limited as long as it dissolves (A) the alkali-soluble resin, (B) the photosensitizer, (C) the crosslinker, and other components. Examples include N,N'-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N,N'-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, γ-butyrolactone, and diethylene glycol monomethyl ether. These solvents may be used alone or in combination. The amount of solvent used can be determined appropriately depending on the coating film thickness and viscosity. For example, it can be used in the range of 50 to 9,000 parts by mass per 100 parts by mass of the alkali-soluble resin (A).

[0069] [Dry film] The dry film of the present invention has a resin layer obtained by applying the above-mentioned negative photosensitive resin composition to at least one surface of a substrate film and then drying the applied resin layer, and is used by laminating the resin layer in contact with the substrate.

[0070] The dry film can be produced by uniformly applying the photosensitive resin composition of the present invention to a film by an appropriate method such as a blade coater, lip coater, comma coater, or film coater, drying the applied film to form the above-mentioned resin layer, and preferably laminating a protective film (so-called cover film) thereon. The protective film and the substrate film may be made of the same film material or different films.

[0071] In the dry film, the film materials for the base film and the protective film can be any of those known to be used for dry films. The base film can be a thermoplastic film such as a polyester film, for example, polyethylene terephthalate, having a thickness of 2 to 150 μm. The protective film can be a polyethylene film, a polypropylene film, or the like, but it is preferable that the adhesive strength with the resin layer is weaker than that of the base film.

[0072] The thickness of the resin layer on the dry film is preferably 100 μm or less, more preferably in the range of 5 to 50 μm.

[0073] [Cured product] The cured product of the present invention is obtained by curing the above-mentioned negative photosensitive resin composition in a predetermined step. The patterned film, which is the cured product, may be produced by a known, commonly used method, for example, as follows.

[0074] First, in step 1, a coating film is obtained by applying a negative photosensitive resin composition to a substrate and drying it, or by transferring a resin layer from a dry film onto the substrate. Methods for applying the negative photosensitive resin composition to a substrate include conventional methods for applying photosensitive resin compositions, such as coating with a spin coater, bar coater, blade coater, curtain coater, or screen printer, spray coating with a spray coater, and even inkjet printing. Methods for drying the coating film include air drying, heat drying in an oven or hot plate, and vacuum drying. Furthermore, it is desirable to dry the coating film under conditions that do not cause cyclization of the polyamic acid in the negative photosensitive resin composition or reaction between the polyamic acid and the crosslinker. Specifically, natural drying, air drying, or heat drying can be performed at 70 to 110°C for 1 to 30 minutes. Preferably, drying is performed on a hot plate for 1 to 10 minutes. Vacuum drying is also possible, and in this case, it can be carried out at room temperature for 20 minutes to 1 hour. There are no particular restrictions on the substrate on which the coating film of the negative photosensitive resin composition is formed, and it can be widely applied to semiconductor substrates such as silicon wafers, wiring boards, various resins, metals, etc.

[0075] Next, in step 2, the coating film is exposed directly or through a patterned photomask. The exposure light has a wavelength that can generate radical active species as the photosensitizer (B). Specifically, the exposure light preferably has a maximum wavelength in the range of 350 to 440 nm. As mentioned above, the photosensitivity can be adjusted by appropriately blending a sensitizer. The exposure device may be a contact aligner, a mirror projection, a stepper, a laser direct exposure device, or the like.

[0076] Next, in step 3, the coating film is treated with a developer, thereby removing the exposed portions of the coating film, and forming a patterned film of the negative photosensitive resin composition of the present invention.

[0077] The development method can be selected from conventional photoresist development methods, such as the rotary spray method, the paddle method, and the immersion method accompanied by ultrasonic treatment. Examples of the developer include aqueous solutions of inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, and aqueous ammonia; organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine; and quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide. If necessary, an appropriate amount of a water-soluble organic solvent or surfactant such as methanol, ethanol, or isopropyl alcohol may be added to the developer. The coating film is then washed with a rinse solution, if necessary, to obtain a patterned film. As the rinse solution, distilled water, methanol, ethanol, isopropyl alcohol, or the like may be used alone or in combination. The above-mentioned solvents may also be used as the developer.

