TW201708957A - Negative photosensitive resin composition, cured film, method for producing cured film, and semiconductor device - Google Patents

Abstract

The present invention provides a negative photosensitive resin composition having a wide exposure latitude, a cured film, a method for producing a cured film, and a semiconductor device. A negative photosensitive resin composition comprising: a polyimide intermediate; a radical polymerization initiator; a first polymerization inhibitor selected from at least one of a compound having an aromatic hydroxyl group; and a second polymerization The inhibitor is at least one selected from the group consisting of a nitroso compound, an N-oxide compound, an anthracene compound, an N-oxyl compound, and a phenothiazine compound.

Description

Negative photosensitive resin composition, cured film, method for producing cured film, and semiconductor device

The present invention relates to a negative photosensitive resin composition, a cured film, a method for producing a cured film, and a semiconductor device. In particular, there is a negative photosensitive resin composition suitable for an interlayer insulating film for a rewiring layer.

The thermosetting resin which is cyclized and cured by polyimine or the like is excellent in heat resistance and insulating properties, and is used for an insulating layer of a semiconductor element or the like.

Here, since the polyimine has low solubility in a solvent, it is used in the state of a precursor (the heterocyclic-containing polymer precursor) before a cyclization reaction, and is applied to a substrate or the like, and then heated and contained. The heterocyclic polymer precursor is cyclized to form a cured film. Patent Document 1 discloses a negative photosensitive resin composition containing (A) having the following general formula (1) as a photosensitive resin composition using such a polyimide precursor; [Chemical 1] (In the formula (1), X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n is an integer of 2 to 150, and R ₁ and R ₂ are each independently a hydrogen atom, and are represented by the following formula: (2): [Chemical 2] (wherein R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10), or a carbon number of 1 a saturated aliphatic group of ～4; wherein, in the case where both of R _{1 1} and R _{2 2} are simultaneously a hydrogen atom, the polyimine precursor of the structure represented by: 100 parts by mass; (B) photopolymerization Starting agent: 1 part by mass to 20 parts by mass; and (C) a monocarboxylic acid compound having 2 to 30 carbon atoms having one or more functional groups selected from the group consisting of a hydroxyl group, an ether group and an ester group: 0.01 parts by mass to 10 parts by mass.

On the other hand, Patent Document 2 describes a negative photosensitive material containing an aerobic polymerization inhibitor and an anaerobic polymerization inhibitor. [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-191749 (Patent Document 2) International Publication No. WO2010/008514

[Problems to be Solved by the Invention] When used as an interlayer insulating film for a rewiring layer of a semiconductor, etc., it is required that a suitable exposure range of a negative photosensitive resin composition is broad, that is, a wide exposure latitude. A negative photosensitive resin composition. However, the negative photosensitive resin compositions described in Patent Document 1 and Patent Document 2 have a narrow exposure latitude. Here, in Patent Document 2, there is a description about high image resolution. However, there is neither description nor teaching regarding an image in which sharpness having a good edge is obtained with a wide range of exposure energy. The present invention has been made to solve the above problems, and an object of the invention is to provide a negative photosensitive resin composition, a cured film, a cured film, and a semiconductor device having a wide exposure latitude. [Means for solving the problem]

Based on the above-mentioned problems, the inventors have found that the exposure latitude of the negative photosensitive resin composition can be obtained by using a polyimide precursor having a predetermined structure in the negative photosensitive resin composition. The problem has been solved by broadening the scope. Specifically, the above problem is solved by the following <1>, preferably by <2> to <19>. <1> A negative photosensitive resin composition comprising: a polyimine precursor; a radical polymerization initiator; a first polymerization inhibitor selected from at least one of a compound having an aromatic hydroxyl group; The second polymerization inhibitor is at least one selected from the group consisting of a nitroso compound, an N-oxide compound, an anthracene compound, an N-oxyl compound, and a phenothiazine compound. The negative photosensitive resin composition as described in <1>, wherein the polyimine precursor contains a repeating unit represented by the following general formula (1); general formula (1) [Chemical 3] In the formula (1), A ¹ and A ² each independently represent an oxygen atom or -NH-, R ¹¹ represents a divalent organic group, R ^{1 2} represents a tetravalent organic group, and R ¹³ and R ¹⁴ are each independently Represents a hydrogen atom or a monovalent organic group. <3> The negative photosensitive resin composition according to <2>, wherein, in the formula (1), at least one of R ¹³ and R ¹⁴ includes a radical polymerizable group. The negative photosensitive resin composition as described in any one of <1> which further contains a radically polymerizable compound. <5> The negative photosensitive resin composition as described in <4>, wherein the radically polymerizable compound has two or more radical polymerizable groups. The negative photosensitive resin composition according to any one of <1> to <5> wherein the second polymerization inhibitor is selected from the group consisting of an anthracene compound and an N-oxyl compound. The negative photosensitive resin composition according to any one of the above aspects, wherein the mass ratio of the first polymerization inhibitor to the second polymerization inhibitor is from 10:90 to 90:10. The negative photosensitive resin composition according to any one of the above aspects, wherein the mass ratio of the first polymerization inhibitor to the radical polymerization initiator is 1:99 to 10:90 . <9> The <1> to <8> negative photosensitive resin composition as claimed in any one of the general formula (1), R ^{1 2} is a tetravalent group containing an aromatic ring. The negative photosensitive resin composition as described in any one of <1> which further contains a thermal base generator. <11> The negative photosensitive resin composition according to <10>, wherein the thermal base generating agent has an ammonium cation represented by the following general formula (Y); In the general formula (Y), Ar ¹⁰ represents an aromatic group, and R ¹¹ to R ¹⁵ each independently represent a hydrogen atom or a hydrocarbon group, and R ^{1 4} and R ¹⁵ may bond each other to form a ring, and n represents an integer of 1 or more. The negative photosensitive resin composition as described in any one of <1> to <11> which is used for the interlayer insulation film for rewiring layers. <13> A cured film obtained by curing the negative photosensitive resin composition according to any one of <1> to <12>. <14> The cured film according to <13>, which is an interlayer insulating film for a rewiring layer. <15> A method for producing a cured film, comprising the negative photosensitive resin composition according to any one of <1> to <12>. <16> The method for producing a cured film according to <15>, comprising: a step of applying a negative photosensitive resin composition to a substrate; and irradiating the negative photosensitive resin composition on the substrate with actinic light a step of exposing the radiation or radiation; and a step of developing the exposed negative photosensitive resin composition. <17> The method for producing a cured film according to <16>, comprising the step of heating the developed negative photosensitive resin composition at a temperature of from 50 ° C to 500 ° C after the step of performing the development treatment . The method for producing a cured film according to any one of the above aspects, wherein the cured film has a film thickness of from 3 μm to 30 μm. <19> A cured film produced by the method according to any one of <15> to <18>, or a cured film produced by the method according to any one of <15> to <18>. [Effects of the Invention]

According to the present invention, it is possible to provide a negative photosensitive resin composition, a cured film, a method for producing a cured film, and a semiconductor element having a wide exposure latitude.

The description of the constituent elements of the present invention described below may be carried out based on representative embodiments of the present invention, but the present invention is not limited to such an embodiment. In the expression of the group (atomic group) in the present specification, the substituted and unsubstituted expressions are not described as including a group having no substituent (atomic group), and also a group having a substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In the present specification, "actinic ray" means, for example, a bright line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, an extreme ultraviolet ray (Extreme Ultraviolet (EUV) light), an X-ray, an electron beam, or the like. . Further, in the present invention, light means actinic rays or radiation. The "exposure" in this specification includes exposure using a mercury lamp, a far-ultraviolet light represented by a quasi-molecular laser, X-rays, EUV light, etc., using a particle beam such as an electron beam or an ion beam, unless otherwise specified. The depiction is also included in the exposure. In the present specification, the numerical range expressed by "~" means a range including the numerical values described before and after "~" as the lower limit and the upper limit. In the present specification, "(meth) acrylate" means either or both of "acrylate" and "methacrylate", and "(meth)allyl" means "allyl" and "(meth)acrylic acid" means either or both of "acrylic" and "methacrylic acid", "(meth)acrylic acid" "It means either or both of "acryloyl thiol" and "methacryl fluorenyl". In the present specification, the term "step" means not only an independent step, but even if it cannot be clearly distinguished from other steps, it is included in the term as long as the intended effect of the step is achieved. In the present specification, the solid content concentration means the mass percentage of the mass of the components other than the solvent with respect to the total mass of the composition. Further, the solid content concentration means a concentration at 25 ° C unless otherwise specified. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene-converted values measured by gel permeation chromatography (GPC) unless otherwise specified. . In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be, for example, by using HLC-8220 (manufactured by Tosoh Co., Ltd.), and the protective column HZ-L, TSKgel Super HZM -M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation) were used as the pipe string. Unless otherwise specified, the solution was measured using tetrahydrofuran (THF). Further, unless otherwise stated, the detection was performed using an ultraviolet (UV (ultraviolet)) 254 nm detector.

Negative photosensitive resin composition The negative photosensitive resin composition of the present invention is characterized by comprising: a polyimine precursor; a radical polymerization initiator; and a first polymerization inhibitor selected from the group consisting of aromatic hydroxyl groups At least one of the compounds; and a second polymerization inhibitor selected from at least one of a nitroso compound, an N-oxide compound, an anthracene compound, an N-oxyl compound, and a phenothiazine compound. With such a configuration, a negative photosensitive resin composition having a wide exposure latitude can be obtained. The negative photosensitive resin composition containing the polyimide precursor is hardened by exposure, but by blending two polymerization inhibitors, mainly on the side close to the surface layer, mainly the first polymerization inhibitor acts on the film. On the side away from the surface layer, the second polymerization inhibitor is mainly used, and as a result, the polymerization inhibitory effect of the negative photosensitive resin composition layer is substantially uniform, and the exposure latitude can be broadened. In particular, it is advantageous in the case where the difference in the manner of irradiation of light is large and the film thickness is large. Further, the resin used in the examples of Patent Document 2 is an acrylic resin, and there is a problem in terms of heat resistance. However, in the present invention, since a polyimide precursor is used, heat resistance can be formed. Excellent.

<Polyimine precursor> The negative photosensitive resin composition of the present invention contains a polyimide precursor. The polyimine precursor may be used alone or in combination of two or more. The polyimine precursor is preferably a polyimine precursor comprising a repeating unit represented by the formula (1). General formula (1) [Chemical 5] In the formula (1), A ¹ and A ² each independently represent an oxygen atom or -NH-, R ¹¹ represents a divalent organic group, R ¹² represents a tetravalent organic group, and R ¹³ and R ¹⁴ are each independently represented. A hydrogen atom or a monovalent organic group.

A ¹ and A ² each independently represent an oxygen atom or -NH-, preferably an oxygen atom.

R ¹¹ represents a divalent organic group. The divalent organic group may, for example, be a linear or branched aliphatic group, a cyclic aliphatic group or a group containing an aryl group, preferably a linear or branched aliphatic group having 2 to 20 carbon atoms, and carbon. The cyclic aliphatic group having 6 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, or a group containing the combination thereof is more preferably a group containing an aryl group having 6 to 60 carbon atoms. Examples of the aryl group include the following.

[Chemical 6] In the formula, A is preferably a single bond or a hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) ₂ - and -NHCO-, and a group in the combination of these, more preferably a single bond, selected from alkyl groups having 1 to 3 carbon atoms which may be substituted by a fluorine atom, -O-, -C(=O)- a group in -S-, -SO ₂ -, and more preferably selected from -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) The divalent group in ₂ -.

Specifically, R ¹¹ may, for example, be a diamine residue or the like remaining after removal of an amine group of the following diamine. Selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane or 1,4-diamine Cyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane, Bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophorone II Amine; m-phenylenediamine and p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl and 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl Ether and 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4,4'-diaminodi Phenylhydrazine and 3,3'-diaminodiphenylphosphonium, 4,4'-diaminodiphenyl sulfide and 3,3'-diaminodiphenyl sulfide, 4,4'- Diaminobenzophenone and 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl- 4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-amine Phenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxyl 4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoro Propane, bis(3-amino-4-hydroxyphenyl)anthracene, bis(4-amino-3-hydroxyphenyl)anthracene, 4,4'-diaminolated terphenyl, 4,4'-double (4-Aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]anthracene, bis[4-(3-aminophenoxy)phenyl]indole, bis[ 4-(2-Aminophenoxy)phenyl]anthracene, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3 '-Dimethyl-4,4'-diaminodiphenylanthracene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene , 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminophenoxy)benzene, 3,3'-diethyl-4,4'-diaminodi Phenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diamino octafluorobiphenyl, 2,2-bis[4-(4- Aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10 -hydroquinone, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4 '-tetraaminodiphenyl ether, 1,4-diamino hydrazine, 1,5-diamino hydrazine, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9, 9'-bis(4-aminophenyl)anthracene, 4,4'-dimethyl-3,3'-diaminodiphenylanthracene, 3,3',5,5'-tetramethyl- 4,4'-diaminodiphenylmethane, 2,4-diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetamide , 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldioxane, An ester of 2,7-diaminopurine, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzilide, diaminobenzoic acid, 1,5-Diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecfluoroheptane, 2,2-bis[4-(3-amine Phenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminobenzene) Oxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl] Hexafluoropropane, pair of double ( 4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis (4 -amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylanthracene, 4,4'-double (3-Amino-5-trifluoromethylphenoxy)diphenylphosphonium, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoro Propane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4, 4'-Diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotoluidine and 4,4'-diamine At least one of the base tetrabens.

Further, examples of the diamine residue remaining after the removal of the amine group of the diamine (DA-1) to the diamine (DA-18) shown below are exemplified as R ¹¹ .

[Chemistry 7]

[化8]

Further, examples of the diamine residue remaining after the removal of the amine group of the diamine having two or more alkanediol units in the main chain are exemplified as R ¹¹ . It is preferably a diamine residue containing one or both of two or more ethylene glycol chains and propylene glycol chains in one molecule, more preferably a diamine residue containing no aromatic ring. As an example, Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D- can be cited. 2000, D-4000 (above is the trade name, manufactured by HUNTSMAN (share)), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane- 2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, etc., but is not limited thereto. The structures of Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, and EDR-176 are shown below.

[Chemistry 9]

In the above, x, y, and z are average values.

In the formula (1), R ^{1 2} represents a tetravalent organic group, preferably a tetravalent group containing an aromatic ring, more preferably from the following formula (1-1) or formula (1-2) The base represented.

General formula (1-1) [Chemical 10] In the formula (1-1), R ^{112 is} preferably a single bond or a hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ - And -NHCO-, and a group in the combination of these, more preferably a single bond, or an alkylene group having from 1 to 3 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S- And a divalent group in -SO ₂ -, more preferably selected from -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, - A divalent group in the group consisting of S- and -SO ₂ -.

General formula (1-2) [Chemical 11]

R ^{1 2} may, for example, be a tetracarboxylic acid residue remaining after removing an anhydride group from a tetracarboxylic dianhydride. Specifically, a tetracarboxylic acid residue or the like remaining after removing an anhydride group from the following tetracarboxylic dianhydride can be mentioned. Selected from pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic acid Acid dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4 , 4'-diphenylmethanetetracarboxylic dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid Anhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid Anhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl) Propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-decanetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-double (2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, and 1,2,3,4-benzenetetracarboxylic dianhydride And the alkane having 1 to 6 carbon atoms At least one tetracarboxylic dianhydride derivatives and derivative carbons, alkoxy of 1 to 6.

Further, the tetracarboxylic acid residue remaining after removing the anhydride group from the tetracarboxylic dianhydride (DAA-1) to the tetracarboxylic dianhydride (DAA-5) shown below may be mentioned as R ^{1 2} . example. [化12]

From the viewpoint of the solubility of the alkaline developer, R ^{1 2} preferably has an OH group. More specifically, examples of R ^{1 2} include a tetracarboxylic acid residue remaining after the anhydride group is removed from the above (DAA-1) to (DAA-5).

In the formula (1), R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a monovalent organic group. As the monovalent organic group represented by R ¹³ and R ¹⁴ , a substituent which enhances the solubility to the developer can be preferably used.

From the viewpoint of the solubility of the aqueous developing solution, R ¹³ and R ¹⁴ are a hydrogen atom or a monovalent organic group, and as the monovalent organic group, one or two having a carbon atom bonded to the aryl group may be mentioned. One or three, preferably one, an acidic aryl group, an aralkyl group or the like. Specific examples thereof include an aryl group having 6 to 20 carbon atoms having an acidic group and an aralkyl group having 7 to 25 carbon atoms having an acidic group. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group are exemplified. The acidic group is preferably an OH group. In terms of solubility in an aqueous developing solution, R ¹³ and R ¹⁴ are preferably a hydrogen atom, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group or a 4-hydroxybenzyl group.

From the viewpoint of the solubility of the organic solvent, R ¹³ and R ^{14 are} preferably a monovalent organic group. The monovalent organic group is preferably an alkyl group, a cycloalkyl group, an aryl group, more preferably an aryl group-substituted alkyl group. The alkyl group preferably has 1 to 30 carbon atoms. The alkyl group may be any of a straight chain, a branched chain, and a cyclic chain. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a dodecyl group, and a tetradecyl group. Octadecyl, isopropyl, isobutyl, t-butyl, tert-butyl, 1-ethylpentyl, and 2-ethylhexyl. The cyclic alkyl group (cycloalkyl group) may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. Examples of the monocyclic cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic cycloalkyl group include an adamantyl group, a norbornyl group, a borneyl group, a nonenyl group, a decahydronaphthyl group, a tricyclodecylalkyl group, a tetracyclodecyl group, a fluorenyl group, and a second group. Cyclohexyl, and decenyl. Among them, from the viewpoint of coexistence with high sensitivity, the cyclohexyl group is most preferable. Further, the alkyl group substituted with an aryl group is preferably a linear alkyl group substituted with an aryl group described later. As the aryl group, specifically, a substituted or unsubstituted benzene ring, a naphthalene ring, a pentylene ring, an anthracene ring, an anthracene ring, a heptene ring, a terpene ring, an anthracene ring, a fused pentabenzene ring, Ethane naphthalene (acenaphthene) ring, phenanthrene ring, anthracene ring, thick tetraphenyl ring, Ring, triphenylene, anthracene, biphenyl, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, pyridazine Ring, anthracene ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolizine ring, quinoline ring, pyridazine ring, naphthyridine ring, quinoxaline ring, quinoxaline ring, different Quinoline ring, carbazole ring, phenazin ring, acridine ring, phenanthroline ring, thioxan ring, benzopyran ring, xanthene ring, morphine ring, phenothiazine ring or phenazine ring. The best is the benzene ring.

