TWI662367B - Negative photosensitive resin composition, cured film, method for producing cured film, and semiconductor element - Google Patents

Abstract

The present invention provides a negative photosensitive resin composition with wide exposure latitude, a cured film, a method for producing a cured film, and a semiconductor element. A negative-type photosensitive resin composition comprising: a polyimide precursor; a radical polymerization initiator; a first polymerization inhibitor selected from at least one 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, a quinone compound, an N-oxy compound, and a phenothiazine compound.

Description

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

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, the present invention relates to a negative photosensitive resin composition suitable for an interlayer insulating film for a redistribution layer.

A thermosetting resin that undergoes cyclization and curing of polyimide and the like is excellent in heat resistance and insulation, and is therefore used for an insulating layer of a semiconductor element and the like.

Here, because polyimide has low solubility in a solvent, it is used as a precursor before a cyclization reaction (a polymer precursor containing a heterocyclic ring). After being applied to a substrate or the like, it is heated and contained. The heterocyclic polymer precursor is cyclized to form a hardened film. As a photosensitive resin composition using such a polyfluorene imide precursor, Patent Document 1 discloses the following negative photosensitive resin composition, which contains: (A) a compound having the following general formula (1): [Chemical 1] (In 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. (2): [化 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 monovalent organic group represented by 1 or carbon number 1 ～ 4 saturated aliphatic group; wherein there is no polyimide precursor having a structure represented by R _{1 1} and R _{2 2} when they are both hydrogen atoms): 100 parts by mass; (B) photopolymerization Starter: 1 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 to 10 parts by mass.

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

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

[Problems to be Solved by the Invention] Here, when it is used for an interlayer insulating film for a redistribution layer of a semiconductor, etc., it is required to have a wide range of appropriate exposure for the resolution of a negative photosensitive resin composition, that is, a wide exposure latitude. Negative photosensitive resin composition. However, each of the negative photosensitive resin compositions described in Patent Literature 1 and Patent Literature 2 has a narrow exposure latitude. Here, in Patent Document 2, there is a description about high image resolution, but there is neither description nor teaching about obtaining an image with good edge sharpness with a wide exposure energy. This invention is made in order to solve the said subject, and an object is to provide the negative photosensitive resin composition with wide exposure latitude, a hardened film, the manufacturing method of a hardened film, and a semiconductor element. [Means for solving problems]

Based on the above-mentioned problems, the inventors conducted research, and found that by using a polyimide precursor having a predetermined structure in the negative photosensitive resin composition, the exposure latitude of the negative photosensitive resin composition can be made. Widened, thereby solving the problem. Specifically, the problem is solved by the following <1>, preferably by <2> to <19>. <1> A negative photosensitive resin composition comprising: a polyimide precursor; a radical polymerization initiator; a first polymerization inhibitor selected from at least one compound having an aromatic hydroxyl group; and The second polymerization inhibitor is selected from at least one of a nitroso compound, an N-oxide compound, a quinone compound, an N-oxy compound, and a phenothiazine compound. <2> The negative photosensitive resin composition according to <1>, wherein the polyfluorene imide precursor includes a repeating unit represented by the following general formula (1); General formula (1) [Chemical Formula 3] In the general 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 at least one of R ¹³ and R ¹⁴ in the general formula (1) contains a radical polymerizable group. <4> The negative photosensitive resin composition according to any one of <1> to <3>, further comprising a radical polymerizable compound. <5> The negative-type photosensitive resin composition according to <4>, wherein the radical polymerizable compound has two or more radical polymerizable groups. <6> The negative photosensitive resin composition according to any one of <1> to <5>, wherein the second polymerization inhibitor is selected from a quinone compound and an N-oxy compound. <7> The negative photosensitive resin composition according to any one of <1> to <6>, wherein the mass ratio of the first polymerization inhibitor to the second polymerization inhibitor is 10:90 to 90:10. <8> The negative photosensitive resin composition according to any one of <1> to <7>, wherein the mass ratio of the first polymerization inhibitor to the radical polymerization initiator is 1:99 to 10:90 . <9> The negative photosensitive resin composition according to any one of <1> to <8>, wherein in the general formula (1), R ^{1 2} is a tetravalent group containing an aromatic ring. <10> The negative photosensitive resin composition according to any one of <1> to <9>, further comprising a hot alkali generator. <11> The negative photosensitive resin composition according to <10>, wherein the thermal alkali generator has an ammonium cation represented by the following general formula (Y); In the general formula (Y), Ar ¹⁰ represents an aromatic group, R ¹¹ to 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, and n represents an integer of 1 or more. <12> The negative photosensitive resin composition according to any one of <1> to <11>, which is used for an interlayer insulating film for a redistribution layer. <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 redistribution layer. <15> A method for producing a cured film, comprising using the negative-type 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 applied to the substrate with actinic light. A step of performing exposure by radiation or radiation; and a step of performing development processing on the exposed negative photosensitive resin composition. <17> The method for producing a cured film according to <16>, which includes a step of heating the developed negative photosensitive resin composition at a temperature of 50 ° C. to 500 ° C. after the step of performing a development treatment. . <18> The method for producing a cured film according to any one of <15> to <17>, wherein the film thickness of the cured film is 3 μm to 30 μm. <19> A semiconductor element having a cured film according to <13> or <14>, or a cured film produced by the method according to any one of <15> to <18>. [Effect of the invention]