[0078] Thereafter, in step 4, the patterned film is heated to obtain a cured coating film (cured product). This heating cyclizes the polyamic acid to obtain a polyimide. The heating temperature is appropriately set so as to be able to cure the patterned film of the negative photosensitive resin composition. For example, heating is performed in an inert gas at a temperature of 150°C or higher but lower than 350°C for about 5 to 120 minutes. A more preferred range of heating temperature is 180 to 250°C. Heating is performed using, for example, a hot plate, an oven, or a temperature-programmable heating oven. The atmosphere (gas) used in this process may be air, or an inert gas such as nitrogen or argon.

[0079] The use of the negative photosensitive resin composition of the present invention is not particularly limited, and it is suitably used, for example, as a paint, printing ink, adhesive, or a forming material for display devices, semiconductor devices, electronic components, optical components, or building materials. Specifically, as a forming material for display devices, it can be used as a layer-forming material or image-forming material for color filters, flexible display films, resist materials, alignment films, etc., as a forming material for semiconductor devices. It can also be used as a layer-forming material for resist materials, buffer coat films, etc., as a forming material for electronic components. It can also be used as a sealing material or layer-forming material for printed wiring boards, interlayer insulating films, wiring coating films, etc., as a forming material for optical components. It can also be used as an optical material or layer-forming material for holograms, optical waveguides, optical circuits, optical circuit components, anti-reflection films, etc., as a forming material for optical components. It can also be used as a building material for paints, coating agents, etc.

[0080] It is mainly used as a pattern-forming material, and the pattern film formed thereby functions as a component that imparts heat resistance and insulating properties as a permanent film made of, for example, polyimide, and is therefore particularly suitable for use as a surface protective film for semiconductor devices, display devices, and light-emitting devices, an interlayer insulating film, a rewiring insulating film, a protective film for flip-chip devices, a protective film for devices having a bump structure, an interlayer insulating film for multilayer circuits, an insulating material for passive components, a protective film for printed wiring boards such as solder resist and coverlay film, and a liquid crystal alignment film, etc. In particular, the photosensitive resin composition of the present invention has excellent chemical resistance in the cured product, and is therefore suitable as a material for forming layers to be laminated, for example, an interlayer insulating film and a rewiring insulating film. [Example]

[0081] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following, "parts" and "%" are all by mass unless otherwise specified.

[0082] (A) Preparation of alkali-soluble resin The following six resins were prepared: (1) Alkali-soluble resin 1 5.54 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) and 3.30 g of 4,4'-diaminodiphenyl ether (ODA) were weighed into a screw tube and dissolved in 71 mL of N-methylpyrrolidone in a dry atmosphere (20 °C, 20% RH). After stirring to dissolve, 7.31 g of 4,4'-oxydiphthalic anhydride (ODPA) was slowly added in a dry atmosphere and reacted overnight (16 hours) at room temperature. 5-Norbornene-2,3-dicarboxylic anhydride (NA) was then added and reacted at room temperature for 8 hours to obtain alkali-soluble resin 1. The molecular weight of the resulting alkali-soluble resin 1, measured by GPC in terms of polystyrene, was found to be a number average molecular weight (Mn) of 4,300 and a weight average molecular weight (Mw) of 10,500.

[0083] (2) Alkali-soluble resin 2 5.54 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) and 3.30 g of 4,4'-diaminodiphenyl ether (ODA) were weighed into a screw tube and dissolved in 71 mL of N-methylpyrrolidone in a dry atmosphere (20 °C, 20% RH). After stirring to dissolve, 7.91 g of 4,4'-oxydiphthalic anhydride (ODPA) was slowly added in a dry atmosphere and reacted overnight (16 hours) at room temperature. 5-Norbornene-2,3-dicarboxylic anhydride (NA) was then added and reacted at room temperature for 8 hours to obtain alkali-soluble resin 2. The molecular weight of the resulting alkali-soluble resin 2, measured by GPC in terms of polystyrene, was found to be number-average molecular weight (Mn) of 6,000 and weight-average molecular weight (Mw) of 16,000.