Examples of the polymerizable group of R ¹³ and R ¹⁴ include an epoxy group, an oxetanyl group, a group having an ethylenically unsaturated bond, a blocked isocyanate group, an alkoxymethyl group, and a hydroxymethyl group. Amine and the like. In the present invention, a preferred embodiment of R ¹³ and R ^{14 is} a form containing a radical polymerizable group, and more preferably a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, and a group represented by the following formula (III).

[Chemistry 13]

In the formula (III), R ²⁰⁰ represents hydrogen or a methyl group, more preferably a methyl group. In the formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH(OH)CH ₂ - or a polyoxyalkylene group having 4 to 30 carbon atoms. Examples of suitable R ²⁰¹ include an exoethyl group, a propyl group, a trimethylene group, a tetramethylene group, a 1,2-butanediyl group, a 1,3-butanediyl group, a pentamethylene group, and a hexamethylene group. Further, octamethylene, dodecamethylene, -CH ₂ CH(OH)CH ₂ -, more preferably ethyl, propyl, trimethylene, -CH ₂ CH(OH)CH ₂ -. Particularly preferably, R ²⁰⁰ is a methyl group and R ²⁰¹ is a stretching ethyl group.

When R ¹³ and R ¹⁴ in the formula (1) contain a polymerizable group (preferably a radical polymerizable group), the polymerizable group: a molar group containing no polymerizable group is preferably 100:0 to 5: 95, more preferably 100:0 to 20:80, and even more preferably 100:0 to 50:50.

When in the formula (1), A ² is an oxygen atom and R ¹³ is a hydrogen atom, or / and A ¹ is an oxygen atom and R ¹⁴ is a hydrogen atom, it may also be a tertiary stage having an ethylenically unsaturated bond. The amine compound forms a counter salt. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

Further, in the case of performing alkali development, the polyimine precursor preferably has a fluorine atom in the structural unit in terms of improving the resolution. By the fluorine atom, water repellency can be imparted to the surface of the film at the time of alkali development, thereby suppressing penetration from the surface and the like. The content of the fluorine atom in the polyimide precursor is preferably 10% by mass or more, and is preferably 20% by mass or less in terms of solubility in the alkaline aqueous solution.

Further, for the purpose of improving the adhesion to the substrate, the polyimide precursor may also copolymerize an aliphatic group having a decane structure. Specific examples of the diamine component include bis(3-aminopropyl)tetramethyldioxane and bis(p-aminophenyl)octamethylpentaoxane.

Further, in order to enhance the storage stability of the negative photosensitive resin composition, the polyimide precursor is preferably a host using a terminal blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monofluorinated chlorine compound or a monoactive ester compound. The end of the chain is closed. Among these, it is more preferred to use a monoamine. Preferred examples of the monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, and 1-hydroxy-7-amine. Naphthyl, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-amine Naphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-amine Naphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylide Acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6 - Dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, and the like. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of blocking agents.

The polyimine precursor used in the present invention may further comprise a repeating unit represented by the formula (1) and other repeating units as other quinone imine precursors. When other repeating units are included, the proportion of other repeating units in the polyimide intermediate is preferably from 1 mol% to 60 mol%, more preferably from 5 mol% to 50 mol%.

The negative photosensitive resin composition of the present invention may be configured to substantially contain no polyimine precursor other than the polyimine precursor including the repeating unit represented by the general formula (1). The content of the other polyimide intermediate precursor contained in the negative photosensitive resin composition of the present invention is 3% by mass or less of the content of the polyimide precursor.

The weight average molecular weight (Mw) of the polyimide precursor is preferably from 20,000 to 28,000, more preferably from 22,000 to 27,000, still more preferably from 23,000 to 25,000. The degree of dispersion (Mw/Mn) of the polyimide precursor is not particularly limited, but is preferably 1.0 or more, more preferably 2.5 or more, still more preferably 2.8 or more. The upper limit of the degree of dispersion of the polyimide precursor is not particularly limited, and is preferably 4.5 or less, and may be 3.4 or less.

The content of the polyimine precursor in the negative photosensitive resin composition of the present invention is preferably 20% by mass to 100% by mass, and more preferably 50% by mass based on the total solid content of the negative photosensitive resin composition. From 9% to 99% by mass, more preferably from 60% by mass to 99% by mass, particularly preferably from 70% by mass to 99% by mass.

<Other Resin Component> The negative photosensitive resin composition of the present invention may contain other resin components within a range not departing from the gist of the present invention. Examples of the other resin component include a polybenzoxazole precursor and a polyimide resin. Further, in the present invention, a configuration in which a resin other than the polyimide precursor is substantially not contained may be used. The content of the resin other than the polyimine precursor contained in the negative photosensitive resin composition of the present invention is 3% by mass or less of the content of the polyimide precursor.

<Radical Polymerization Starter> The negative photosensitive resin composition of the present invention contains a radical polymerization initiator. The radical polymerization initiator can be negatively developed by starting polymerization of a radical polymerizable group which the polyimide precursor precursor can have, or a polymerization of a radical polymerizable compound described later. The radical polymerization initiator may be a photoradical polymerization initiator or a thermal radical polymerization initiator, but is preferably a photoradical polymerization initiator. More specifically, when a negative-type photosensitive resin composition is applied to a semiconductor wafer or the like to form a layered composition layer, light is irradiated, whereby hardening by radicals occurs, and the light irradiation portion can be The solubility is reduced. Therefore, for example, the composition layer is exposed through a photomask having a pattern covering only the electrode portions, whereby it is possible to easily produce regions having different solubility depending on the pattern of the electrodes.

The photoradical polymerization initiator is not particularly limited as long as it has a polymerization reaction (crosslinking reaction) such as a radical polymerizable compound, and can be suitably selected from known photoradical polymerization initiators. . For example, it is preferred that the light from the ultraviolet region to the visible region is photosensitive. Alternatively, it may be an active agent that produces a reactive radical with a certain effect on the photoexcited sensitizer. The photoradical polymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 in the range of from about 300 nm to 800 nm, preferably from 330 nm to 500 nm. The molar absorption coefficient of the compound can be determined by a known method. For example, it is preferably measured by a UV-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Co., Ltd.) using an ethyl acetate solvent at a concentration of 0.01 g/L.

As a photoradical polymerization initiator, a known compound can be used without limitation, and examples thereof include a halogenated hydrocarbon derivative (for example, a triazine skeleton, a oxadiazole skeleton, a trihalomethyl group, etc.), a mercaptophosphine compound such as a mercaptophosphine oxide, an antimony compound such as a hexaarylbiimidazole or an anthracene derivative, an organic peroxide, a sulfur compound, a ketone compound, an aromatic onium salt, a ketoxime ether, an aminoacetophenone compound, Hydroxyacetophenone, azo compound, azide compound, metallocene compound, organoboron compound, iron aromatic hydrocarbon complex, and the like.

Examples of the halogenated hydrocarbon derivative having a triazine skeleton include a compound described in Japanese Society of Chemical Engineering (Bull. Chem. Soc. Japan), 42, 2924 (1969), and British Patent No. 1,888,492. A compound described in the specification, a compound described in JP-A-53-133428, a compound described in the specification of German Patent No. 3337024, and an organic chemical journal (J. Org. Chem, FC Schaefer, etc.) The compound described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The compound described in the publication No. 34920, and the compound described in the specification of U.S. Patent No. 4,212,976.

Examples of the compound described in the specification of U.S. Patent No. 4,212,976 include compounds having an oxadiazole skeleton (e.g., 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2- Trichloromethyl-5-(4-chlorophenyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(1-naphthyl)-1,3,4-oxadiazole , 2-trichloromethyl-5-(2-naphthyl)-1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2 -Tribromomethyl-5-(2-naphthyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2- Trichloromethyl-5-(4-chlorostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-methoxystyryl)-1,3, 4-oxadiazole, 2-trichloromethyl-5-(1-naphthyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-n-butoxystyrene Base)-1,3,4-oxadiazole, 2-tribromomethyl-5-styryl-1,3,4-oxadiazole, etc.).

Further, examples of the photoradical polymerization initiator other than the above include an acridine derivative (for example, 9-phenyl acridine, 1,7-bis(9,9'-acridinyl)heptane, etc.). , N-phenylglycine, etc., polyhalogen compounds (such as carbon tetrabromide, phenyltribromomethylhydrazine, phenyltrichloromethyl ketone, etc.), coumarins (such as 3-(2-benzene) And furanyl)-7-diethylamino coumarin, 3-(2-benzofuranyl)-7-(1-pyrrolidyl)coumarin, 3-benzylidene- 7-Diethylamino coumarin, 3-(2-methoxybenzimidyl)-7-diethylamino coumarin, 3-(4-dimethylaminobenzimidyl )-7-diethylamino coumarin, 3,3'-carbonyl bis(5,7-di-n-propoxycoumarin), 3,3'-carbonyl bis(7-diethylamine) Ketocoumarin), 3-benzylidene-7-methoxycoumarin, 3-(2-furanyl)-7-diethylaminocoumarin, 3-(4-di Ethylamino cinnamonyl)-7-diethylamino coumarin, 7-methoxy-3-(3-pyridylcarbonyl)coumarin, 3-benzylidene-5,7- Dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, and Japanese Patent Laid-Open No. Hei 5-19475, Japanese Patent Laid-Open The incense described in Japanese Patent Laid-Open No. 2002-363206, Japanese Patent Laid-Open Publication No. 2002-363207, Japanese Patent Laid-Open Publication No. 2002-363208, and Japanese Patent Laid-Open Publication No. 2002-363209 Bean-based compounds, etc., fluorenylphosphine oxides (for example, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, bis(2,6-dimethoxybenzylidene) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc., metallocenes (for example, as described in Paragraph No. 0076 of JP-A-2011-13602) Titanocene compound, bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, η5- Cyclopentadienyl-η6- cumenyl-iron (1+)-hexafluorophosphate (1-), etc., Japanese Patent Laid-Open No. Sho 53-133428, Japanese Patent Publication No. Sho 57-1819, The compound described in Japanese Patent Publication No. Sho 57-6096, and the specification of U.S. Patent No. 3,615,455.

Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, and 4-methoxybenzophenone. 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenone tetracarboxylic acid Or a tetramethyl ester thereof, 4,4'-bis(dialkylamino)benzophenone (for example, 4,4'-bis(dimethylamino)benzophenone, 4,4'-double (dicyclohexylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dihydroxyethylamino)benzophenone, 4 -Methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone), 4-dimethyl Aminoacetophenone, benzophenone, anthracene, 2-tert-butylhydrazine, 2-methylindole, phenanthrenequinone, xanthone, thioxanthone, 2-chloro-thiaxanthone , 2,4-Diethylthianone, anthrone, 2-benzyl-dimethylamino-1-(4-morpholinylphenyl)-1-butanone, 2-methyl-1 -[4-(Methylthio)phenyl]-2-morpholinyl-1-propanone, 2-hydroxy-2-methyl-[4-(1-methylvinyl)phenyl]propanol , benzoin, benzoin ethers (eg, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloroacridone, N- Acridine, N-butylacridone, N-butyl-chloroacridone, and the like. In the commercial product, Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be suitably used.

As the photoradical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a mercaptophosphine compound can also be suitably used. More specifically, for example, an amino acetophenone-based initiator as described in JP-A-10-291969, and a sulfhydryl phosphine oxide-based initiator described in Japanese Patent No. 4,258,899 can be used. As a hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, Yanjia can be used. IRGACURE-127 (trade name: all manufactured by BASF). As the aminoacetophenone-based initiator, IRGACURE-907, IRGACURE-369, and IRGACURE-379 can be used as commercially available products (trade name: Made for BASF). IRGACURE is a registered trademark. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179, which has an absorption wavelength matched with a light source of 365 nm or 405 nm, can also be used. As the mercaptophosphine-based initiator, IRGACURE-819 or DAROCUR-TPO (trade name: all manufactured by BASF) can be used as a commercial product.

As the photoradical polymerization initiator, a ruthenium compound is more preferable. As a specific example of the oxime-based initiator, a compound described in JP-A-2001-233842, a compound described in JP-A-2000-80068, and JP-A-2006-342166 can be used. The compound described. Preferred examples of the hydrazine compound include 3-benzylideneoxyimidobutan-2-one, 3-ethyloxyiminobutane-2-one, and 3-propoxycarbonyl group. Iminobutan-2-one, 2-ethyloxyiminopentan-3-one, 2-ethyloxyimino-1-phenylpropan-1-one, 2-phenyl Nonyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimido -1-Phenylpropan-1-one and the like.

As the ruthenium compound, "JCS Perkin II" (JCS Perkin II) (1979) pp. 1653-1660, "British Chemical Society, Berkin Journal II" (1979) Pp. 156-162, and the compounds described in "Journal of Photopolymer Science and Technology" (1995) pp. 202-232, and Japanese Patent Laid-Open No. 2000-66385, The compounds described in each of the publications of Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open Publication No. 2004-534797, and Japanese Patent Laid-Open No. Hei. No. 2006-342166. Among the commercially available products, IRGACURE-OXE01 (BASF), IRGACURE-OXE02 (BASF), N-1919 (Adi) can also be suitably used. ADEKA company).

In addition, the compound described in Japanese Patent Laid-Open Publication No. 2009-519904, which is linked to the N-position of the carbazole ring, and the U.S. Patent No. 7,626,957, the disclosure of which is incorporated herein by reference. The compound described in Japanese Patent Laid-Open Publication No. 2010-15025, and the ketone-based compound described in WO2009/131189, A compound described in Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Wait. In addition, the cyclic anthraquinone compound described in JP-A-2007-2320, and JP-A-2007-322744 can also be suitably used. Among the cyclic ruthenium compounds, the cyclic ruthenium compound condensed in the carbazole dye described in Japanese Patent Laid-Open Publication No. 2010-185072, and the Japanese Patent Publication No. 2010-185072, has high light absorbing properties. It is preferable from the viewpoint of high sensitivity. In addition, a compound described in JP-A-2009-242469, which is a compound having an unsaturated bond at a specific site of a ruthenium compound, can be suitably used. Further, an anthracene compound having a fluorine atom can also be used. Specific examples of such a starter include the compound described in JP-A-2010-262028, and the compound 24 and the compound 36 described in paragraph 0345 of JP-A-2014-500852. The compound (C-3) described in Paragraph No. 0101 of JP-A-2013-164471. Specific examples thereof include the following compounds. [Chemistry 14] The ruthenium compound having a specific substituent as shown in Japanese Laid-Open Patent Publication No. 2007-269779, or the thioaryl group shown in Japanese Patent Laid-Open Publication No. 2009-191061肟 compounds, etc.

From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably selected from the group consisting of a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, Mercaptophosphine compound, phosphine oxide compound, metallocene compound, hydrazine compound, triallyl imidazole dimer, hydrazine compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentane A compound of the group consisting of a diene-benzene-iron complex and a salt thereof, a halomethyl oxadiazole compound, and a 3-aryl-substituted coumarin compound. More preferably, it is a trihalomethyltriazine compound, an α-amino ketone compound, a mercaptophosphine compound, a phosphine oxide compound, an anthraquinone compound, a triaryl imidazole dimer, an anthraquinone compound, a benzophenone compound, an acetophenone compound. More preferably, it is a trihalomethyltriazine compound, an α-aminoketone compound, an anthraquinone compound, a triaryl imidazole dimer, or a benzophenone compound, and is preferably an anthracene compound.

The content of the radical polymerization initiator is preferably from 0.1% by mass to 30% by mass, more preferably from 0.1% by mass to 20% by mass, even more preferably 0.1% by mass based on the total solid content of the negative photosensitive resin composition. % to 10% by mass. In addition, it is preferably contained in an amount of from 1 part by mass to 20 parts by mass, more preferably from 3 parts by mass to 10 parts by mass, per 100 parts by mass of the radical polymerization initiator. The radical polymerization initiator may be used alone or in combination of two or more. When the number of radical polymerization initiators is two or more, it is preferred that the total is in the above range.

<First polymerization inhibitor> The negative photosensitive resin composition of the present invention contains a first polymerization inhibitor selected from at least one of compounds having an aromatic hydroxyl group. With respect to such a polymerization inhibitor, the polymerization inhibitory effect of the compound having a radical polymerizable group is strong mainly in the presence of oxygen.

The compound having an aromatic hydroxyl group is preferably a compound represented by the formula (101). Formula (101) [Chem. 15] In the formula (101), m represents an integer of 1 to 5, n represents an integer of 1 to 4, and n of R ¹⁰¹ each independently represent a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a cyano group, or the like. a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, or a carbon number of 1 to 5 The alkynyl group may be bonded via a benzene ring represented by the formula (101) to a linking group, and examples of the linking group include a carbonyl group, a carbonyloxy group (-COO-), and an oxycarbonyl group (-OCO-). , thio, sulfonyl, sulfinyl, oxy, imino (-NH-), decylamino, alkyl 1 to 6 alkyl, aryl 6 to 12, phosphine A polyvalent heterocyclic group, an alkylamine group, and a 3-membered to 8-membered ring of an acid ester group, a phosphate group, and a heterocyclic ring such as a triazine or a dioxane. A multivalent linking group from a combination of such linking groups. Further, two or more groups represented by R ¹⁰¹ may be bonded to each other to form a ring structure.

The group represented by R ¹⁰¹ may have a substituent on a carbon atom which can be introduced. The substituent which can be introduced may, for example, be an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a cyano group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), an amine group, an alkylamine group or an alkoxy group. And (meth) acrylonitrile and the like.

X ¹⁰¹ does not exist when m is 1, and represents a m-valent linking group when m is 2 or more, and specific examples thereof include a single bond, a carbonyl group, a carbonyloxy group, a thio group, a sulfonyl group, and a sulfinyl group. , an oxy group, a phosphonate group, an alkylene group having 1 to 6 carbon atoms, an extended aryl group having 6 to 12 carbon atoms, an imine group, and an aliphatic hydrocarbon group having 1 to 6 carbon atoms obtained by removing m hydrogen atoms. An m-valent aromatic hydrocarbon group having 6 to 12 carbon atoms obtained by removing m hydrogen atoms, and a 6-membered ring to 12-membered ring obtained by removing m hydrogen atoms from a heterocyclic ring such as triazine or dioxane. The ring group, a combination of these linking groups, and the like may have a substituent on a carbon atom which can be introduced. The substituent is preferably the same substituent as R ¹⁰¹ .