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

The description of the constituent elements in the present invention described below may be made based on a representative embodiment of the present invention, but the present invention is not limited to such embodiments. In the description of the group (atomic group) in the present specification, the descriptions of the substituted and unsubstituted expressions include a group (atomic group) having no substituent, and also include a group (atomic group) having a substituent. For example, "alkyl" includes not only an alkyl group (unsubstituted alkyl group) having no substituent, but also an alkyl group (substituted alkyl group) having a substituent. In this specification, "actinic rays" means, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser light, extreme ultraviolet rays (Extreme Ultraviolet (EUV) light), X-rays, electron beams, and the like . In the present invention, light means actinic rays or radiation. Unless otherwise specified, "exposure" in this specification includes not only exposure using a mercury lamp, far ultraviolet rays such as excimer lasers, X-rays, EUV light, etc., but also particle beams such as electron beams and ion beams The depiction of is also included in the exposure. In this specification, a numerical range expressed using "~" means a range including numerical values described before and after "~" as a lower limit value and an upper limit value. In this specification, "(meth) acrylate" means both or both of "acrylate" and "methacrylate", and "(meth) allyl" means "allyl" and "Methallyl" or both, "(meth) acrylic" means both "acrylic" and "methacrylic", or either, "(meth) acryl" "" Means both "acrylfluorenyl" and "methacrylfluorenyl", or either. In this specification, the term "step" refers not only to an independent step, but even if it cannot be clearly distinguished from other steps, as long as the intended function of the step is achieved, it is included in the term. In the present specification, the solid content concentration refers to the mass percentage of the mass of other components other than the solvent with respect to the total mass of the composition. In addition, unless otherwise stated, solid content concentration means the density | concentration at 25 degreeC. In this specification, unless otherwise specified, weight average molecular weight (Mw) and number average molecular weight (Mn) are defined as polystyrene conversion values measured by gel permeation chromatography (GPC). . In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be, for example, HLC-8220 (manufactured by Tosoh), 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 column to obtain them. Unless otherwise stated, the eluate was measured by using tetrahydrofuran (THF). In addition, unless otherwise stated, the detection was performed using a UV (ultraviolet) 254 nm detector.

Negative photosensitive resin composition The negative photosensitive resin composition of the present invention includes: a polyimide precursor; a radical polymerization initiator; and a first polymerization inhibitor selected from the group consisting of aromatic hydroxyl groups. At least one of compounds; and a second polymerization inhibitor selected from at least one of a nitroso compound, an N-oxide compound, a quinone compound, an N-oxy compound, and a phenothiazine compound. With such a configuration, a negative photosensitive resin composition having a wide exposure latitude can be obtained. A negative photosensitive resin composition containing a polyimide precursor is hardened by exposure, but by blending two polymerization inhibitors, the first polymerization inhibitor acts mainly on the side close to the surface layer, which acts on the film. The side farther away from the surface layer mainly acts as a second polymerization inhibitor. As a result, it is considered that the polymerization inhibition effect is exerted almost uniformly in the entire negative photosensitive resin composition layer, and the exposure latitude can be widened. In particular, it is advantageous in the case of large differences in light irradiation methods and film thickness. In addition, the resin used in the examples of Patent Document 2 is an acrylic resin, and there is a problem from the viewpoint of heat resistance. However, since a polyimide precursor is used in the present invention, heat resistance can also be formed. Outstanding.