[0084] (3) Alkali-soluble resin 3 5.54 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) and 3.30 g of 4,4'-diaminodiphenyl ether (ODA) were weighed into a screw tube and dissolved in 73 mL of N-methylpyrrolidone in a dry atmosphere (20 °C, 20% RH). After stirring to dissolve, 8.38 g of 4,4'-oxydiphthalic anhydride (ODPA) was slowly added in a dry atmosphere and allowed to react overnight (16 hours) at room temperature. 5-Norbornene-2,3-dicarboxylic anhydride (NA) was then added and allowed to react at room temperature for 8 hours to obtain alkali-soluble resin 3. The molecular weight of the resulting alkali-soluble resin 3, measured by GPC in terms of polystyrene, was found to be number-average molecular weight (Mn) of 8,000 and weight-average molecular weight (Mw) of 23,000.

[0085] (4) Alkali-soluble resin 4 5.54 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) and 3.30 g of 4,4'-diaminodiphenyl ether (ODA) were weighed into a screw tube and dissolved in 73 mL of N-methylpyrrolidone in a dry atmosphere (20 °C, 20% RH). After stirring to dissolve, 5.52 g of 4,4'-oxydiphthalic anhydride (ODPA) was slowly added in a dry atmosphere and allowed to react overnight (16 hours) at room temperature. 5-Norbornene-2,3-dicarboxylic anhydride (NA) was then added and allowed to react at room temperature for 8 hours to obtain alkali-soluble resin 4. The molecular weight of the resulting alkali-soluble resin 4, measured by GPC in terms of polystyrene, was found to be number average molecular weight (Mn) of 2,500 and weight average molecular weight (Mw) of 8,000.

[0086] (5) Alkali-soluble resin 5 5.85 g of 1,3-bis(4-aminophenoxy)benzene (TPE-R) was weighed into a screw tube and dissolved in 48 mL of N-methylpyrrolidone in a dry atmosphere (20°C, 20% RH). After stirring to dissolve, 4.72 g of 4,4'-oxydiphthalic anhydride (ODPA) was gradually added in a dry atmosphere and allowed to react overnight (16 hours) at room temperature. 5-Norbornene-2,3-dicarboxylic anhydride (NA) was then added and allowed to react at room temperature for 8 hours to obtain alkali-soluble resin 5. The molecular weight of the resulting alkali-soluble resin 5, measured by GPC in terms of polystyrene, was found to be number average molecular weight (Mn) of 4,000 and weight average molecular weight (Mw) of 10,000.

[0087] (6) Alkali-soluble resin 6 5.54 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) and 3.30 g of 4,4'-diaminodiphenyl ether (ODA) were weighed into a screw tube and dissolved in 73 mL of N-methylpyrrolidone in a dry atmosphere (20 °C, 20% RH). After stirring to dissolve, 8.70 g of 4,4'-oxydiphthalic anhydride (ODPA) was slowly added in a dry atmosphere and reacted overnight (16 hours) at room temperature. 5-Norbornene-2,3-dicarboxylic anhydride (NA) was then added and reacted at room temperature for 8 hours to obtain alkali-soluble resin 6. The molecular weight of the resulting alkali-soluble resin 6, measured by GPC in terms of polystyrene, was found to be a number average molecular weight (Mn) of 20,000 and a weight average molecular weight (Mw) of 41,000.

[0088] (B) Preparation of photosensitizer As photosensitizers, the following three types of photopolymerization initiators were prepared. Photosensitizer 1: Oxime ester photopolymerization initiator (BASF Japan, IRGACURE OXE01) Photosensitizer 2: Acylphosphine oxide photopolymerization initiator (IGM Resins, Omnirad 819) Photosensitizer 3: Acetophenone photopolymerization initiator (IGM Resins, Omunirad 369)

[0089] (C) Preparation of crosslinker The following three types of thiol compounds were prepared as crosslinking agents. Crosslinker 1: 4-functional primary thiol compound (TS-G, manufactured by Shikoku Chemicals Co., Ltd.) [ka]

[0090] Crosslinker 2: Hexafunctional primary thiol compound (DPMP, manufactured by SC Organic Chemical Co., Ltd.) [ka]

[0091] Crosslinker 3: Trifunctional primary thiol compound (TEMPIC, manufactured by SC Organic Chemical Co., Ltd.) [ka]

[0092] [Examples 1 to 8 and Comparative Examples 1 to 4] Each component was mixed with 100 parts by mass of each alkali-soluble resin synthesized above in the proportions shown in Table 1, and completely dissolved to obtain a varnish of a negative photosensitive resin composition. Note that all the blending amounts in Table 1 are blending amounts calculated as non-volatile components.