In the formula (101), when m is 1, it is of course not bonded to the group X ¹⁰¹ . In this case, a monovalent substituent may be substituted for X ¹⁰¹ , and as the monovalent substituent, the same group as R ¹⁰¹ may be exemplified, or a ring structure may be bonded to R ¹⁰¹ substituted on the benzene ring to form a ring structure. It can also be bonded via a benzene ring and a linking group.

Specific examples of the first polymerization inhibitor include 4-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, and pentaerythritol tetra[3-(3,5-di- Tributyl-4-hydroxyphenyl)propionate], thiodiethylidene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 18 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, N,N'-hexane-1,6-diyl bis[3-(3,5-di -T-butyl-4-hydroxyphenyl)propanamine],3,3',3'',5,5',5''-hexa-t-butyl-a,a',a'' -(homotriene-2,4,6-triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, exoethyl bis(oxy-ethyl) bis[ 3-(5-t-butyl-4-hydroxym-tolyl)propionate], hexamethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoic acid Ester], 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H) -triketone, 2,6-di-t-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, catechol, Third butyl-catechol, 4,4',4''-(1-methylpropanil-3-ylidene)tris(6-tert-butyl-m-cresol), 6 ,6'-di-t-butyl-4,4'-butylene-m-cresol, 3 ,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propanoxy]-1,1-dimethylethyl]-2,4, 8,10-Tetraoxaspiro[5,5]undecane, hydroquinone, methyl hydroquinone, tert-butyl hydroquinone, di-tert-butyl-p-cresol, gallnut Phenol, 4,4-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), phenol resin Classes, and cresol resins. Further, an alkyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate is also exemplified as a preferred example. The alkyl ester of the alkyl ester herein preferably has a carbon number of 7 to 9. The content of the first polymerization inhibitor in the negative photosensitive resin composition is preferably 0.01% by mass to 5% by mass based on the total solid content of the negative photosensitive resin composition. The lower limit of the content of the first polymerization inhibitor is more preferably 0.02% by mass or more, and still more preferably 0.03% by mass or more. The upper limit is more preferably 3% by mass or less, still more preferably 1% by mass or less. The first polymerization inhibitor may be used alone or in combination of two or more. When the number of the first polymerization inhibitors is two or more, it is preferred that the total is in the above range.

<Second polymerization inhibitor> The negative photosensitive resin composition of the present invention contains at least one selected from the group consisting of a nitroso compound, an N-oxide compound, an anthracene compound, an N-oxyl compound, and a phenothiazine compound. 2 polymerization inhibitor. With respect to such a polymerization inhibitor, the polymerization inhibitory effect of the compound having a radical polymerizable group is strong mainly in the presence of non-oxygen.

As the nitroso compound of the second polymerization inhibitor, nitrosobenzene, 2-nitrosotoluene, 1,2,4,5-tetramethyl-3-nitrosobenzene, 4-nitrous acid can be exemplified. Phenol, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 4-nitroso-diphenylamine, 3,5-dibromo-4-nitrosobenzenesulfonate Acid, N-nitrosopyrrolidine, N-tert-butyl-N-nitrosoaniline, N-nitrosodimethylamine, N-nitrosodiethylamine, 1-nitrosopipe Pyridine, 4-nitrosomorpholine, N-nitroso-N-methylbutylamine, N-nitroso-N-ethylurea, N-nitrosohexamethyleneimine, N- Nitrosophenylhydroxylamine trivalent phosphonium salt and N-nitrosophenylhydroxylamine aluminum salt, 2,4,6-tris-tert-butyl-nitrosobenzene, N-nitrosodiphenyl amine.

As the N-oxide compound, phenyl-tert-butyl nitrone, 3,3,5,5-tetramethyl-1-pyrroline-N-oxide, 5,5-dimethyl- can be exemplified. 1-pyrroline N-oxide, 4-methylmorpholine N-oxide, pyridine N-oxide, 4-nitropyridine N-oxide, 3-hydroxypyridine N-oxide, picolinic acid N-oxidation , nicotinic acid N-oxide, and isonicotinic acid N-oxide.

As the ruthenium compound, p-benzoquinone, p-xyloquinone, p-formamidine, 2,6-dimethyl-1,4-benzoquinone, tetramethyl-1,4-benzoquinone, 2-tert-butyl-p-benzoquinone, 2,5-di-t-butyl-1,4-benzoquinone, 2,6-di-tris-1,4-benzoquinone, ruthenium herb, 2 ,5-di-third amyl phenylhydrazine, 2-bromo-1,4-benzoquinone, 2,5-dibromo-1,4-benzoquinone, 2,5-dichloro-1,4-benzoquinone , 2,6-dichloro-1,4-benzoquinone, 2-bromo-5-methyl-1,4-benzoquinone, tetrafluoro-1,4-benzoquinone, tetrabromo-1,4-benzoquinone , 2-chloro-5-methyl-1,4-benzoquinone, tetrachloro-1,4-benzoquinone, methoxy-1,4-benzoquinone, 2,5-dihydroxy-1,4-benzene Bismuth, 2,5-dimethoxy-1,4-benzoquinone, 2,6-dimethoxy-1,4-benzoquinone, 2,3-dimethoxy-5-methyl-1, 4-phenylhydrazine, tetrahydroxy-1,4-benzoquinone, 2,5-diphenyl-1,4-benzoquinone, 1,4-naphthoquinone, 1,4-quinone, 2-methyl-1 , 4-naphthoquinone, 5,8-dihydroxy-1,4-naphthoquinone, 2-hydroxy-1,4-naphthoquinone, 5-hydroxy-1,4-naphthoquinone, 5-hydroxy-2-methyl -1,4-naphthoquinone, 1-nitroindole, anthracene, 1-aminoindole, 1,2-benzopyrene, 1,4-diaminopurine, 2,3-dimethyl Base, 2-ethylhydrazine, 2-methylindole, 5,12-naphthacenequinone.

As the N-oxyl compound, 2,2,6,6-tetramethylpiperidine 1-oxyl, 4-cyano-2,2,6,6-tetramethylpiperidine 1-oxy group can be exemplified. 4-amino-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-carboxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-methoxy 2-,2,6,6-tetramethylpiperidine 1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-methylpropenyloxy -2,2,6,6-tetramethylpiperidine 1-oxyl, piperidinyl 1-oxyl radical, 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl Free radical, 4-acetamide-2,2,6,6-tetramethylpiperidine 1-oxyl radical, 4-m-butyleneimine-2,2,6,6-tetramethyl Piperidine 1-oxyl radical, and 4-phosphoniumoxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical, pyrrolidine 1-oxyl radical compound, 3- Carboxy proxyl radical (3-carboxy-2,2,5,5-tetramethylpyrrolidine 1-oxyl radical).

As the phenothiazine compound, phenothiazine, 10-methylphenothiazine, 2-methylthiophenothiazine, 2-chloromorphothazine, 2-ethylthiophenothiazine, 2-(three) can be exemplified. Fluoromethyl) phenothiazine, 2-methoxymorphothiazine.

In addition, since the compound which is a structure of any of the first polymerization inhibitor and the second polymerization inhibitor can exhibit polymerization inhibition in the vicinity of the surface layer of the film and in the inside of the film, it is regarded as a second polymerization inhibitor.

The second polymerization inhibitor is preferably selected from the group consisting of an anthracene compound and an N-oxyl compound. The content of the second polymerization inhibitor in the negative photosensitive resin composition is preferably 0.01% by mass to 5% by mass based on the total solid content of the negative photosensitive resin composition. The lower limit of the content of the second polymerization inhibitor is more preferably 0.02% by mass or more, and still more preferably 0.03% by mass or more. The upper limit is more preferably 3% by mass or less, still more preferably 1% by mass or less. The second polymerization inhibitor may be used alone or in combination of two or more. When the number of the second polymerization inhibitors is two or more, it is preferred that the total is in the above range.

<The ratio of the polymerization inhibitor> The mass ratio of the first polymerization inhibitor to the second polymerization inhibitor is not particularly limited, but is preferably from 1:99 to 99:1, more preferably from 90:10 to 10:90. More preferably, it is 70:30 to 30:70. By setting it as such a range, there exists a tendency for the exposure latitude to become wider. Further, in the present invention, a polymerization inhibitor other than the first polymerization inhibitor and the second polymerization inhibitor may be contained. Further, in the present invention, a configuration in which the polymerization inhibitor other than the first polymerization inhibitor and the second polymerization inhibitor is substantially not contained may be used. The amount of the other polymerization inhibitor contained in the polymerization inhibitor contained in the photosensitive resin composition of the present invention is 5% by mass or less based on the amount of all the polymerization inhibitors. Further, the mass ratio of the first polymerization inhibitor to the radical polymerization initiator is preferably from 0.01:99.99 to 20:80, more preferably from 1:99 to 10:90. By setting it as such a range, there exists a tendency for the exposure latitude to become wider.

<Radical Polymerizable Compound> The negative photosensitive resin composition of the present invention may contain a radically polymerizable compound other than the polyimide intermediate. By containing a radically polymerizable compound, a cured film having more excellent heat resistance can be formed. Further, pattern formation can be performed by photolithography. The radically polymerizable compound is preferably a compound having an ethylenically unsaturated bond, and more preferably a compound containing two or more ethylenically unsaturated groups. The radically polymerizable compound may be, for example, any of a chemical form such as a monomer, a prepolymer, an oligomer, a mixture thereof, or a polymer of the above.

In the present invention, the monomeric radically polymerizable compound (hereinafter also referred to as a radical polymerizable monomer) is a compound different from the polymer compound. The radical polymerizable monomer is typically a low molecular compound, preferably a low molecular weight compound having a molecular weight of 2,000 or less, more preferably a low molecular weight compound having a molecular weight of 1,500 or less, and still more preferably a low molecular weight compound having a molecular weight of 900 or less. Further, the molecular weight of the radical polymerizable monomer is usually 100 or more. Further, the oligomer-type radical polymerizable compound is typically a polymer having a relatively low molecular weight, and is preferably a polymer in which 10 to 100 radical polymerizable monomers are bonded. The polystyrene-equivalent weight average molecular weight obtained by gel permeation chromatography (GPC) is preferably from 2,000 to 20,000, more preferably from 2,000 to 15,000, still more preferably from 2,000 to 10,000.

The number of functional groups of the radically polymerizable compound in the present invention means the number of radical polymerizable groups in one molecule. From the viewpoint of the analytical property, the radical polymerizable compound preferably contains at least one of a difunctional or higher radical polymerizable compound containing two or more radical polymerizable groups, and more preferably contains at least one difunctional to tetra A functional free radically polymerizable compound.

<<Compound having an ethylenically unsaturated bond>> As a group having an ethylenically unsaturated bond, a styryl group, a vinyl group, a (meth)acryl fluorenyl group, and a (meth)allyl group are preferable. It is a (meth) acrylonitrile group.

Specific examples of the compound having an ethylenically unsaturated bond include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters thereof. The guanamines and the multimers thereof are preferably esters of an unsaturated carboxylic acid and a polyol compound, and guanamines of an unsaturated carboxylic acid and a polyamine compound, and a multimer of these. Further, an ester or an oxime of an unsaturated carboxylic acid having a nucleophilic substituent such as a hydroxyl group, an amine group or a fluorenyl group, or an addition reaction product with a monofunctional or polyfunctional isocyanate or an epoxy group may be suitably used. Or a dehydration condensation reaction with a monofunctional or polyfunctional carboxylic acid or the like. Further, an ester of an unsaturated carboxylic acid having an electrophilic substituent such as an isocyanate group or an epoxy group, or an addition reaction product of a monofunctional or polyfunctional alcohol, an amine or a thiol, A substituted reactant of an unsaturated carboxylic acid having a detachable substituent such as a halogen group or a tosyloxy group or a guanamine and a monofunctional or polyfunctional alcohol, an amine or a thiol is also suitable. Further, as another example, a group of compounds substituted with a vinylbenzene derivative such as unsaturated phosphonic acid or styrene, vinyl ether or allyl ether may be used instead of the unsaturated carboxylic acid.

Specific examples of the monomer of the ester of the polyol compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butylene glycol diacrylate, and the like as the acrylate. Methylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris(propylene oxypropyl) ether, trishydroxyl Ethylene triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, Dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tris(propylene methoxyethyl) iso-tri Polycyanate, iso-cyanuric acid ethylene oxide modified triacrylate, polyester acrylate oligomer, and the like.

Examples of the methacrylate include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, and trimethylolpropane trimethacrylate. Trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, Pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, double (3-Methoxypropenyloxy-2-hydroxypropoxy)phenyl]dimethylmethane, bis-[p-(methacryloxyethoxy)phenyl]dimethylmethane, etc. .

As itaconate, there are ethylene glycol diitaric acid ester, propylene glycol II itaconate, 1,3-butylene glycol isaconate, 1,4-butanediol diitaric acid ester, and four Methylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetraconate, and the like.

Examples of the crotonate include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetra-dicrotonate.

Examples of the isocrotonate include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

As the maleic acid ester, there are ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramaleic acid. Ester and the like.

As an example of the other ester, for example, an aliphatic alcohol ester described in Japanese Patent Publication No. Sho 46-27926, Japanese Patent Publication No. Sho 51-47334, and Japanese Patent Laid-Open Publication No. SHO 57-196231 A compound having an aromatic skeleton described in Japanese Patent Laid-Open No. Hei 59-5241, Japanese Patent Laid-Open Publication No. Hei No. Hei No. Hei. A compound containing an amine group described in JP-A-165613.

Further, specific examples of the monomer of the polyamine compound and the decylamine of the unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methyl acrylamide, and 1,6-hexamethylene group. Bis-acrylamide, 1,6-hexamethylenebis-methylpropenylamine, diethylenetriaminetripropenylamine, xylylenebisacrylamide, xylylene bismethacrylamide, and the like.

As an example of another preferable amide-based monomer, a monomer having a cyclohexylene structure described in Japanese Patent Publication No. Sho 54-21726 can be cited.

In addition, a urethane-based addition polymerizable monomer produced by an addition reaction of an isocyanate and a hydroxyl group is also suitable, and as such a specific example, for example, it is described in JP-A-48-41708. a vinyl urethane containing two or more polymerizable vinyl groups in one molecule, which is obtained by adding a vinyl monomer containing a hydroxyl group to a polyisocyanate compound having two or more isocyanate groups in one molecule. Compounds, etc. In addition, the urethane urethanes described in Japanese Patent Application Laid-Open No. Hei. No. Hei. An aminocarboxylic acid having an ethylene oxide skeleton described in Japanese Patent Publication No. Sho 62-39417, Japanese Patent Publication No. Sho 62-39417, and Japanese Patent Publication No. Sho 62-39418 Ester compounds are also suitable.

Further, in the present invention, as the compound having an ethylenically unsaturated bond, the compound described in Paragraph No. 0095 to Paragraph No. 0108 of JP-A-2009-288705 can also be suitably used.

Further, as the compound having an ethylenically unsaturated bond, a compound having a boiling point of 100 ° C or higher at normal pressure is also preferable. Examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate. Polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol IV (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexane diol (meth) acrylate, trimethylolpropane tri (propylene oxypropyl propyl) (meth)acrylic acid after addition of ethylene oxide or propylene oxide to a polyfunctional alcohol, such as ether, tris(propylene methoxyethyl) isomeric cyanurate, glycerin or trimethylolethane The (meth)acrylic acid urethane described in each of the publications of the Japanese Patent Publication No. Sho-48-41708, the Japanese Patent Publication No. Sho. Classes, Japanese Patent Laid-Open No. 48-64183, Japanese Patent Special Publication No. Sho 49-43191, and Japanese Patent Special Publication No. 52-30490 Polyester acrylates as described, as a reaction product of an epoxy resin and (meth) acrylic acid esters of polyfunctional epoxy acrylates acrylates and methacrylates, and mixtures of the plurality. Further, the compound described in Paragraph No. 0254 to Paragraph No. 0257 of JP-A-2008-292970 is also suitable. In addition, a polyfunctional (meth)acrylate obtained by reacting a compound having a cyclic ether group and an ethylenically unsaturated group such as glycidyl (meth)acrylate with a polyfunctional carboxylic acid may be mentioned. In addition, as another preferable compound having an ethylenic unsaturated bond, those described in JP-A-2010-160418, JP-A-2010-129825, and JP-A No. 4364216, etc., may be used. A compound having an anthracene ring and having two or more groups containing an ethylenically unsaturated bond, a cardo resin. Further, as another example, a specific unsaturated compound described in Japanese Patent Publication No. Sho 46-43946, Japanese Patent Publication No. Hei. No. Hei. A vinylphosphonic acid-based compound or the like described in JP-A No. 2-25493. In addition, in some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is suitably used. Further, it is also possible to use as a radical polymerizable monomer and oligomer in "Japan Next Association" vol. 20, No. 7, 300 pages to 308 (1984).

In addition to the above, a compound having an ethylenically unsaturated bond represented by the following formula (MO-1) to formula (MO-5) can be suitably used. Further, in the formula, when T is an alkyloxy group, the terminal on the carbon atom side is bonded to R.

[Chemistry 16]

[化17]

In the formula, n is an integer of 0 to 14, and m is an integer of 1 to 8. R and T in a single molecule may be the same or different. In each of the polymerizable compounds represented by the general formula (MO-1) to the general formula (MO-5), at least one of the plurality of R represents -OC(=O)CH=CH ₂ , or -OC(=O)C(CH ₃ )=the group represented by CH ₂ . In the present invention, as a specific example of the compound having an ethylenically unsaturated bond represented by the above formula (MO-1) to (MO-5), Japanese Patent Laid-Open No. 2007- The compound described in Paragraph No. 0248 to Paragraph No. 0251 of 269779.

The following compounds which are described in the general formula (1) and the general formula (2) together with the specific examples thereof can also be used as a polymerizable compound in a polyfunctional alcohol, as disclosed in Japanese Laid-Open Patent Publication No. Hei 10-62986. A compound obtained by (meth)acrylation after addition of ethylene oxide or propylene oxide.