<Polyimide precursor> The negative photosensitive resin composition of the present invention contains a polyimide precursor. There may be only one kind of polyimide precursor, or two or more kinds. The polyimide precursor is preferably a polyimide precursor containing a repeating unit represented by the general formula (1). Formula (1) In the general 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 each independently represent A hydrogen atom or a monovalent organic group.

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

R ¹¹ represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and a group containing an aryl group. A linear or branched aliphatic group having 2 to 20 carbon atoms and carbon are preferable. A cyclic aliphatic group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a group containing a combination of these, 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 can be substituted with a fluorine atom, -O-, -C (= O)-, -S-, -S (= O) ₂ -And -NHCO-, and groups in these combinations are more preferably a single bond, selected from alkylene groups having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C (= O)- , -S-, -SO _2- , and more preferably selected from -CH _2- , -O-, -S-, -SO _2- , -C (CF ₃ ) _2- , -C (CH _{3) 2} - in the divalent group.

Specific examples of R ¹¹ include diamine residues remaining after removal of the 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 di 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'-diaminodiphenyl Phenylphosphonium and 3,3'-diaminodiphenylphosphonium, 4,4'-diaminodiphenylsulfide and 3,3'-diaminodiphenylsulfide, 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-hydroxy 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) fluorene, bis (4-amino-3-hydroxyphenyl) fluorene, 4,4'-diamine p-terphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] fluorene, bis [4- (3-aminophenoxy) phenyl] fluorene, bis [ 4- (2-aminophenoxy) phenyl] fluorene, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis (4-aminophenyl) anthracene, 3,3 '-Dimethyl-4,4'-diaminodiphenylphosphonium, 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'-diaminooctafluorobiphenyl, 2,2-bis [4- (4- Aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9,9-bis (4-aminophenyl) -10 -Hydroanthracene, 3,3 ', 4,4'-tetraaminobiphenyl, 3,3', 4,4 '-Tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9, 9'-bis (4-aminophenyl) fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylfluorene, 3,3 ', 5,5'-tetramethyl- 4,4'-diaminodiphenylmethane, 2,4-diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine , 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis (3-aminopropyl) tetramethyldisilazane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-aminophenyl) ethane, diaminobenzidineaniline, esters of 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) tetradecafluoroheptane, 2,2-bis [4- (3-amine Phenylphenoxy) 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, p-bis ( 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) diphenylphosphonium, 4,4'-bis (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'-hexafluorobenzylamine and 4,4'-diamine At least one of tetraphenyl.

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

[Chemical 7]

[Chemical 8]

Further, the main chain may include a diamine residue having a diamine group after two or more alkylene glycol units to remove the remaining Examples of R ^11. A diamine residue containing one or more of two or more ethylene glycol chains and propylene glycol chains in one molecule is preferred, and a diamine residue not containing an aromatic ring is more preferred. As examples, Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D- 2000, D-4000 (the above are the trade names, manufactured by HUNTSMAN), 1- (2- (2- (2-aminopropyloxy) ethoxy) propoxy) propane- 2-amine, 1- (1- (1- (2-aminopropyloxy) propane-2-yl) oxy) propane-2-amine, and the like are 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.

[Chemical 9]

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

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

Formula (1-1) In the general formula (1-1), R ^{112 is} preferably a single bond or a hydrocarbon group having 1 to 10 carbon atoms, -O-, -CO-, -S-, -SO ₂ -which may be substituted with a fluorine atom. And -NHCO-, and the groups in these combinations are more preferably a single bond or an alkylene group having 1 to 3 carbon atoms, which can be substituted with a fluorine atom, -O-, -CO-, -S- And -SO ₂ -are more preferably a divalent group selected from -CH _2- , -C (CF ₃ ) _2- , -C (CH ₃ ) _2- , -O-, -CO-,- Divalent radicals in the group consisting of S- and -SO _2- .

Formula (1-2)

Examples of R ^{1 2} include tetracarboxylic acid residues remaining after removing anhydride groups from tetracarboxylic dianhydride. Specific examples thereof include tetracarboxylic acid residues remaining after removing anhydride groups from the following tetracarboxylic dianhydrides. Selected from pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfide 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 dianhydride Anhydride, 2,3,3 ', 4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride 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-diphenyl hexafluoropropane-3,3,4,4-tetracarboxylic dianhydride , 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2 ', 3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-fluorenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, and 1,2,3,4-benzenetetracarboxylic dianhydride And these 1 to 6 carbon alkane At least one tetracarboxylic dianhydride derivatives and derivative carbons, alkoxy of 1 to 6.