[0093] [Elongation of cured product] The varnish was applied to a copper-sputtered silicon substrate using a spin coater so that the dried film thickness was 45 μm, and then dried on a hot plate at 100°C for 2 minutes. Next, the dried varnish film was exposed to an exposure dose of 2000 mJ / cm. 2 The film was then heated in an inert gas oven (KOYO THERMO SYSTEMS CO., LTD., CLH-21CD-S) under a nitrogen atmosphere at 110°C for 10 minutes, then held at 150°C for 30 minutes, and then further heated to the curing temperature shown in Table 1 for 60 minutes to obtain a cured film. The cured film thus obtained was peeled off, and then the breaking elongation was measured by a tensile test using EZ-SX manufactured by Shimadzu Corporation. The evaluation criteria were as follows: ⊚: The elongation at break was 15% or more. ◯: Breaking elongation was less than 15% and 10% or more. △: Breaking elongation was less than 10% and 5% or more. ×: The breaking elongation was less than 5, or a free-standing film was not obtained. The results of the elongation evaluation are shown in Table 1 below.

[0094] [Resolution] The varnish was applied to a copper-sputtered silicon substrate using a spin coater so that the film thickness after drying would be 12 μm, and then dried on a hot plate at 100° C. for 2 minutes. Next, the dried varnish film was exposed to an exposure dose of 1000 mJ / cm 2 2 After irradiating (exposing) the i-line, the film was developed with a 1% aqueous sodium carbonate solution for 80 seconds and rinsed with water to obtain a positive pattern. The contrast was calculated using the following formula. Contrast = development speed of unexposed area (film thickness / development time) / development speed of exposed area (film thickness / development time) Film thickness (μm): The film thickness before development minus the film thickness after development Development time (min): Time spent immersed in the developer The contrast was evaluated as follows: ◎: 15 or more 〇: Less than 15, 5 or more ×: Less than 5 The results of the evaluation of the resolution are shown in Table 1 below.

[0095] [Table 1]

Claims

1. (A) an alkali-soluble resin; (B) a photosensitizer; (C) a crosslinking agent; A negative-type photosensitive resin composition (excluding a negative-type photosensitive resin composition containing a colorant), The alkali-soluble resin (A) is represented by the following formula (1): 【Chemistry 1】 (In general formula (1), X represents a tetravalent organic group, Y represents a divalent organic group, and n represents an integer.) and a polyamic acid having a number average molecular weight of less than 20,000, which has a repeating unit represented by the formula: the (B) photosensitizer contains an oxime-based photopolymerization initiator, the (C) crosslinking agent contains a polyfunctional primary thiol compound having two or more functional thiol groups in one molecule; A negative photosensitive resin composition comprising:

2. 2. The negative photosensitive resin composition according to claim 1, wherein the polyamic acid is derived from a compound in which an unsaturated carbon bond at a molecular chain terminal has a norbornene structure.

3. 3. The negative photosensitive resin composition according to claim 1, wherein the polyfunctional primary thiol compound has 2 to 6 thiol groups in one molecule.

4. 4. The negative photosensitive resin composition according to claim 1, wherein at least one organic group of X and Y in formula (1) has an ether bond (—O—).

5. 5. The negative photosensitive resin composition according to claim 1, wherein the polyamic acid has a number average molecular weight of more than 4,000 and not more than 10,000.

6. A dry film comprising a base film and a resin layer provided on at least one side of the base film, A dry film, wherein the resin layer is a product obtained by applying and drying the negative photosensitive resin composition according to any one of claims 1 to 5.

7. A cured product of the negative photosensitive resin composition according to any one of claims 1 to 5 or the resin layer of the dry film according to claim 6.

8. An electronic component comprising the cured product according to claim 7.

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