As the compound having an ethylenically unsaturated bond, dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (preferably) The products sold are KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; Nippon Kayak) Pharmaceutical Co., Ltd.), dipentaerythritol hexa(meth) acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.), and these (meth) acrylonitrile groups A structure bonded via an ethylene glycol residue or a propylene glycol residue. These oligomer types can also be used.

The compound having an ethylenically unsaturated bond may also be a polyfunctional monomer having an acid group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group. The polyfunctional monomer having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, more preferably an acid group based on reacting a non-aromatic carboxylic anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound. The polyfunctional monomer, particularly preferably in the ester, is an aliphatic polyhydroxy compound which is pentaerythritol and/or dipentaerythritol. As a commercial item, M-510, M-520, etc. which are polyacid-acid-modified acrylic oligomer manufactured by the East Asia Synthetic Co., Ltd. are mentioned, for example. The polyfunctional monomer having an acid group may be used singly or in combination of two or more. Further, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as needed. The preferred acid value of the polyfunctional monomer having an acid group is from 0.1 mgKOH/g to 40 mgKOH/g, particularly preferably from 5 mgKOH/g to 30 mgKOH/g. When the acid value of the polyfunctional monomer is in the above range, the production or handling property is excellent, and further, the developability is excellent. Further, the radical polymerizability is good.

As the compound having an ethylenically unsaturated bond, a compound having a caprolactone structure can also be used. The compound having a caprolactone structure and an ethylenically unsaturated bond is not particularly limited as long as it has a caprolactone structure in the molecule, and examples thereof include trishydroxymethylethane and di-trimethylol B. Alkane, trimethylolpropane, di-trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerin, trimethylol melamine, and the like, and (meth)acrylic acid and ε-caprolactone The ε-caprolactone obtained by esterification is modified with a polyfunctional (meth) acrylate. Among them, a polymerizable compound having a caprolactone structure represented by the following formula (C) is preferred.

General formula (C) [Chem. 18]

(In the formula, all of the six R's are represented by the following formula (D), or one to five of the six R's are represented by the following formula (D), and the remainder is a group represented by the following general formula (E)

General formula (D) [Chem. 19]

(wherein R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and "*" represents a bond)

General formula (E) [Chem. 20]

(wherein R ¹ represents a hydrogen atom or a methyl group, and "*" represents a bond)

Such a polymerizable compound having a caprolactone structure is commercially available, for example, as a KAYARAD DPCA series from Nippon Kayaku Co., Ltd., and may be exemplified by DPCA-20 (the above formula (C) to the formula In (E), m = 1, a compound represented by the formula (D) = 2, a compound in which R ¹ is a hydrogen atom), DPCA-30 (the above formula (C) to a formula (E) In the formula (C) to (E), m = 1, a compound represented by the formula (D) = 3, a compound in which R ¹ is a hydrogen atom), and DPCA-60 (in the formula (C) to (E) , m = 1, a compound represented by the formula (D) = 6 and a compound in which R ¹ is a hydrogen atom), DPCA-120 (in the above formula (C) to (E), m = 2, the number of the groups represented by the formula (D) = 6, the compound in which R ¹ is a hydrogen atom) and the like. In the present invention, the compound having a caprolactone structure and an ethylenically unsaturated bond may be used singly or in combination of two or more.

The compound having an ethylenically unsaturated bond is preferably at least one selected from the group consisting of compounds represented by the following formula (i) or formula (ii).

[Chem. 21]

In the general formula (i) and the general formula (ii), E independently represents -((CH ₂ ) _y CH ₂ O)-, or -((CH ₂ ) _y CH(CH ₃ )O)-, y respectively Independently, an integer of 0 to 10 is represented, and X each independently represents a (meth)acryloyl group, a hydrogen atom, or a carboxyl group. In the general formula (i), the total of (meth)acrylonyl groups is three or four, and m each independently represents an integer of from 0 to 10, and the total of each m is an integer of from 0 to 40. However, when the total of each m is 0, any one of X is a carboxyl group. In the general formula (ii), the total of (meth)acrylonyl groups is 5 or 6, and n each independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60. However, when the total of each n is 0, any one of X is a carboxyl group.

In the formula (i), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. Further, the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8. In the formula (ii), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. Further, the total of each n is preferably an integer of from 3 to 60, more preferably an integer of from 3 to 24, and particularly preferably an integer of from 6 to 12. -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)- in the formula (i) or the formula (ii) is preferably a terminal bond on the oxygen atom side Formed on X. In particular, it is preferred that in the general formula (ii), six Xs are in the form of an acrylonitrile group.

The compound represented by the formula (i) or the formula (ii) can be synthesized by the following steps as a previously known step: ring-opening addition reaction of ethylene oxide or propylene oxide with pentaerythritol or dipentaerythritol The step of bonding the ring-opening skeleton and the step of introducing a (meth)acrylonitrile group by reacting a terminal hydroxyl group of the ring-opening skeleton with, for example, (meth)acryloyl chloride. Each step is a well-known step, and a person represented by the formula (i) or the formula (ii) can be easily synthesized by a person skilled in the art.

Among the compounds represented by the general formula (i) and the general formula (ii), a pentaerythritol derivative and a dipentaerythritol derivative are more preferable. Specifically, a compound represented by the following formula (a) to formula (f) (hereinafter also referred to as "exemplary compound (a) to exemplary compound (f)")), preferably an exemplified compound (a), exemplified compound (b), exemplified compound (e), and exemplified compound (f).

[化22]

[化23]

As a commercial item of the polymerizable compound represented by the general formula (i) and the general formula (ii), for example, a tetrafunctional acrylic acid having four ethylene ethoxylate chains manufactured by Sartomer Co., Ltd. is mentioned. Ester SR-494, DPCA-60 manufactured by Nippon Kayaku Co., Ltd. as a hexafunctional acrylate having 6 pentyloxy chains, and TPA as a trifunctional acrylate having 3 extended isobutoxy chains -330 and so on.

As a compound having an ethylenic unsaturated bond, for example, Japanese Patent Publication No. Sho 48-41708, Japanese Patent Laid-Open No. Sho 51-37193, Japanese Patent Laid-Open No. 2-32293, Japanese Patent Publication No. Hei 2-16765 The urethane amides described in Japanese Patent Publication No. Sho 58-49860, Japanese Patent Publication No. SHO 56-17654, Japanese Patent Publication No. Sho 62-39417, and Japanese Patent Publication No. SHO 62-39418 A urethane compound having an ethylene oxide skeleton described in the publication is also suitable. Further, as the polymerizable compound, an amine having a molecule in the molecule as described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 An addition polymerizable monomer of a base structure or a thioether structure. Commercial products of the compound having an ethylenically unsaturated bond include urethane oligomer UAS-10, UAB-140 (made by Sanyo Kokusaku Pulp Co., Ltd.), and NK ESTER (NK ESTER). ) M-40G, NK Ester 4G, NK ESTER M-9300, NK ESTER A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPHA-40H (Manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (made by Nippon Oil Co., Ltd.).

From the viewpoint of heat resistance, the compound having an ethylenically unsaturated bond preferably has a partial structure represented by the following formula. Where * in the formula is a link key.

[Chem. 24]

Specific examples of the compound having an ethylenically unsaturated bond having the partial structure include, for example, trimethylolpropane tri(meth)acrylate and isomeric cyanuric acid ethylene oxide modified di(methyl). Acrylate, iso-cyanuric acid ethylene oxide modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dimethylolpropane tetra(methyl) ) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tetramethylol methane tetra (meth) acrylate, etc., which are particularly preferably used in the present invention Polymeric compound.

In the negative photosensitive resin composition, the content of the radical polymerizable compound is preferably 1 in terms of the total solid content of the negative photosensitive resin composition from the viewpoint of good radical polymerizability and heat resistance. Mass% to 50% by mass. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 30% by mass or less. The radically polymerizable compound may be used singly or in combination of two or more. Further, the mass ratio of the polyimine precursor to the compound having a radical polymerizable compound (polyimine precursor/radical polymerizable compound) is preferably 98/2 to 10/90, more preferably 95/ 5 to 30/70, and more preferably 90/10 to 50/50. When the mass ratio of the polyimine precursor to the radically polymerizable compound is in the above range, a cured film having more excellent curability and heat resistance can be formed. The radically polymerizable compound may be used alone or in combination of two or more. When two or more types are used, it is preferable that the total amount is the above range.

<Photobase generator> The negative photosensitive resin composition of the present invention may further contain a photobase generator. The photobase generator is a substance which generates an alkali by exposure, and does not exhibit activity under normal conditions of normal temperature and normal pressure, and is an alkali (basic substance) which is generated when electromagnetic waves are irradiated and heated as an external stimulus. There is no particular limitation. Since the base generated by the exposure acts as a catalyst when the polyimide precursor is hardened by heating, it can be suitably used in the negative type.

The content of the photobase generating agent is not particularly limited as long as it can form a desired pattern, and can be set to a normal content. The content of the photobase generator is preferably 0.01 parts by mass or more and less than 30 parts by mass, more preferably 0.05 parts by mass to 25 parts by mass, per 100 parts by mass of the negative photosensitive resin composition. Further, it is more preferably in the range of 0.1 part by mass to 20 parts by mass.

In the present invention, those known as photobase generators can be used. For example, M. Shirai, and M. Tsunooka, Progress in Polymer Science, Prog. Polym. Sci., 21, 1 (1996) Kakuoka Masahiro, "Polymer Processing", 46, 2 (1997); C. Kutal, "Coordination Chemistry Reviews, Coord. Chem. Rev.", 211, 353 (2001); Y. Gold and A. Sarke, and D. Neckers, "Chemistry of Materials, Chem. Mater.", 11, 170 (1999); H .. and H. Tachi, M. Shirai, and M. Tsunooka, Journal of Photopolymer Science and Technology, J. Photopolym. Sci. Technol .)", 13, 153 (2000); M. Winkle, and Graziano, J. Photopolym. Sci. Technol. 3, 419 (1990); M. Kakuoka and H. T. and M. Tsunooka, H. Tachi, and S. Yoshitaka, J. Photopolym. Sci. Technol.)", 9, 13 (1996); K. Shoushan and H. Araki and M. Shirai, "Photopolymer Science and Technology Journal (J. Photopolym. Sci. Technol.)", 19, 81 (2006), a transition metal compound complex, or a structure having an ammonium salt or the like, or a potential formation by forming a salt with a carboxylic acid moiety An ionic compound neutralized by the formation of a salt by an alkali component, or a carbamate derivative, an oxime ester derivative, a mercapto compound or the like by an alkali component or the like A nonionic compound. The photobase generator which can be used in the present invention can be used without any particular limitation, and examples thereof include a carbamate derivative, a decylamine derivative, a quinone imine derivative, an α cobalt complex, and an imidazole derivative. , cinnamate decylamine derivatives, anthraquinone derivatives, and the like.

The basic substance produced by the photobase generator is not particularly limited, and examples thereof include a compound having an amine group, particularly a polyamine such as a monoamine or a diamine, or hydrazine. The alkaline substance produced is preferably a compound having an amine group having a higher basicity. The reason for this is that the catalyst is strongly added to the dehydration condensation reaction in the ruthenium imidization of the polyimide precursor, and is added in a smaller amount, and exhibits a dehydration condensation reaction at a lower temperature. The catalyst effect in the medium. That is, since the catalytic effect of the generated alkaline substance is large, the apparent sensitivity as a negative photosensitive resin composition is improved. From the viewpoint of the catalytic effect, it is preferably an anthracene or an aliphatic amine.

The photobase generator is preferably a photobase generator which does not contain a salt in the structure. In the photobase generator, it is preferred that no charge is present on the nitrogen atom of the base moiety produced. The photobase generator preferably uses a covalent bond to form a base, and more preferably, the base is generated by a covalent bond between the nitrogen atom of the generated base and the adjacent atom. A compound that produces a base. In the case of a photobase generator which does not contain a salt in the structure, the photobase generator can be made neutral, so that the solvent solubility is good and the pot life is improved. For this reason, the amine produced by the photobase generator used in the present invention is preferably a primary amine or a secondary amine.

Further, for the reason as described above, it is preferred that the photobase generator is metabolized by using a covalent bond in the base produced as described above. Further, it is more preferable to use a guanamine bond, a urethane bond or a hydrazone bond to cause a potential to be generated. The base generator of the present invention may, for example, be an alkali generator having a guanyl cinnamate structure as disclosed in Japanese Laid-Open Patent Publication No. 2009-80452 and the International Publication No. WO2009/123122, such as a Japanese patent. An alkali-generating agent having a urethane structure as disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. 2008-247747, and Japanese Patent Laid-Open No. Hei. An alkali generating agent having a fluorene structure or an amine formamidine structure as disclosed in JP-A-003581 is not limited thereto, and a known alkali-generating agent may be used.

Hereinafter, the photobase generating agent which can be used in the present invention will be described by way of specific examples. Examples of the ionic compound include those having the following structural formula.

[化25]

Examples of the mercapto compound include compounds represented by the following formulas.

[Chem. 26]

In addition, examples of the photobase generator include compounds represented by the following formula (PB-1).

[化27] (PB-1)

(In the formula (PB-1), R ⁴¹ and R ⁴² are each independently a hydrogen atom or an organic group, and may be the same or different; wherein at least one of R ⁴¹ and R ⁴² is an organic group; or, R ⁴¹ And R ⁴² , these may be bonded to form a ring structure, and may also contain a bond of a hetero atom; R ⁴³ and R ⁴⁴ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a thioether group, a decyl group, or a decane. An alcohol group, a nitro group, a nitroso group, a sulfinic acid group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonium group, a phosphonate group, or an organic group, which may be the same or different; R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a thioether group, a decyl group, a decyl alcohol group, a nitro group, a nitroso group, a sulfinic acid group, a sulfo group or a sulfonic acid group. a base, a phosphino group, a phosphinyl group, a phosphonium group, a phosphonate group, an amine group, an ammonium group or an organic group, which may be the same or different; or, in R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ , two or more may be bonded to form a ring structure may also include a hetero atom bond; R ⁴⁹ is a hydrogen atom, or can be heated by the irradiation and / or electromagnetic waves deprotected Protecting group)

Specific examples of the general formula (PB-1) are listed below, but are not limited thereto.

[化28]

[化29]

[化30]

In addition, examples of the photobase generator include compounds described in paragraphs 0185 to 0188, paragraphs 0199 to 0200, and paragraph 0020 of JP-A-2012-93746, and Japanese Patent No. The compound described in Paragraph No. 0022 to Paragraph No. 0069 of the Japanese Patent Publication No. 2013-194205, the compound described in Paragraph No. 0026 to Paragraph No. 0074 of JP-A-2013-204019, and the paragraph number of WO2010/064631 The compound described in 0052 is taken as an example.

<Thermal base generator> The negative photosensitive resin composition of the present invention may further contain a thermal base generator. The type of the caustic generator is not particularly limited, and preferably includes at least one selected from the group consisting of an acidic compound selected to be a base heated to 40° C. or higher, and an ammonium salt having an anion of pKa1 of 0 to 4 and an ammonium cation. Thermal base generator. Here, pKa1 represents a logarithmic mark (-Log ₁₀ Ka) of the dissociation constant (Ka) of the first proton of the polybasic acid. By blending such a compound, the cyclization reaction of the polyimide precursor can be carried out at a low temperature, and a negative photosensitive resin composition having more excellent stability can be formed. Further, since the hot base generator does not generate an alkali without heating, even if it is coexisted with the polyimide precursor, cyclization of the polyimide precursor during storage can be suppressed, and the storage stability is excellent.

The thermal base generator in the present invention contains at least one selected from the group consisting of an acidic compound (A1) which generates a base when heated to 40 ° C or more, and an ammonium salt (A2) which has an anion of pKa1 of 0 to 4 and an ammonium cation. When the acidic compound (A1) and the ammonium salt (A2) are heated to generate a base, the cyclization reaction of the polyimide precursor can be promoted by the alkali generated from the compounds. The cyclization of the polyimine precursor is carried out at a low temperature. Further, even if these compounds are coexisted with a polyimine precursor which is cyclized and hardened by a base, the cyclization of the polyimide precursor is hardly carried out unless heating is performed. A negative photosensitive resin composition excellent in stability was prepared. In the present specification, the term "acid compound" means a compound obtained by extracting 1 g of the compound into a container and adding a mixture of ion-exchanged water and tetrahydrofuran (mass ratio of water/tetrahydrofuran = 1/4) 50 mL. The mixture was stirred at room temperature for 1 hour, and the value obtained by measuring the obtained solution at 20 ° C was less than 7 using a potentiometer (pH).

In the present invention, the alkali generating temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40 ° C or higher, more preferably 120 ° C to 200 ° C. The upper limit of the alkali generation temperature is more preferably 190 ° C or lower, further preferably 180 ° C or lower, and still more preferably 165 ° C or lower. The lower limit of the base generation temperature is more preferably 130 ° C or higher, and still more preferably 135 ° C or higher. When the alkali production temperature of the acidic compound (A1) and the ammonium salt (A2) is 120 ° C or more, it is difficult to generate an alkali during storage, and thus a negative photosensitive resin composition excellent in stability can be prepared. When the base production temperature of the acidic compound (A1) and the ammonium salt (A2) is 200 ° C or lower, the cyclization temperature of the polyimide precursor can be lowered. The alkali generation temperature can be measured, for example, by differential scanning calorimetry, and the compound is heated to 250 ° C at 5 ° C / min in a pressure resistant capsule, the peak temperature of the heat generation peak having the lowest temperature is read, and the peak temperature is used as the alkali generation temperature. Determination.

In the present invention, the base produced by the hot base generator is preferably a secondary amine or a tertiary amine, more preferably a tertiary amine. Since the tertiary amine has a high basicity, the cyclization temperature of the polyimide precursor can be further lowered. Further, the boiling point of the base produced by the hot alkali generating agent is preferably 80 ° C or higher, more preferably 100 ° C or higher, and most preferably 140 ° C or higher. Further, the molecular weight of the produced base is preferably from 80 to 2,000. The lower limit is more preferably 100 or more. The upper limit is preferably 500 or less. Further, the value of the molecular weight is a theoretical value obtained from the structural formula.

In the present invention, the acidic compound (A1) preferably contains one or more selected from the group consisting of an ammonium salt and a compound represented by the formula (A1) described later.