In addition, the remaining tetracarboxylic acid residues after removing the anhydride group from the tetracarboxylic dianhydride (DAA-1) to tetracarboxylic dianhydride (DAA-5) shown below can be cited as R ^{1 2} example. [Chemical 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 tetracarboxylic acid residues remaining after removing anhydride groups from the above (DAA-1) to (DAA-5).

In the general 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 capable of improving solubility in a developing solution can be preferably used.

From the viewpoint of the solubility of the aqueous developer, R ¹³ and R ¹⁴ are a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include one or two having a carbon atom bonded to an aryl group. One or three, preferably one, aryl and aralkyl groups of an acidic group. Specific examples 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 specific examples include a phenyl group having an acidic group and a benzyl group having an acidic group. The acidic group is preferably an OH group. In terms of solubility in an aqueous developer, it is preferable that R ¹³ and R ¹⁴ are a hydrogen atom, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group, and a 4-hydroxybenzyl group.

From the viewpoint of the solubility of an 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, or an aryl group, and more preferably an aryl-substituted alkyl group. The carbon number of the alkyl group is preferably 1 to 30. The alkyl group may be any of linear, branched, and cyclic. Examples of the linear or branched alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, Octadecyl, isopropyl, isobutyl, second butyl, third butyl, 1-ethylpentyl, and 2-ethylhexyl. The cyclic alkyl (cycloalkyl) may be a monocyclic cycloalkyl or a polycyclic cycloalkyl. Examples of the monocyclic cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of the polycyclic cycloalkyl group include adamantyl, norbornyl, norbornyl, pinenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, fluorenedifluorenyl, and Cyclohexyl, and pinenyl. Among them, from the viewpoint of coexistence with high sensitivity, cyclohexyl is the best. The aryl-substituted alkyl 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 pentenene ring, an inden ring, a fluorene ring, a heptene ring, an indenene ring, a fluorene ring, a fused pentaphenyl ring, Acenaphthene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring, Ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indoxazine Ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinazine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, iso A quinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, a thiathracene ring, a benzopyran ring, a xanthene ring, a phenothiazine ring, a phenothiazine ring or a morphazine ring. The best is benzene ring.

Examples of the polymerizable group possessed by R ¹³ and R ¹⁴ include an epoxy group, an oxetanyl group, a group having an ethylenically unsaturated bond, a block isocyanate group, an alkoxymethyl group, a methylol group, Amine groups, etc. In the present invention, examples of preferred embodiments of R ¹³ and R ¹⁴ include 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).

[Chemical 13]

In the formula (III), R ²⁰⁰ represents hydrogen or a methyl group, and more preferably a methyl group. In 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: ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene Group, octamethylene, dodecylmethylene, -CH ₂ CH (OH) CH _2- , and more preferably ethylene, propyl, trimethylene, -CH ₂ CH (OH) CH _2- . Particularly preferably, R ²⁰⁰ is methyl, and R ²⁰¹ is ethylene.

When R ¹³ and R ¹⁴ in the general formula (1) contain a polymerizable group (preferably, a radical polymerizable group), the polymerizable group: Mole without a polymerizable group is more preferably 100: 0 to 5: 95, more preferably 100: 0 to 20:80, and still more preferably 100: 0 to 50:50.

In the general formula (1), when A ² is an oxygen atom and R ¹³ is a hydrogen atom, or / and when A ¹ is an oxygen atom and R ¹⁴ is a hydrogen atom, it may also be tertiary with an ethylenically unsaturated bond. The amine compound forms a counter salt. Examples of such tertiary amine compounds having an ethylenically unsaturated bond include N, N-dimethylaminopropylmethacrylate.

In addition, in the case of performing alkali development, it is preferable that the polyfluorene imide precursor has a fluorine atom in the structural unit in terms of improving the resolution. The fluorine atom can impart water repellency to the surface of the film during alkali development, thereby suppressing permeation from the surface and the like. The fluorine atom content in the polyfluorene imide precursor is preferably 10% by mass or more, and in terms of solubility in an alkaline aqueous solution, it is preferably 20% by mass or less.

In addition, for the purpose of improving the adhesion to the substrate, the polyimide precursor may also copolymerize an aliphatic group having a siloxane structure. Specifically, examples of the diamine component include bis (3-aminopropyl) tetramethyldisilazane and bis (p-aminophenyl) octamethylpentasiloxane.