In the present invention, the ammonium salt (A2) is preferably an acidic compound. Further, the ammonium salt (A2) may be a compound containing an acidic compound which generates a base when heated to 40 ° C or higher (preferably 120 ° C to 200 ° C), or may be heated to 40 ° C or higher (more) It is preferably from 120 ° C to 200 ° C to produce a compound other than an acidic compound of a base.

<<Ammonium salt>> In the present invention, the ammonium salt refers to a salt of an ammonium cation and an anion represented by the following formula (1) or formula (2). The anion may be bonded to any part of the ammonium cation via a covalent bond or may be present outside the molecule of the ammonium cation, preferably outside the molecule of the ammonium cation. Further, the fact that the anion is present outside the molecule of the ammonium cation means that the ammonium cation and the anion are not bonded via a covalent bond. Hereinafter, the extra-molecular anion of the cation portion is also referred to as a counter anion. [化31] In the above formula (1) and formula (2), R ¹ to R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, and the formula R ⁷ represents a hydrocarbon group. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , and R ⁵ and R ⁷ may each bond to form a ring.

In the present invention, the ammonium salt is preferably an anion having an pKa1 of 0 to 4 and an ammonium cation. The upper limit of the pKa1 of the anion is more preferably 3.5 or less, still more preferably 3.2 or less. The lower limit is more preferably 0.5 or more, and still more preferably 1.0 or more. When the pKa1 of the anion is in the above range, the polyimide precursor can be cyclized at a low temperature, and the stability of the negative photosensitive resin composition can be improved. When pKa1 is 4 or less, the stability of the thermal base generator is good, and it is possible to suppress the occurrence of alkali without heating, and the stability of the negative photosensitive resin composition is good. When pKa1 is 0 or more, the generated alkali is difficult to be neutralized, and the cyclization efficiency of the polyimide precursor is good. The type of the anion is preferably one selected from the group consisting of a carboxylate anion, a phenol anion, a phosphate anion, and a sulfate anion, and the carboxylate anion is more preferable because the stability of the salt and the thermal decomposition are coexisting. . That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion. The carboxylate anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxyl groups, more preferably an anion of a divalent carboxylic acid. According to this aspect, a hot alkali generating agent which can further improve the stability, curability, and developability of the negative photosensitive resin composition can be obtained. In particular, by using an anion of a divalent carboxylic acid, the stability, curability, and developability of the negative photosensitive resin composition can be further improved. In the present invention, the carboxylate anion is preferably an anion of a carboxylic acid having a pKa1 of 4 or less. The pKa1 is more preferably 3.5 or less, and still more preferably 3.2 or less. According to this aspect, the stability of the negative photosensitive resin composition can be further improved. Here, pKa1 represents the logarithm of the reciprocal of the first dissociation constant of the acid, and can be referred to as "Determination of Organic Structures by Physical Methods" (author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; Editor: Braude, EA, Nachod, FC; American Academic Press (New York, 1955), or "Data for Biochemical Research" (author: Dawson) , RMC, et al; Oxford, Clarendon Press, 1959). For the compounds not described in these documents, a value calculated by a structural formula using ACD/pKa (manufactured by ACD/Labs) was used.

In the present invention, the carboxylate anion is preferably represented by the following formula (X1). [化32] In the formula (X1), EWG represents an electron withdrawing group.

In the present invention, the term "electron withdrawing group" means that the substituent constant σm of Hammett shows a positive value. Here, σm is described in detail in the general theory of Tono Hiroshi, "Organic Synthetic Chemistry Association", Vol. 23, No. 8 (1965) P.631-642. Furthermore, the electron withdrawing group of the present invention is not limited to the substituents described in the above documents. Examples of the substituent having a positive value of σm include a CF ₃ group (σm = 0.43), a CF ₃ CO group (σm = 0.63), a HC ≡ C group (σm = 0.21), and a CH ₂ = CH group ( Σm=0.06), Ac group (σm=0.38), MeOCO group (σm=0.37), MeCOCH=CH group (σm=0.21), PhCO group (σm=0.34), H ₂ NCOCH ₂ group (σm=0.06), etc. . Further, Me represents a methyl group, Ac represents an ethyl group, and Ph represents a phenyl group.

In the present invention, EWG preferably represents a group represented by the following formula (EWG-1) to formula (EWG-6). [化33] In the formula, R ^x1 to R ^x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group or a carboxyl group, and Ar represents an aryl group. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 10 carbon atoms. The alkyl group may be any of a straight chain, a branched chain, and a cyclic group, and is preferably a straight chain or a branched chain, and more preferably a straight chain. The alkyl group may have a substituent or may be unsubstituted. The substituent may be mentioned as a substituent which the organic group represented by A ¹ mentioned later may have. As a substituent, a carboxyl group is preferable. The number of carbon atoms of the alkenyl group is preferably from 2 to 30, more preferably from 2 to 20, still more preferably from 2 to 10. The alkenyl group may be any of a straight chain, a branched chain, and a cyclic group, and is preferably a straight chain or a branched chain, and more preferably a straight chain. The alkenyl group may have a substituent or may be unsubstituted. The substituent may be mentioned as a substituent which the organic group represented by A ¹ mentioned later may have. As a substituent, a carboxyl group is preferable. The carbon number of the aryl group is preferably from 6 to 30, more preferably from 6 to 20, still more preferably from 6 to 12. The aryl group may have a substituent or may be unsubstituted. The substituent may be mentioned as a substituent which the organic group represented by A ¹ mentioned later may have. As a substituent, a carboxyl group is preferable.

In the present invention, the carboxylate anion is also preferably represented by the following formula (X). [化34] In the formula (X), L ¹⁰ represents a single bond, or a divalent linking group selected from the group consisting of an alkyl group, an alkenyl group, an extended aryl group, -NR ^X - and a combination thereof, and R ^X represents hydrogen. Atom, alkyl, alkenyl or aryl.

The carbon number of the alkylene group represented by L ¹⁰ is preferably from 1 to 30, more preferably from 1 to 20, still more preferably from 1 to 10. The alkylene group may be any of a straight chain, a branched chain, and a cyclic chain, and is preferably a straight chain or a branched chain, and more preferably a straight chain. The alkylene group may have a substituent or may be unsubstituted. The substituent may be mentioned as a substituent which the organic group represented by A ¹ mentioned later may have. The carbon number of the alkenyl group represented by L ¹⁰ is preferably from 2 to 30, more preferably from 2 to 20, still more preferably from 2 to 10. The alkenyl group may be any of a straight chain, a branched chain, and a cyclic group, and is preferably a straight chain or a branched chain, and more preferably a straight chain. The alkenyl group may have a substituent or may be unsubstituted. The substituent may be mentioned as a substituent which the organic group represented by A ¹ mentioned later may have. The carbon number of the aryl group represented by L ¹⁰ is preferably from 6 to 30, more preferably from 6 to 20, still more preferably from 6 to 12. The aryl group may have a substituent or may be unsubstituted. The substituent may be mentioned as a substituent which the organic group represented by A ¹ mentioned later may have.

The alkyl group represented by R ^X preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 10 carbon atoms. The alkyl group may be any of a straight chain, a branched chain, and a cyclic group, and is preferably a straight chain or a branched chain, and more preferably a straight chain. The alkyl group may have a substituent or may be unsubstituted. The substituent may be mentioned as a substituent which the organic group represented by A ¹ mentioned later may have. The number of carbon atoms of the alkenyl group represented by R ^X is preferably from 2 to 30, more preferably from 2 to 20, still more preferably from 2 to 10. The alkenyl group may be any of a straight chain, a branched chain, and a cyclic group, and is preferably a straight chain or a branched chain, and more preferably a straight chain. The alkenyl group may have a substituent or may be unsubstituted. The substituent may be mentioned as a substituent which the organic group represented by A ¹ mentioned later may have. The carbon number of the aryl group represented by R ^X is preferably from 6 to 30, more preferably from 6 to 20, still more preferably from 6 to 12. The aryl group may have a substituent or may be unsubstituted. The substituent may be mentioned as a substituent which the organic group represented by A ¹ mentioned later may have.

Specific examples of the carboxylate anion include a maleate anion, a phthalate anion, an N-phenyliminodiacetate anion, and an oxalate anion. These specific examples can be preferably used.

The ammonium cation is preferably represented by any one of the following general formulae (Y1-1) to (Y1-6). [化35]

In the above formula, R ¹⁰¹ represents an n-valent organic group, R ¹⁰² to R ¹¹¹ each independently represent a hydrogen atom or a hydrocarbon group, and R ¹⁵⁰ and R ¹⁵¹ each independently represent a hydrocarbon group, R ¹⁰⁴ and R ¹⁰⁵ , R ¹⁰⁴ R ¹⁵⁰ , R ¹⁰⁷ and R ¹⁰⁸ , and R ¹⁰⁹ and R ¹¹⁰ may be bonded to each other to form a ring, and Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group, n represents an integer of 1 or more, and m represents an integer of 0 to 5. .

R ¹⁰¹ represents an n-valent organic group. The monovalent organic group may, for example, be an alkyl group, an alkylene group or an aryl group. Examples of the divalent or higher organic group include one in which one or more hydrogen atoms are removed from the monovalent organic group to form an n-valent group. R ^{101 is} preferably an aryl group. Specific examples of the aryl group include those described in Ar ¹⁰ to be described later.

R ¹⁰² to R ¹¹¹ each independently represent a hydrogen atom or a hydrocarbon group, and R ¹⁵⁰ and R ¹⁵¹ each independently represent a hydrocarbon group. The hydrocarbon group represented by R ¹⁰² to R ¹¹¹ , R ¹⁵⁰ and R ¹⁵¹ is preferably an alkyl group, an alkenyl group or an aryl group. The alkyl group, the alkenyl group and the aryl group may further have a substituent. The substituent may be mentioned as a substituent which the organic group represented by A ¹ mentioned later may have.

The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 10 carbon atoms. The alkyl group may be any of a straight chain, a branched chain, and a cyclic group, and is preferably a straight chain or a branched chain, and more preferably a straight chain. The alkyl group may have a substituent or may be unsubstituted. The number of carbon atoms of the alkenyl group is preferably from 2 to 30, more preferably from 2 to 20, still more preferably from 2 to 10. The alkenyl group may be any of a straight chain, a branched chain, and a cyclic group, and is preferably a straight chain or a branched chain, and more preferably a straight chain. The alkenyl group may have a substituent or may be unsubstituted. The carbon number of the aryl group is preferably from 6 to 30, more preferably from 6 to 20, still more preferably from 6 to 12. The aryl group may have a substituent or may be unsubstituted.

Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group. The carbon number of the aryl group is preferably from 6 to 30, more preferably from 6 to 20, still more preferably from 6 to 12. The aryl group may have a substituent or may be unsubstituted.

R ¹⁰⁴ and R ¹⁰⁵ , R ¹⁰⁴ and R ¹⁵⁰ , R ¹⁰⁷ and R ¹⁰⁸ , and R ¹⁰⁹ and R ¹¹⁰ may be bonded to each other to form a ring. Examples of the ring include an aliphatic ring (non-aromatic hydrocarbon ring), an aromatic ring, and a hetero ring. The ring may be a single ring or a double ring. The linking group when the group is bonded to form a ring may be selected from the group consisting of -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aryl group, and a combination thereof. A divalent linkage in the group. Specific examples of the ring to be formed include a pyrrolidine ring, a pyrrole ring, a piperidine ring, a pyridine ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, a pyrazine ring, a morpholine ring, and a thiophene ring. a azine ring, an anthracene ring, an isoindole ring, a benzimidazole ring, an anthracene ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, A porphyrin ring, an oxazole ring, and the like.

In the present invention, the ammonium cation is preferably a structure represented by the formula (Y1-1) or the formula (Y1-2), more preferably a formula (Y1-1) or a formula (Y1-2). The structure in which R ¹⁰¹ is an aryl group is particularly preferably a structure represented by the formula (Y1-1) and R ¹⁰¹ is an aryl group. That is, in the present invention, the ammonium cation is more preferably represented by the following formula (Y). [化36] In the general formula (Y), Ar ¹⁰ represents an aromatic group, and R ¹¹ to R ¹⁵ each independently represent a hydrogen atom or a hydrocarbon group, and R ¹⁴ and R ¹⁵ may bond each other to form a ring, and n represents an integer of 1 or more.

Ar ¹⁰ represents an aryl group. Specific examples of the aryl group include a substituted or unsubstituted benzene ring, a naphthalene ring, a pentylene ring, an anthracene ring, an anthracene ring, a heptene ring, a terpene ring, an anthracene ring, and a fused pentabenzene. Ring, ethane naphthalene ring, phenanthrene ring, anthracene ring, thick tetraphenyl ring, Ring, triphenylene, anthracene, biphenyl, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, pyridazine Ring, anthracene ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolizine ring, quinoline ring, pyridazine ring, naphthyridine ring, quinoxaline ring, quinoxaline ring, different Quinoline ring, carbazole ring, phenazin ring, acridine ring, phenanthroline ring, thioxan ring, benzopyran ring, xanthene ring, morphine ring, phenothiazine ring, and phenazine ring. Among them, from the viewpoint of storage stability and high sensitivity, a benzene ring, a naphthalene ring, an anthracene ring, a phenothiazine ring, or an oxazole ring is preferred, and a benzene ring or a naphthalene ring is preferred. Examples of the aryl group may have a substituent group, A ¹ described later include an organic group represented by may have a substituent group as those described.

R ¹¹ and R ¹² each independently represent a hydrogen atom or a hydrocarbon group. The hydrocarbon group is not particularly limited, and is preferably an alkyl group, an alkenyl group or an aryl group. R ¹¹ and R ^{12 are} preferably a hydrogen atom.

The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 10 carbon atoms. The alkyl group may be any of a straight chain, a branched chain, and a cyclic chain. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a dodecyl group, and a tetradecyl group. Octadecyl, isopropyl, isobutyl, t-butyl, tert-butyl, 1-ethylpentyl, and 2-ethylhexyl. The cyclic alkyl group (cycloalkyl group) may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. Examples of the monocyclic cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic cycloalkyl group include an adamantyl group, a norbornyl group, a borneyl group, a nonenyl group, a decahydronaphthyl group, a tricyclodecylalkyl group, a tetracyclodecyl group, a fluorenyl group, and a second group. Cyclohexyl and decenyl. Among them, from the viewpoint of coexistence with high sensitivity, the cyclohexyl group is most preferable. The number of carbon atoms of the alkenyl group is preferably from 2 to 30, more preferably from 2 to 20, still more preferably from 2 to 10. The alkenyl group may be any of a straight chain, a branched chain, and a cyclic group, and is preferably a straight chain or a branched chain, and more preferably a straight chain. The carbon number of the aryl group is preferably from 6 to 30, more preferably from 6 to 20, still more preferably from 6 to 12.

R ¹³ to R ¹⁵ represent a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include the hydrocarbon groups described in the above R ¹¹ and R ¹² . R ¹³ to R ^{15 are} particularly preferably an alkyl group, and a preferred embodiment is also the same as those described for R ¹¹ and R ¹² .

R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring. Examples of the ring include a cyclic aliphatic group (non-aromatic hydrocarbon ring), an aromatic ring, and a hetero ring. The ring may be a single ring or a double ring. Examples of the linking group when R ⁴ and R ⁵ are bonded to each other to form a ring include -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aryl group, and a combination thereof. A divalent linking group in the group formed. Specific examples of the ring to be formed include a pyrrolidine ring, a pyrrole ring, a piperidine ring, a pyridine ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, a pyrazine ring, a morpholine ring, and a thiophene ring. a azine ring, an anthracene ring, an isoindole ring, a benzimidazole ring, an anthracene ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, A porphyrin ring, an oxazole ring, and the like.

R ¹³ to R ^{15 are} preferably a ring in which R ¹⁴ and R ¹⁵ are bonded to each other to form a ring, or R ¹³ is a linear alkyl group having 5 to 30 carbon atoms (more preferably 6 to 18 carbon atoms), R ¹⁴ and R ^{15 .} Each is independently an alkyl group having 1 to 3 carbon atoms (more preferably 1 or 2 carbon atoms). According to this aspect, an amine species having a high boiling point can be easily produced. Further, from the viewpoint of the basicity or boiling point of the amine species to be produced, R ¹³ to R ^{15 are} preferably a total of 7 to 30, more preferably 10 to 20 carbon atoms of R ¹³ and R ¹⁴ and R ¹⁵ . . Further, the reason for the fact that the amine group having a high boiling point is likely to be generated is preferably a chemical formula of "-NR ¹³ R ¹⁴ R ¹⁵ " in the formula (Y) of from 80 to 2,000, more preferably from 100 to 500.

On the other hand, as an embodiment for further improving the adhesion to the copper wiring, in the general formula (Y), R ¹³ and R ¹⁴ are a methyl group or an ethyl group, and R ¹⁵ is a carbon number. 5 or more linear, branched or cyclic alkyl groups or aryl groups. In the present embodiment, R ¹³ and R ¹⁴ are preferably a methyl group, and R ¹⁵ is a linear alkyl group having 5 to 20 carbon atoms, a branched alkyl group having 6 to 17 carbon atoms, or a ring having 6 to 10 carbon atoms. More preferably, R ¹³ and R ¹⁴ are a methyl group, R ¹⁵ is a linear alkyl group having 5 to 10 carbon atoms, a branched alkyl group having 6 to 10 carbon atoms, or a carbon number of 6 to 8. Cyclic alkyl or phenyl. By thus reducing the hydrophobicity of the amine species, even when the amine is attached to the copper wiring, the affinity between the copper surface and the polyimide may be more effectively suppressed. In the present embodiment, the preferred ranges of Ar ¹⁰ , R ¹¹ , R ¹² and n are the same as described above.

<Compound represented by the general formula (A1)> In the present invention, the acidic compound is preferably a compound represented by the following formula (A1). This compound is acidic at room temperature, but disappears by heating, carboxy decarbonation or dehydration cyclization, whereby the amine moiety which has been previously neutralized and deactivated becomes active, thereby becoming alkaline. Hereinafter, the general formula (A1) will be described.

[化37] In the formula (A1), A ¹ represents a p-valent organic group, R ¹ represents a monovalent organic group, L ¹ represents an (m+1)-valent organic group, m represents an integer of 1 or more, and p represents 1 or more. The integer.

In the formula (A1), A ¹ represents a p-valent organic group. The organic group may, for example, be an aliphatic group or an aryl group, and is preferably an aryl group. By setting A ¹ as an aryl group, it is easy to produce a base having a high boiling point at a lower temperature. By increasing the boiling point of the base to be produced, volatilization or decomposition due to heating during curing of the polyimide precursor can be suppressed, and cyclization of the polyimide precursor can be more efficiently carried out. Examples of the monovalent aliphatic group include an alkyl group and an alkenyl group. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 10 carbon atoms. The alkyl group may be any of a straight chain, a branched chain, and a cyclic chain. The alkyl group may have a substituent or may be unsubstituted. Specific examples of the alkyl group include a methyl group, an ethyl group, a tert-butyl group, a dodecyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and an adamantyl group. The number of carbon atoms of the alkenyl group is preferably from 2 to 30, more preferably from 2 to 20, still more preferably from 2 to 10. The alkenyl group may be any of a straight chain, a branched chain, and a cyclic chain. The alkenyl group may have a substituent or may be unsubstituted. Examples of the alkenyl group include a vinyl group and a (meth)allyl group. Examples of the divalent or higher aliphatic group include a group in which one or more hydrogen atoms are removed from the monovalent aliphatic group. The aryl group may be a single ring or a polycyclic ring. The aryl group may also be a heteroaryl group containing a hetero atom. The aryl group may have a substituent or may be unsubstituted. It is preferably unsubstituted. Specific examples of the aryl group include a benzene ring, a naphthalene ring, a pentylene ring, an anthracene ring, an anthracene ring, a heptene ring, a terpene ring, an anthracene ring, a condensed pentabenzene ring, and an ethane naphthalene ring. Philippine ring, anthracene ring, thick tetraphenyl ring, Ring, triphenylene, anthracene, biphenyl, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, pyridazine Ring, anthracene ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolizine ring, quinoline ring, pyridazine ring, naphthyridine ring, quinoxaline ring, quinoxaline ring, different Quinoline ring, carbazole ring, phenazin ring, acridine ring, phenanthroline ring, thioxan ring, benzopyran ring, xanthene ring, morphine ring, phenothiazine ring, and phenazine ring, most Good for benzene ring. The aryl group may also be bonded to a plurality of aromatic rings via a single bond or a linking group to be described later. As the linking group, for example, an alkyl group is preferred. It is also preferred that the alkyl group is linear or branched. Specific examples of the aryl group in which a plurality of aromatic rings are bonded via a single bond or a linking group include biphenyl, diphenylmethane, diphenylpropane, diphenylisopropane, triphenylmethane, and tetraphenyl. Methane and the like.

Examples of the substituent which the organic group represented by A ¹ may include, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; or an alkyl group such as a methoxy group, an ethoxy group or a third butoxy group; An oxy group; an aryloxy group such as a phenoxy group and a p-tolyloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group and a butoxycarbonyl group; an aryloxycarbonyl group such as a phenoxycarbonyl group; an ethoxy group or a propyloxy group; And an anthracene group such as an ethenyloxy group; an oxime group such as an ethyl fluorenyl group, a benzamidine group, an isobutyl group, an acryl fluorenyl group, a methacryl fluorenyl group, and a methoxycyanyl group; a methyl fluorenyl group and a tert-butyl group; An alkyl group such as a fluorenyl group; an aryl fluorenyl group such as a phenylfluorenyl group and a p-tolyl fluorenyl group; an alkyl group such as a methyl group, an ethyl group, a tert-butyl group or a dodecyl group; a halogenated alkyl group such as a fluorinated alkyl group; a cyclopentyl group; a cycloalkyl group such as a cyclohexyl group, a cycloheptyl group or an adamantyl group; an aryl group such as a phenyl group, a p-tolyl group, a xylyl group, a cumenyl group, a naphthyl group, an anthracenyl group or a phenanthryl group; a hydroxyl group; a carboxyl group; a formazan group; Sulfo; cyano; alkylaminocarbonyl; arylaminocarbonyl; sulfonylamino; decylalkyl; amine; monoalkylamine; dialkylamine; aryl Group; diaryl group; sulfoxy; or the combination of these.

L ¹ represents a (m+1)-valent linking group. The linking group is not particularly limited, and examples thereof include -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, and an alkylene group (preferably a carbon number). a linear alkyl group or a branched alkyl group of 1 to 10, a cycloalkyl group (preferably a cycloalkyl group having 3 to 10 carbon atoms), an alkenyl group (preferably a linear chain of 210 carbon atoms) An alkenyl group or a branched alkenyl group), or a plurality of linking groups formed by these. The total carbon number of the linking group is preferably 3 or less. The linking group is preferably an alkyl group, a cycloalkyl group, an alkenyl group group, more preferably a linear alkyl group or a branched alkyl group, and more preferably a linear alkyl group, particularly preferably an ethyl group or an alkyl group. Methyl, most preferably methylene.

R ¹ represents a monovalent organic group. Examples of the monovalent organic group include an aliphatic group, an aryl group and the like. Examples of the aliphatic group and the aryl group include those described in the above A ¹ . The monovalent organic group represented by R ¹ may have a substituent. Examples of the substituent include the above. R ^{1 is} preferably a group having a carboxyl group. That is, R ^{1 is} preferably a group represented by the following formula. -L ² -(COOH) _{n In the} formula, L ² represents a (n+1)-valent linking group, and n represents an integer of 1 or more. The linking group represented by L ² may be the group described in the above L ¹ , and the preferred range is also the same, and particularly preferably an ethyl group or a methylene group, and most preferably a methylene group. n represents an integer of 1 or more, preferably 1 or 2, more preferably 1. The upper limit of n is the maximum number of substituents which can be used for the linking group represented by L ² . When n is 1, heating of 200 ° C or lower is likely to cause a tertiary amine having a high boiling point. Further, the stability of the negative photosensitive resin composition can be improved.

m represents an integer of 1 or more, preferably 1 or 2, more preferably 1. The upper limit of m is the maximum number of substituents which can be used for the linking group represented by L ¹ . When m is 1, heating by 200 ° C or lower is likely to cause a tertiary amine having a high boiling point. Further, the stability of the negative photosensitive resin composition can be improved. p represents an integer of 1 or more, preferably 1 or 2, more preferably 1. The upper limit of p is the maximum number of substituents which the organic group represented by A ¹ can employ. When p is 1, heating at 200 ° C or lower is likely to cause a tertiary amine having a high boiling point.

In the present invention, the compound represented by the formula (A1) is preferably a compound represented by the following formula (1a). [化38] In the formula (1a), A ¹ represents a p-valent organic group, L ¹ represents a (m+1)-valent linking group, L ² represents a (n+1)-valent linking group, and m represents an integer of 1 or more, n An integer of 1 or more is represented, and p represents an integer of 1 or more. The meanings of A ¹ , L ¹ , L ² , m, n and p of the formula (1a) are the same as those described in the formula (A1), and the preferred ranges are also the same.

In the present invention, the compound represented by the formula (A1) is preferably N-aryliminodiacetic acid. N-aryliminodiacetic acid is a compound in which A ¹ in the formula (A1) is an aryl group, L ¹ and L ² are a methylene group, m is 1, n is 1, and p is 1. N-aryliminodiacetic acid easily produces a tertiary amine having a high boiling point at 120 ° C to 200 ° C.

Specific examples of the thermal base generator in the present invention are described below, but the present invention is not limited to these specific examples. These may be used alone or in combination of two or more. Me in the following formula represents a methyl group. Among the compounds shown below, (A-1) to (A-11), (A-18), and (A-19) are compounds represented by the above formula (A1). Among the compounds shown below, (A-1) to (A-11), (A-18) to (A-26), and more preferably (A-1) to (A-9). , (A-18) to (A-21), (A-23), (A-24). Moreover, from the viewpoint of improving the adhesion to copper, it is preferably (A-18) to (A-26), (A-38) to (A-43), and more preferably (A-26). (A-38) to (A-43).

[Table 1]

[Table 2] [table 3] [Table 4] [table 5]

As the thermal base generator used in the present invention, the compounds described in Paragraph No. 0015 to Paragraph 0055 of the specification of Japanese Patent Application No. 2015-034388 are preferably used, and the contents are incorporated in the present specification.

When the hot alkali generating agent is used, the content of the hot alkali generating agent in the negative photosensitive resin composition is preferably from 0.1% by mass to 50% by mass based on the total solid content of the negative photosensitive resin composition. The lower limit is more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less. The hot base generator may be used alone or in combination of two or more. When two or more types are used, it is preferred that the total amount is the above range.

<Thermal Radical Polymerization Starter> The negative photosensitive resin composition of the present invention may further contain a thermal radical polymerization initiator. As the thermal radical polymerization initiator, a known thermal radical polymerization initiator can be used. The thermal radical polymerization initiator is a compound which generates radicals by thermal energy and starts or promotes polymerization of a polymerizable compound. When the cyclization reaction of the polyimide precursor is carried out by adding a thermal radical polymerization initiator, the polymerization reaction of the polymerizable compound can be carried out. Further, when the polyimine precursor contains an ethylenically unsaturated bond, the cyclization of the polyimide precursor can be carried out together with the polymerization of the polyimide precursor, so that higher heat resistance can be achieved. . Examples of the thermal radical polymerization initiator include aromatic ketones, phosphonium salt compounds, peroxides, sulfur compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, oxazine compounds, and porphyrin. a metal compound, an active ester compound, a compound having a carbon halogen bond, an azo compound, or the like. Among them, a peroxide or an azo compound is more preferred, and a peroxide is particularly preferred. The 10-hour half-life of the thermal radical polymerization initiator used in the present invention is preferably from 90 ° C to 130 ° C, more preferably from 100 ° C to 120 ° C. Specifically, the compound described in Paragraph No. 0074 to Paragraph No. 0118 of JP-A-2008-63554 is mentioned. Among the commercially available products, Perbutyl Z and Percumyl D (manufactured by Nippon Oil Co., Ltd.) can be suitably used.

When the negative photosensitive resin composition contains a thermal radical polymerization initiator, the content of the thermal radical polymerization initiator is preferably 0.1% by mass to 50% by mass based on the total solid content of the negative photosensitive resin composition. % is more preferably 0.1% by mass to 30% by mass, particularly preferably 0.1% by mass to 20% by mass. In addition, it is preferably contained in an amount of from 0.1 part by mass to 50 parts by mass, more preferably from 0.5 part by mass to 30 parts by mass, based on 100 parts by mass of the polymerizable compound. According to this aspect, it is easy to form a cured film which is more excellent in heat resistance. The thermal radical polymerization initiator may be used alone or in combination of two or more. When the number of the thermal radical polymerization initiators is two or more, it is preferred that the total is in the above range.

<Anticorrosive Agent> In the negative photosensitive resin composition of the present invention, it is preferred to add an anticorrosive agent. The anticorrosive agent is added for the purpose of preventing the ions from flowing out of the metal wiring. For example, the rust preventive agent described in paragraph 0094 of JP-A-2013-15701, Japanese Patent Laid-Open No. 2009-283711 The compound described in Paragraph No. 0073 to Paragraph No. 0076 of the Japanese Patent Publication No. JP-A-2011-59656, Paragraph No. 0052, Paragraph No. 0114, Paragraph No. 0116 of JP-A-2012-194520 And the compound described in Paragraph No. 0118. Among them, a compound having a triazole ring or a compound having a tetrazole ring can be preferably used, more preferably 1,2,4-triazole, 1,2,3-benzotriazole, 5-methyl-1H. - benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, most preferably 1H-tetrazole. When the anticorrosive agent is added, the amount of the anticorrosive agent is preferably in the range of 0.1 part by mass to 10 parts by mass, more preferably 0.2 part by mass to 5 parts by mass, based on 100 parts by mass of the polyimine precursor. The anticorrosive agent may be used alone or in combination of two or more. When two or more types are used, it is preferable to add up to the above range.

<Metal adhesion improver> The negative photosensitive resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to a metal material used for an electrode or a wiring. Examples of the metal adhesion improver include those described in paragraphs 0046 to 0049 of JP-A-2014-186186, and paragraphs 0032 to 0043 of JP-A-2013-072935. a thioether compound. Further, as the metal adhesion improver, the following compounds can also be exemplified. [39] When a metal adhesion improver is used, the amount of the metal adhesion improver is preferably from 0.1 part by mass to 30 parts by mass, more preferably from 0.5 part by mass to 15 parts by mass per 100 parts by mass of the polyimide intermediate precursor. The range of parts by mass. By setting it as 0.1 mass part or more, the adhesiveness of the film after thermosetting and metal is favorable, and it is set as 30 mass parts or less, and the heat resistance and mechanical characteristics of the film after hardening are favorable. The metal adhesion improver may be used alone or in combination of two or more. When two or more types are used, it is preferable to add up to the above range.

<Centane Coupling Agent> The negative photosensitive resin composition of the present invention preferably contains a decane coupling agent in terms of improving adhesion to the substrate. Examples of the decane coupling agent include the compounds described in paragraphs 0062 to 0063 of JP-A-2014-191002, and the compounds described in paragraphs 0063 to 0071 of WO2011/080992A1. The compound described in paragraph No. 0060 to paragraph 0061 of JP-A-2014-191252, and the compound described in paragraph 0045 to paragraph 0052 of JP-A-2014-41264, and WO2014/097594 The compound described in Paragraph No. 0055. Further, it is also preferred to use two or more different decane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. When a decane coupling agent is used, the compounding amount of the decane coupling agent is preferably in the range of 0.1 part by mass to 20 parts by mass, more preferably 1 part by mass to 10 parts by mass, based on 100 parts by mass of the polyimide intermediate precursor. . When it is 0.1 part by mass or more, it is possible to provide more sufficient adhesion to the substrate, and if it is 20 parts by mass or less, it is possible to further suppress problems such as an increase in viscosity at the time of storage at room temperature. The decane coupling agent may be used alone or in combination of two or more. When two or more types are used, it is preferable to add up to the above range.

<Sensitizing dye> The negative photosensitive resin composition of the present invention may further contain a sensitizing dye. The sensitizing dye absorbs specific active radiation and becomes an electronically excited state. The sensitizing dye which is in an electronically excited state is brought into contact with a hot alkali generating agent, a thermal radical polymerization initiator, a photoradical polymerization initiator, and the like, and causes an action of electron movement, energy movement, and heat generation. Thereby, the thermal base generator, the thermal radical polymerization initiator, and the photoradical polymerization initiator are chemically changed to be decomposed, and a radical, an acid or a base is generated.

Examples of preferred sensitizing dyes include those belonging to the following compounds and having an absorption wavelength in a region of 300 nm to 450 nm. For example, polynuclear aromatics (for example, phenanthrene, anthracene, anthracene, anthracene, triphenylene, 9,10-dialkyloxyanthracene), xanthenes (for example, luciferin, eosin, erythromycin, and if Danming B, Bengal Rose Red), thioxanthone (such as 2,4-diethylthiazinone), cyanine (such as thiacarbocyanine, oxacarbocyanine), merocyanine Classes (eg, merocyanine, carbocyanine), thiazides (eg, thiazide, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavon, acridine flavin), 蒽Terpenoids (eg, hydrazine), squaric acid guanidine salts (eg, squaric acid ylide), coumarin (eg 7-diethylamino-4-methylcoumarin), benzene Vinyl benzenes, distyryl benzenes, oxazoles, and the like.

Among them, in the present invention, from the viewpoint of initial efficiency, it is preferred to use a polynuclear aromatic group (for example, phenanthrene, anthracene, anthracene, anthracene, triphenylene), thioxanthone or distyrylbenzene. The class, styrylbenzene, more preferably a compound having an anthracene skeleton. Specific examples of the specific compound include 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene and the like.

When the negative photosensitive resin composition contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01% by mass to 20% by mass, and more preferably 0.1% by mass based on the total solid content of the negative photosensitive resin composition. ～15% by mass, and more preferably 0.5% by mass to 10% by mass. The sensitizing dye may be used alone or in combination of two or more.

<Chain Transfer Agent> The negative photosensitive resin composition of the present invention may further contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by the Society for Polymerics, 2005) at pages 683-684. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, or GeH in the molecule can be used. The chain transfer agents provide hydrogen to the low-activity radical species to form free radicals, or are oxidized and then deprotonated, thereby generating free radicals. In particular, a thiol compound (for example, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 3-mercaptotriazole, 5-mercaptotetrazole, or 5-mercaptotetrazole may be preferably used. Wait).

When the negative photosensitive resin composition contains a chain transfer agent, the content of the chain transfer agent is preferably from 0.01 part by mass to 20 parts by mass, more preferably from 100 parts by mass based on the total solid content of the negative photosensitive resin composition. 1 part by mass to 10 parts by mass, and more preferably 1 part by mass to 5 parts by mass. The chain transfer agent may be used alone or in combination of two or more. When the chain transfer agent is two or more kinds, it is preferred that the total amount is the above range.

<Interacting Agent> In the negative photosensitive resin composition of the present invention, various surfactants may be added from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an anthrone-based surfactant can be used. In particular, by including a fluorine-based surfactant, the liquid properties (especially fluidity) at the time of preparation as a coating liquid are further improved, so that the uniformity of the coating thickness or the liquid-saving property can be further improved. When a film is formed using a coating liquid containing a fluorine-based surfactant, the interfacial tension between the surface to be coated and the coating liquid is lowered, whereby the wettability to the surface to be coated is improved, and the coating is applied. The coating properties of the surface are improved. Therefore, even when a film having a thickness of about several μm is formed with a small amount of liquid, it is effective to form a film having a uniform thickness with a small thickness unevenness.

The fluorine content of the fluorine-based surfactant is suitably from 3% by mass to 40% by mass, more preferably from 5% by mass to 30% by mass, even more preferably from 7% by mass to 25% by mass. The fluorine-containing surfactant having a fluorine content in this range is effective in terms of the uniformity of the thickness of the coating film or the liquid-saving property, and the solubility is also good. Examples of the fluorine-based surfactant include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, and Megafac. F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac F479, Megafac F482, Megafac F554, Megafac F780, Megafac F781 (above, DiCai (DIC) (share) manufacturing), Fluorad FC430 , Fluorad FC431, Fluorad FC171 (above, Sumitomo 3M (share)), Surflon S-382, Surflon SC-101 , Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, sand Surflon SC-383, Sha Fulong (Su Rflon) S393, Surfon KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA). As the fluorine-based surfactant, a block polymer can also be used. Specific examples thereof include a compound described in JP-A-2011-89090. Further, the following compounds can also be exemplified as the fluorine-based surfactant used in the present invention. [化40] The weight average molecular weight of the compound is, for example, 14,000.

Specific examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, Glycerol ethoxylate, etc., polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethyl b Diol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, Pluronic L31, manufactured by BASF) Pluronic L61, Pluronic L62, Pluronic 10R5, Pluronic 17R2, Pluronic 25R2, Tetronic 304, Tetronic 701, Tetronic 704, Tetronic 901, Tetronic 904, Tetronic 150R1), Solsperse 20000 (Japan Lubo Lubrizol ( Parts)) and the like. In addition, Pionin D-6112-W manufactured by Takeshi Oil Co., Ltd., and NCW-101, NCW-1001, and NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. can also be used.

Specific examples of the cation-based surfactant include a phthalocyanine derivative (trade name: Efka (EFKA)-745, manufactured by Morishita Industry Co., Ltd.), and an organic siloxane polymer KP341 (Shin-Etsu Chemical Industry) (Made) manufacturing), (meth)acrylic (co)polymer Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 ( Gongrongshe Chemical (share) manufacturing), W001 (Yu Shang (share) manufacturing) and so on.

Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yusho Co., Ltd.).

Examples of the fluorenone-based surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, and Toray ketone manufactured by Toray Dow Corning Co., Ltd. (Toray Silicone) DC11PA", "Toray Silicone SH21PA", "Toray Silicone SH28PA", "Toray Silicone SH29PA", "Toray Ketone (Toray) Silicone) SH30PA", "Toray Silicone SH8400", "TSF-4440", "TSF-4300", "TSF-4445", "TSF-" manufactured by Momentive Performance Materials 4460", "TSF-4452", "KP341", "KF6001", "KF6002" manufactured by Shintosu Silicon Co., Ltd., "BYK307" and "BYK323" manufactured by BYK Chemie , "BYK330" and so on.

When the negative photosensitive resin composition contains a surfactant, the content of the surfactant is preferably 0.001% by mass to 2.0% by mass, and more preferably 0.005% by mass based on the total solid content of the negative photosensitive resin composition. ~1.0% by mass. The surfactant may be used alone or in combination of two or more. When two or more types of surfactants are contained, it is preferable to add up to the said range.

<Higher Fatty Acid Derivatives and the like> In the negative photosensitive resin composition of the present invention, in order to prevent polymerization inhibition by oxygen, a higher fatty acid derivative such as behenic acid or behenylamine may be added. And the like, and it is biased toward the surface of the negative photosensitive resin composition during the drying after coating. When the negative photosensitive resin composition contains a higher fatty acid derivative or the like, the content of the higher fatty acid derivative or the like is preferably 0.1% by mass to 10% by mass based on the total solid content of the negative photosensitive resin composition. The higher fatty acid derivative or the like may be used alone or in combination of two or more. When two or more kinds of higher fatty acid derivatives and the like are contained, it is preferred that the total is in the above range.

<Solvent> When the negative photosensitive resin composition of the present invention is formed into a layer by coating, it is preferred to prepare a solvent. As long as the negative photosensitive resin composition can be formed into a layer form, the solvent can be used without any limitation. The solvent to be used in the negative photosensitive resin composition of the present invention may, for example, be ethyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate or isoamyl acetate. Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, oxyacetic acid Alkyl esters (such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxyacetate) Ester, ethyl ethoxyacetate, etc.), alkyl 3-oxopropionate (eg methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg 3-methoxypropane) Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-oxopropionate (eg 2 Methyl oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2- Propyl methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionic acid Ester)), methyl 2-oxy-2-methylpropanoate and ethyl 2-oxy-2-methylpropanoate (for example methyl 2-methoxy-2-methylpropionate, 2- Ethyl ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxobutanoate And ethyl 2-oxobutanoate and the like, and examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and methyl soluble fiber. Acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Examples of the ketones include propylene glycol monoethyl ether acetate and propylene glycol monopropyl ether acetate, and examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-glycol. Examples of the ketone, N-methyl-2-pyrrolidone, and the like, and examples of the aromatic hydrocarbons include toluene, xylene, anisole, and limonene, and the like, and may be suitably used as an anthraquinone. Listed dimethyl hydrazine.

From the viewpoint of improvement in the state of the coated surface, etc., a form in which two or more kinds of solvents are mixed is also preferable. Among them, preferred is a mixed solution comprising methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, and diethyl phthalate. Alcohol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl azine, ethyl carbitol Two or more of an acid ester, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate. It is particularly preferred to use dimethyl hydrazine and γ-butyrolactone in combination.

When the negative photosensitive resin composition contains a solvent, the solvent content is preferably such that the total solid content of the negative photosensitive resin composition is 5 to 80% by mass. The amount is more preferably 5% by mass to 70% by mass, still more preferably 10% by mass to 60% by mass. The solvent may be used alone or in combination of two or more. When two or more solvents are contained, it is preferable that they add up to the above range. Further, from the viewpoint of film strength, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-di, relative to the total mass of the negative photosensitive resin composition The content of methyl acetamide and N,N-dimethylformamide is preferably less than 5% by mass, more preferably less than 1% by mass, still more preferably less than 0.5% by mass, particularly preferably not Full 0.1% by mass.

<Other Additives> The negative photosensitive resin composition of the present invention may be formulated with various additives such as inorganic particles, hardeners, hardening catalysts, fillers, antioxidants, ultraviolet rays, as needed within the scope of the effects of the present invention. Absorbent, anti-agglomerating agent, etc. When the additives are blended, the total amount of the additives is preferably 3% by mass or less of the solid content of the negative photosensitive resin composition.

The moisture content of the negative photosensitive resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, particularly preferably less than 0.6% by mass, from the viewpoint of the surface state of the coating.

The metal content of the negative photosensitive resin composition of the present invention is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, particularly preferably less than 0.5 ppm by mass, from the viewpoint of the insulating property. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel, and the like. When a plurality of metals are contained, it is preferred that the total of the metals is in the range. In addition, as a method of reducing the metal impurities which are unintentionally contained in the negative photosensitive resin composition, a method of selecting a raw material having a small metal content as a raw material constituting the negative photosensitive resin composition, and forming a negative type may be mentioned. The raw material of the photosensitive resin composition is subjected to filter filtration, and is lined with polytetrafluoroethylene or the like in the apparatus to carry out distillation under conditions which suppress contamination as much as possible.

The content of the halogen atom of the negative photosensitive resin composition of the present invention is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 by mass, from the viewpoint of wiring corrosion. Ppm. Among them, the halogen ion is preferably present in an amount of less than 5 ppm by mass, more preferably less than 1 ppm by mass, particularly preferably less than 0.5 ppm by mass. Examples of the halogen atom include a chlorine atom and a bromine atom. Preferably, the total of the chlorine atom and the bromine atom, or the chloride ion and the bromide ion are each in the above range.

<Preparation of Negative Photosensitive Resin Composition> The negative photosensitive resin composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited and can be carried out by a conventionally known method. Moreover, it is preferable to perform filtration using a filter for the purpose of removing foreign matter such as dust or fine particles in the negative photosensitive resin composition. The pore diameter of the filter is preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.1 μm or less. The material of the filter is preferably a filter made of polytetrafluoroethylene, polyethylene or nylon. The filter can also be washed using a solvent previously prepared with an organic solvent. In the filter filtration step, a plurality of filters can be used in series or in parallel. When using a variety of filters, it is also possible to combine filters with different apertures and/or materials. In addition, various materials can be filtered multiple times, and the step of multiple filtration can also be a cyclic filtration step. Further, the filtration may be carried out under pressure, and the pressure of the pressurization is preferably 0.05 MPa or more and 0.3 MPa or less. In addition to filtration using a filter, an adsorbent material may also be used for impurity removal. In addition, regarding the removal of impurities, the filter may be combined with the adsorbent material. As the adsorbent, a known adsorbent can be used. For example, an inorganic adsorbent such as cerium oxide gel or zeolite or an organic adsorbent such as activated carbon can be used.

<Application of Negative Photosensitive Resin Composition> The negative photosensitive resin composition of the present invention can be cured and used as a cured film. Since the negative photosensitive resin composition of the present invention can form a cured film having excellent heat resistance and insulating properties, it can be preferably used for an insulating film of a semiconductor element, an interlayer insulating film for a rewiring layer, or the like. In particular, it can be preferably used for an interlayer insulating film for a rewiring layer or the like in a three-dimensional mounting element. Further, it can also be used for a photoresist (galvanic resist, etch resist, solder top resist) for electronics. In addition, it can also be used in the manufacture of layouts such as lithographic or screen layouts, etching of formed parts, electronics, especially in protective coatings and dielectric layers in microelectronics.

<Method for Producing Cured Film> Next, a method for producing the cured film of the present invention will be described. The method for producing the cured film is not particularly limited as long as it is formed by using the negative photosensitive resin composition of the present invention. The method for producing a cured film of the present invention preferably includes a step of applying the negative photosensitive resin composition of the present invention to a substrate, and a step of curing the negative photosensitive resin composition for use on the substrate.

<<Step of Applying Negative Photosensitive Resin Composition to Substrate>> As a method of applying the negative photosensitive resin composition to the substrate, spin coating, dipping, blade coating, and suspension casting are exemplified ( Spin coating, electrostatic spraying, and reverse roll coating are preferred for the purpose of uniform application to coating, spray coating, electrostatic spray, back roll coating, and the like.

Examples of the substrate include an inorganic substrate, a resin, and a resin composite material. Examples of the inorganic substrate include a glass substrate, a quartz substrate, a tantalum substrate, a tantalum nitride substrate, and a composite substrate obtained by vapor-depositing molybdenum, titanium, aluminum, copper, or the like on the substrate. Examples of the resin substrate include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, and poly. Bismuth, polyether oxime, polyarylate, allyl diglycol carbonate, polyamine, polyimine, polyamidimide, polyether phthalimide, polybenzoxazole, polyphenylene sulfide , polycycloolefin, norbornene resin, fluororesin such as polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, fluorenone resin, ionic polymer resin, cyanate resin, crosslinked antibutene A substrate of a synthetic resin such as an acid diester, a cyclic polyolefin, an aromatic ether, a maleimide, an olefin, a cellulose, or an episulfide compound. These substrates are rarely used in the above-described form, and generally, for example, a multilayer laminated structure such as a thin film transistor (TFT) device can be formed depending on the form of the final product.

The amount of the negative photosensitive resin composition (thickness of the layer) and the type of the substrate (the carrier of the layer) depend on the field of the intended use. It is especially advantageous that the negative photosensitive resin composition can be used in a thickness of a layer which can be widely changed. The thickness of the layer is preferably in the range of 0.5 μm to 100 μm, and is more effective in the method of the present invention when it is 3 μm to 30 μm, and further 5 μm to 30 μm. It is preferred to apply the negative photosensitive resin composition to the substrate and then dry it. Drying is preferably carried out, for example, at 60 ° C to 150 ° C for 10 seconds to 2 minutes.

<<Heating Step>> The negative photosensitive resin composition applied to the substrate is heated, whereby the polyimine precursor is subjected to a cyclization reaction to form a cured film excellent in heat resistance. The heating temperature is preferably from 50 ° C to 300 ° C, more preferably from 100 ° C to 250 ° C. According to the present invention, since a large amount of isomers having a faster cyclization rate are contained, the cyclization reaction of the polyimide precursor can also be carried out at a lower temperature.

From the viewpoint of reducing the internal stress of the cured film or suppressing warpage, it is preferred to adjust at least one selected from the group consisting of heating rate, heating time, and cooling rate. 20 ° C to 150 ° C is used as the heating start temperature, and the heating rate is preferably 3 ° C / min to 5 ° C / min. When the heating temperature is 200 ° C to 240 ° C, the heating time is preferably 180 minutes or more. The upper limit is, for example, preferably 240 minutes or shorter. When the heating temperature is from 240 ° C to 300 ° C, the heating time is preferably 90 minutes or more. The upper limit is preferably, for example, 180 minutes or shorter. When the heating temperature is 300 to 380, the heating time is preferably 60 minutes or more. The upper limit is preferably, for example, 120 minutes or shorter. The cooling rate is preferably from 1 ° C / min to 5 ° C / min. Heating can be carried out in stages. As an example, a step of raising the temperature from 20 ° C to 150 ° C at 5 ° C / min, leaving at 150 ° C for 30 minutes, and then raising the temperature from 150 ° C to 230 ° C at 5 ° C / min, and at 230 ° C Place it for 180 minutes.

In terms of preventing the decomposition of the polyimide precursor such as polyimide, the heating step is preferably carried out in a low oxygen concentration environment by flowing an inert gas such as nitrogen, helium or argon. . The oxygen concentration is preferably 50 ppm by volume or less, more preferably 20 ppm by volume or less.

In the present invention, a pattern forming step may be performed between the step of applying the negative photosensitive resin composition on the substrate and the heating step. The pattern forming step can be performed, for example, by photolithography. For example, the method performed by the exposure process and the process of performing a development process is mentioned. The pattern formation by the photolithography method is preferably carried out using a photosensitive resin composition containing a polyimide precursor and a radical polymerization initiator. Hereinafter, a case where pattern formation is performed by photolithography will be described.

<<Exposure Step>> In the exposure step, the actinic ray or radiation corresponding to a predetermined pattern is applied to the negative photosensitive resin composition used for the substrate. The wavelength of the actinic ray or radiation varies depending on the composition of the negative photosensitive resin composition, but is preferably 200 nm to 600 nm, more preferably 300 nm to 450 nm. As the light source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a chemical lamp, a light emitting diode (LED) light source, an excimer laser generating device, or the like can be used, and i-ray (365 nm) can be preferably used. An actinic ray having a wavelength of 300 nm or more and 450 nm or less, such as h-ray (405 nm) or g-ray (436 nm). Further, the illumination light may be adjusted by a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter as needed. The exposure amount is preferably from 1 mJ/cm ² to 1000 mJ/cm ² , more preferably from 200 mJ/cm ² to 800 mJ/cm ² . The value of the present invention is high in terms of the development in a wide range and high developability in the manner described. As the exposure device, mirror projection aligner, stepper, scanner, proximity, contact, microlens array, lens scanner, laser exposure, etc. can be used. Exposure machine. Further, when (meth) acrylate and the like olefin unsaturated compound are used, such photopolymerization is known as a film, especially in a thin layer due to oxygen in the air. This effect can be alleviated, for example, by a known prior method such as introduction of a temporary coating layer of polyvinyl alcohol or pre-exposure or pre-adjustment in an inert gas.

<<Step of Performing Development Process>> In the step of performing the development process, the unexposed portion of the negative photosensitive resin composition is developed using a developer. As the developer, an aqueous alkaline developer, an organic solvent or the like can be used. Examples of the basic compound used in the aqueous alkaline developing solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium citrate, potassium citrate, and hemiplegia. Sodium, potassium metasilicate, ammonia or amine. Examples of the amine include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, and quaternary ammonium hydroxide. , Tetramethyl Ammonium Hydroxide (TMAH) or tetraethylammonium hydroxide. Among them, a basic compound containing no metal is preferred. Suitable aqueous alkaline developing solutions usually have a base of up to 0.5 N, but may also be suitably diluted prior to use. For example, an aqueous alkaline developing solution of about 0.15 N to 0.4 N, preferably 0.20 N to 0.35 N is also suitable. The basic compound may be used alone or in combination of two or more. When two or more basic compounds are used, it is preferred to add up to the above range. As the organic solvent, the same solvent as that which can be used for the negative photosensitive resin composition can be used. For example, acetic acid-n-butyl ester, γ-butyrolactone, cyclopentanone, and these may be mentioned. Further, it is also preferred to include a step of heating the developed negative photosensitive resin composition at a temperature of from 50 ° C to 500 ° C after the step of performing the development treatment. By such a step, there is an advantage of heat resistance or adhesion to the substrate.

The field of the method for producing a cured film to which the present invention can be applied is preferably used for an insulating film of a semiconductor element, an interlayer insulating film for a rewiring layer, or the like. In particular, since it has good resolution, it can be preferably used for an interlayer insulating film for a rewiring layer in a three-dimensional mounting element. Further, it can also be used for a photoresist (galvanic resist, etch resist, solder top resist) for electronics. In addition, it can also be used in the manufacture of layouts such as lithographic or screen layouts, etching of formed parts, electronics, especially in protective coatings and dielectric layers in microelectronics.

<Semiconductor Element> Next, an embodiment in which a negative photosensitive resin composition is used for a semiconductor element of an interlayer insulating film for a rewiring layer will be described. The semiconductor element 100 shown in FIG. 1 is a so-called three-dimensional mounting element, and a laminated body 101 in which a plurality of semiconductor devices (semiconductor wafer) 101a to semiconductor device (semiconductor wafer) 101d are laminated is disposed on the wiring substrate 120. In this embodiment, the number of layers of the semiconductor device (semiconductor wafer) is four, and the number of layers of the semiconductor device (semiconductor wafer) is not particularly limited. For example, it may be two layers. 8 layers, 16 layers, 32 layers, and the like. In addition, it can also be 1 layer.

Each of the plurality of semiconductor devices 101a to 101d includes a semiconductor wafer such as a germanium substrate. The uppermost semiconductor device 101a does not have a through electrode, and an electrode pad (not shown) is formed on one surface thereof. The semiconductor device 101b to the semiconductor device 101d have a through electrode 102b to a through electrode 102d, and connection pads (not shown) integrally provided on the through electrodes are provided on both surfaces of each semiconductor device.

The laminated body 101 has a structure in which a semiconductor device 101a having no through electrodes and a semiconductor device 101b to a semiconductor device 101d having a through electrode 102b to a through electrode 102d are flip-chip bonded. That is, the electrode pads of the semiconductor device 101a having no through electrodes and the connection pads on the side of the semiconductor device 101a of the semiconductor device 101b having the through electrodes 102b adjacent thereto are connected by metal bumps 103a such as solder bumps, and have a through-hole The connection pad on the other side of the semiconductor device 101b of the electrode 102b and the connection pad on the side of the semiconductor device 101b of the semiconductor device 101c having the through electrode 102c adjacent thereto are connected by a metal bump 103b such as a solder bump. Similarly, the connection pad on the other side of the semiconductor device 101c having the through electrode 102c and the connection pad on the side of the semiconductor device 101c having the semiconductor device 101d having the through electrode 102d adjacent thereto are made of a metal bump 103c such as a solder bump. Come connect.

The underfill layer 110 is formed in a gap between each of the semiconductor devices 101a to 101d, and each of the semiconductor devices 101a to 101d is laminated via the underfill layer 110.

The laminated body 101 is laminated on the wiring substrate 120. As the wiring substrate 120, for example, a multilayer wiring board using an insulating substrate such as a resin substrate, a ceramic substrate, or a glass substrate as a substrate is used. As the wiring substrate 120 to which the resin substrate is applied, a multilayer copper clad laminate (multilayer printed wiring board) or the like can be given.

A surface electrode 120a is provided on one surface of the wiring substrate 120. An insulating layer 115 on which the rewiring layer 105 is formed is disposed between the wiring substrate 120 and the laminated body 101, and the wiring substrate 120 and the laminated body 101 are electrically connected via the rewiring layer 105. The insulating layer 115 is formed using the negative photosensitive resin composition of the present invention. In other words, one end of the rewiring layer 105 is connected to the electrode pad formed on the surface on the side of the rewiring layer 105 of the semiconductor device 101d via the metal bump 103d such as a solder bump. Further, the other end of the rewiring layer 105 is connected to the surface electrode 120a of the wiring board via a metal bump 103e such as a solder bump. Further, an underfill layer 110a is formed between the insulating layer 115 and the laminated body 101. Further, an underfill layer 110b is formed between the insulating layer 115 and the wiring substrate 120. [Examples]

Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited to the following examples as long as the present invention does not exceed the gist of the invention. In addition, "%" and "parts" are quality standards unless otherwise specified. NMR is an abbreviation for nuclear magnetic resonance.

(Synthesis Example 1) [Polyimine precursor derived from pyromellitic dianhydride, 4,4'-oxydiphenylamine, and benzyl alcohol (A-1: Polyimine having no radical polymerizable group) Synthesis of Precursor] 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C for 12 hours) and 14.22 g (131.58 mmol) of benzyl alcohol were suspended in 50 ml of N - Methylpyrrolidone is dried by a molecular sieve. The suspension was heated at 100 ° C for 3 hours. A clear solution was obtained a few minutes after the start of heating. The reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) of pyridine and 90 ml of N-methylpyrrolidone were added. Then, the reaction mixture was cooled to -10 ° C while maintaining the temperature at -10 ° C ± 4 ° C, and 16.12 g (135.5 mmol) of SOCl _{2 was} added over 10 minutes. The viscosity increases during the addition of SOCl ₂ . After dilution with 50 ml of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, a solution of 11.08 g (58.7 mmol) of 4,4'-oxydiphenylamine dissolved in 100 ml of N-methylpyrrolidone at 20 ° C to 23 ° C for 20 minutes. It was added dropwise to the reaction mixture. The reaction mixture was then stirred at room temperature for 1 night. Then, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimine precursor mixture was stirred at 5000 rpm for 15 minutes. The polyimine precursor was filtered, again poured into 4 liters of water and stirred for 30 minutes and filtered again. Then, the obtained polyimine precursor was dried at 45 ° C for 3 days under reduced pressure to obtain a polyimine precursor (A-1) having a structure represented by the following formula. [化41]

(Synthesis Example 2) [Polyimine precursor derived from pyromellitic dianhydride, 4,4'-oxydiphenylamine, and 2-hydroxyethyl methacrylate (A-2: having radical polymerizability) Synthesis of a base polyimine precursor] 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C for 12 hours), 18.6 g (129 mmol) of methacrylic acid 2-hydroxyethyl ester, 0.05 g of hydroquinone, 10.7 g of pyridine, and 140 g of diethylene glycol dimethyl dimethyl ether (diglyme) were mixed and stirred at 60 ° C for 18 hours to produce benzene A diester of tetracarboxylic acid and 2-hydroxyethyl methacrylate. Then, the obtained diester was chlorinated by SOCl ₂ , and converted into a polyimine precursor by 4,4'-oxydiphenylamine in the same manner as in Synthesis Example 1, and Synthesis Example 1 was used. The same method was used to obtain a polyimine precursor (A-2) containing a structure represented by the following formula. [化42]

(Synthesis Example 3) [Polyimine precursor from 4,4'-oxydiphthalic anhydride, 4,4'-oxydiphenylamine and 2-hydroxyethyl methacrylate (A- 3: Synthesis of a polyethylenimine precursor having a radical polymerizable group] 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140 ° C for 12 hours) ), 18.6 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 10.7 g of pyridine, and 140 g of diethylene glycol dimethyl ether, and at 60 The mixture was stirred at a temperature of ° C for 18 hours to produce a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Then, the obtained diester was chlorinated by SOCl ₂ , and converted into a polyimine precursor by 4,4'-oxydiphenylamine in the same manner as in Synthesis Example 1, and Synthesis Example 1 was used. The same method was used to obtain a polyimine precursor (A-3) containing a structure represented by the following formula. [化43]

(Synthesis Example 4) [Polyimine precursor derived from 4,4'-oxydiphthalic anhydride and 4,4'-oxydiphenylamine (A-4: Polyimine having a carboxyl group) Synthesis of Precursor] 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140 ° C for 12 hours) was dissolved in 180 ml of N-methyl-2- Further, 21.43 g (270.9 mmol) of pyridine was added to the N-methyl-2-pyrrolidone (NMP), and the reaction liquid was cooled to -10 ° C while maintaining the temperature at -10 ° C ± 4 ° C. A solution obtained by dissolving 11.08 g (58.7 mmol) of 4,4'-oxydiphenylamine in 100 ml of NMP was added dropwise over 30 minutes, and then the reaction mixture was stirred at room temperature for 1 night. Then, the polyimine precursor was precipitated by pouring into 5 liters of water, and the water-polyimine precursor mixture was stirred at 5000 rpm for 15 minutes. The polyimine precursor was filtered, and again poured into 4 liters of water and stirred for 30 minutes, and filtered again. Then, the obtained polyimine precursor was dried at 45 ° C for 3 days under reduced pressure to obtain a polyimine precursor (A-4) containing a structure represented by the following formula. [化44]

(Synthesis Example 5) [Synthesis of Polymer (RA-1) for Comparative Example] 27.0 g (153.2 mmol) of benzyl methacrylate, 20 g (157.3 mmol) of N-isopropyl A Acrylamide, 39 g (309.2 mmol) of allyl methacrylate, 13 g (151.0 mmol) of methacrylic acid, polymerization initiator (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) 3.55 g (15.4 mmol) and 3-methoxy-2-propanol 300 g were mixed. The mixed liquid was added to 300 g of 3-methoxy-2-propanol heated at 75 ° C over 2 hours under a nitrogen atmosphere. After completion of the dropwise addition, the mixture was further stirred at 75 ° C for 2 hours under a nitrogen atmosphere. After the reaction was completed, the mixture was poured into 5 liters of water to precipitate a polymer, and stirred at 5000 rpm for 15 minutes. The acrylic resin was filtered, and again poured into 4 liters of water and stirred for 30 minutes, and filtered again. Then, the obtained acrylic resin was dried at 45 ° C for 3 days under reduced pressure to obtain a comparative polymer (RA-1) represented by the following formula. [化45]

<Examples and Comparative Examples> The components described below were mixed to prepare a uniform solution, and a coating liquid of a photosensitive resin composition was prepared. <<Composition of photosensitive resin composition>> Polyimine precursor: Mass parts of the radical polymerization initiator described in Table 6: Parts by mass of the first polymerization inhibitor described in Table 6: Parts by mass of Table 6 (2) The polymerization inhibitor: the mass fraction of the radically polymerizable compound described in Table 6: the mass fraction of the hot base generator described in Table 6: parts by mass (other components) described in Table 6 γ-butyrolactone: 60.00 parts by mass

[Table 6]

The abbreviations described in Table 6 are as follows. (A) Polyimine precursor or comparative resin A-1 to A-4 and RA-1: resins synthesized in Synthesis Examples 1 to 5

(B) Photoradical polymerization initiator B-1: Irgacure-OXE01 (manufactured by BASF) B-2: Irgacure 369 (manufactured by BASF) B- 3: Irgacure 784 (made by BASF)

(C) First polymerization inhibitor C-1: 4-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) C-2: 2,6-di-t-butyl-4-methylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) C-3: Pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (Manufactured by BASF, Irganox 1010) C- 4: thiodiethyl bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (Manufactured by BASF, Irganox 1035) C-5: octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (Manufactured by BASF, Irganox 1076) C -6: N,N'-hexane-1,6-diylbis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanamide] (Manufactured by BASF) , Irganox 1098) C-7: 3, 3', 3'', 5, 5', 5''-hexa-t-butyl-a, a', a''- (both Trimethyl-2,4,6-triyl)tri-p-cresol (manufactured by BASF, Irganox 1330) C-8: Ethyl bis(oxyethyl) double 3-(5-t-butyl-4-hydroxym-tolyl)propionate] (BASF) Manufactured, Irganox 245) C-9: Hexamethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (BASF) Manufactured by the company, Irganox 259) C-10: 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine -2,4,6(1H,3H,5H)-trione (manufactured by BASF Corporation, Irganox 3114) C-11: catechol (manufactured by Tokyo Chemical Industry Co., Ltd.) C-12: Third butyl-catechol (manufactured by Tokyo Chemical Industry Co., Ltd.)

(D) 2nd polymerization inhibitor D-1: 2,4,6-tri-tert-butyl-nitrosobenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) D-2: phenyl-t-butylnitrone (Tokyo Chemical manufacturing) D-3: 3,3,5,5-tetramethyl-1-pyrroline-N-oxide (manufactured by Tokyo Chemical Industry Co., Ltd.) D-4: p-benzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) D- 5: Pair of formazan (manufactured by Tokyo Chemical Industry Co., Ltd.) D-6: 2-Terbutyl-p-benzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) D-7: 2,2,6,6-tetramethylpiperidine 1- Oxygen (manufactured by Tokyo Chemical Industry Co., Ltd.) D-8: 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (manufactured by Tokyo Chemical Industry Co., Ltd.) D-9: 4-methyl propylene oxime Base-2,2,6,6-tetramethylpiperidine 1-oxyl (manufactured by Tokyo Chemical Industry Co., Ltd.) D-10: N-nitrosodiphenylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) D-11: morphine Pyrazine (manufactured by Tokyo Chemical Industry Co., Ltd.)

(E) Radical polymerizable compound E-1: NK ester (NK ESTER) M-40G (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.; monofunctional methacrylate; the following structure) [Chem. 46] E-2: NK Ester 4G (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.; difunctional methacrylate; the following structure) [Chem. 47] E-3: NK Ester A-9300 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.; trifunctional acrylate; structure described below)

(F) Thermal base generator [Chem. 49] F-1: F-2:

Comparative Example Polymer (RA-2): Polymethyl methacrylate (Mw: 15,000, manufactured by Aldrich)

Each of the negative photosensitive resin compositions was subjected to pressure filtration through a filter having a pore width of 0.8 μm, and then spin-coated on a tantalum wafer for application. The tantalum wafer to which the negative photosensitive resin composition was applied was dried at 100 ° C for 5 minutes on a hot plate to form a uniform polymer layer having the thickness shown in Table 6 on the tantalum wafer.

<Evaluation> [Exposure latitude] The photosensitive resin composition layer on the germanium wafer was exposed using a stepper (Nikon NSR2005i9C). Exposure is performed using i-rays at a wavelength of 365 nm at 200 mJ/cm ² , 300 mJ/cm ² , 400 mJ/cm ² , 500 mJ/cm ² , 600 mJ/cm ² , 700 mJ/cm ² Each exposure energy of 800 mJ/cm ² was exposed using a line and space mask of 1 μm from 5 μm to 25 μm.

The exposed photosensitive resin composition layer was developed with cyclopentanone for 60 seconds. The line width which can have sharpness of a good edge is evaluated by the following criteria. The smaller the line width of the photosensitive resin composition layer is, the larger the difference in solubility of the light-irradiating portion and the non-light-irradiating portion with respect to the developer is, which is a preferable result. Further, the smaller the change in the line width with respect to the change in the exposure energy, the wider the exposure latitude, which is a preferable result. The measurement limit is 5 μm. The results are shown in Table 7. A: 5 μm or more and 8 μm or less B: More than 8 μm, 10 μm or less C: More than 10 μm, 15 μm or less D: More than 15 μm, 20 μm or less E: More than 20 μm

[Heat resistance] After the exposed photosensitive resin composition layer was heated at 300 ° C for 3 hours in a nitrogen atmosphere, the exposed photosensitive resin composition layer was peeled off, and the temperature was raised at 10 ° C / min in nitrogen gas. The conditions were measured by thermal mass spectrometry, and the thermal decomposition temperature was measured and evaluated by the following criteria. The results are shown in Table 7. A: 5% mass reduction temperature is above 300 °C B: 5% mass reduction temperature is less than 300 °C

[Table 7]

The numerical value of the exposure latitude in Table 7 indicates the exposure energy (unit: mJ/cm ² ). In Comparative Example 4, since all the components were dissolved by the development treatment of cyclopentanone, measurement was impossible.

<Example 100> The negative photosensitive resin composition of Example 1 was subjected to pressure filtration through a filter having a pore width of 0.8 μm, and then spin-coated on a resin substrate on which a copper thin layer was formed (3500 rpm) , 30 seconds) to apply. The negative photosensitive resin composition applied to the resin substrate was dried at 100 ° C for 5 minutes, and then exposed using an aligner (Karl-Suss MA150). Exposure was performed using a high pressure mercury lamp to measure the exposure energy at a wavelength of 365 nm. After exposure, the image was developed with cyclopentanone for 75 seconds. Then, heating was carried out at 180 ° C for 20 minutes. Thus, an interlayer insulating film for a rewiring layer is formed. The interlayer insulating film for a rewiring layer is excellent in insulation properties. In addition, the semiconductor element was produced using the interlayer insulating film for a rewiring layer, and as a result, it was confirmed that the operation was performed without any problem.

100‧‧‧Semiconductor components
101‧‧‧Layer
101a～101d‧‧‧ semiconductor devices (semiconductor wafers)
102b～102d‧‧‧through electrodes
103a～103e‧‧‧Metal bumps
105‧‧‧Rewiring layer
110, 110a, 110b‧‧‧ underfill layer
115‧‧‧Insulation
120‧‧‧Wiring substrate
120a‧‧‧ surface electrode

Fig. 1 is a schematic view showing a configuration of an embodiment of a semiconductor device.

100‧‧‧Semiconductor components

101‧‧‧Layer

101a~101d‧‧‧ semiconductor devices (semiconductor wafers)

102b~102d‧‧‧through electrode

103a~103e‧‧‧Metal bumps

105‧‧‧Rewiring layer

110, 110a, 110b‧‧‧ underfill layer

115‧‧‧Insulation

120‧‧‧Wiring substrate

120a‧‧‧ surface electrode

Claims (19)

A negative photosensitive resin composition comprising: a polyimide intermediate; a radical polymerization initiator; a first polymerization inhibitor selected from at least one of a compound having an aromatic hydroxyl group; and a second polymerization The inhibitor is at least one selected from the group consisting of a nitroso compound, an N-oxide compound, an anthracene compound, an N-oxyl compound, and a phenothiazine compound. The negative photosensitive resin composition according to claim 1, wherein the polyimine precursor comprises a repeating unit represented by the following formula (1); In the formula (1), A ¹ and A ² each independently represent an oxygen atom or -NH-, R ¹¹ represents a divalent organic group, R ^{1 2} represents a tetravalent organic group, and R ¹³ and R ¹⁴ are each independently Represents a hydrogen atom or a monovalent organic group. The negative photosensitive resin composition according to the second aspect of the invention, wherein at least one of R ¹³ and R ¹⁴ in the formula (1) contains a radical polymerizable group. The negative photosensitive resin composition as described in claim 1 or 2, further comprising a radically polymerizable compound. The negative photosensitive resin composition as described in claim 4, wherein the radically polymerizable compound has two or more radical polymerizable groups. The negative photosensitive resin composition according to the above aspect, wherein the second polymerization inhibitor is selected from the group consisting of an anthracene compound and an N-oxyl compound. The negative photosensitive resin composition according to the first or second aspect of the invention, wherein the mass ratio of the first polymerization inhibitor to the second polymerization inhibitor is from 10:90 to 90:10. The negative photosensitive resin composition according to claim 1 or 2, wherein a mass ratio of the first polymerization inhibitor to the radical polymerization initiator is 1:99 to 10:90 . The negative photosensitive resin composition according to Item 1 or 2, wherein, in the above formula (1), R ^{1 2} is a tetravalent group containing an aromatic ring. The negative photosensitive resin composition according to claim 1 or 2, further comprising a thermal base generating agent. The negative photosensitive resin composition according to claim 10, wherein the thermal base generating agent is represented by the following general formula (Y); In the general formula (Y), Ar ¹⁰ represents an aromatic group, R ¹¹ ~ R ¹⁵ each independently represent a hydrogen atom or a hydrocarbon group, R ^{1 4} and R ¹⁵ may be bonded to each other to form a ring, n represents an integer of 1 or more. The negative photosensitive resin composition according to claim 1 or 2, which is used for an interlayer insulating film for a rewiring layer. A cured film obtained by curing the negative photosensitive resin composition according to any one of claims 1 to 12. The cured film according to claim 13, which is an interlayer insulating film for a rewiring layer. A method for producing a cured film, comprising: using the negative photosensitive resin composition according to any one of claims 1 to 12. The method for producing a cured film according to claim 15, comprising: a step of applying the negative photosensitive resin composition to a substrate; and applying the negative photosensitive property to the substrate a step of exposing the resin composition to actinic radiation or radiation; and a step of developing the exposed negative photosensitive resin composition. The method for producing a cured film according to claim 16, which comprises, after the step of performing the development treatment, the developed negative photosensitive resin composition at a temperature of from 50 ° C to 500 ° C. The step of heating. The method for producing a cured film according to the above aspect, wherein the cured film has a film thickness of from 3 μm to 30 μm. A semiconductor element having a cured film as described in claim 13 or claim 14.