In addition, in order to improve the storage stability of the negative photosensitive resin composition, the polyfluorene imide precursor is preferably a monoamine, an acid anhydride, a monocarboxylic acid, a monofluorinated chlorine compound, a monoactive ester compound, and other end-capping agents. The chain ends are closed. Among these, it is more preferable to use a monoamine. Preferred compounds of the monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, and 1-hydroxy-7-amine. Naphthalene, 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-aminosalicylic acid 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 end-capping agents.

The polyfluorene imide precursor used in the present invention may include a repeating unit represented by the general formula (1) and other repeating units as other fluorene imine precursors. When other repeating units are included, the proportion of other repeating units in the polyimide precursor is preferably 1 mol% to 60 mol%, and more preferably 5 mol% to 50 mol%.

The negative photosensitive resin composition of the present invention may have a configuration that does not substantially contain a polyimide precursor other than a polyimide precursor containing a repeating unit represented by the general formula (1). The term "substantially free" means that the content of the other polyimide 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 20,000 to 28,000, more preferably 22,000 to 27,000, and even more preferably 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, and even more preferably 2.8 or more. The upper limit of the dispersion degree of the polyfluorene imide precursor is not particularly limited, but is preferably 4.5 or less, and may be set to 3.4 or less.

The content of the polyimide precursor in the negative photosensitive resin composition of the present invention is preferably 20% to 100% by mass, and more preferably 50% by mass relative to the total solid content of the negative photosensitive resin composition. % To 99% by mass, more preferably 60% to 99% by mass, and particularly preferably 70% to 99% by mass.

<Other resin component> The negative photosensitive resin composition of this invention may contain other resin components in the range which does not deviate from the meaning of this invention. Examples of the other resin components include polybenzoxazole precursors and polyimide resins. Moreover, in this invention, it can also be set as the structure which does not contain resin other than a polyimide precursor substantially. The term “substantially free” means, for example, that the content of the resin other than the polyfluorene imide precursor contained in the negative photosensitive resin composition of the present invention is 3% by mass or less of the content of the polyfluorene imide precursor.

<Radical polymerization initiator> The negative photosensitive resin composition of this invention contains a radical polymerization initiator. The radical polymerization initiator can perform negative development by starting the polymerization of a radically polymerizable group that the polyfluorene imide precursor can have, or a radically polymerizable compound described later. The radical polymerization initiator may be a photo radical polymerization initiator or a thermal radical polymerization initiator, but a photo radical polymerization initiator is preferred. More specifically, after a negative photosensitive resin composition is applied to a semiconductor wafer or the like to form a layered composition layer, light is irradiated to generate hardening caused by free radicals, and the light-irradiated portion can be exposed to light. The solubility decreases. Therefore, for example, by exposing the composition layer through a photomask having a pattern covering only the electrode portion, there is an advantage that regions having different solubility can be easily produced according to the pattern of the electrode.

The photo radical polymerization initiator is not particularly limited as long as it has the ability to start a polymerization reaction (crosslinking reaction) of a radical polymerizable compound and the like, and can be appropriately selected from known photo radical polymerization initiators. . For example, it is preferable to have sensitivity to light from the ultraviolet region to the visible region. In addition, it may be an active agent that generates an active radical by having a certain effect with a photo-excited sensitizer. The photoradical polymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 in a range of about 300 nm to 800 nm (preferably 330 nm to 500 nm). The molar absorption coefficient of a compound can be measured using a well-known method. For example, it is preferable to use a UV-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) to measure at a concentration of 0.01 g / L using an ethyl acetate solvent.

As the photoradical polymerization initiator, known compounds can be used without limitation, and examples thereof include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, those having a trihalomethyl group, etc.), Fluorenyl phosphine compounds such as fluorenylphosphine oxide, oxime compounds such as hexaarylbiimidazole, oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, Hydroxyacetophenone, azo-based compounds, azide-based compounds, metallocene compounds, organoboron compounds, iron aromatic compounds, and the like.

Examples of the halogenated hydrocarbon derivative having a triazine skeleton include the compounds described in "Bull. Chem. Soc. Japan", 42, 2924 (1969) by Wakabayashi et al., British Patent No. 1348492 The compounds described in the specification are the compounds described in Japanese Patent Laid-Open No. 53-133428, the compounds described in German Patent No. 3337024, FC Schaefer, and other "J. Org. Chem" .) ", 29, 1527 (1964), compounds described in Japanese Patent Laid-Open No. 62-58241, compounds described in Japanese Patent Laid-open No. 5-281728, and Japanese Patent Laid-Open No. 5-281728. Compounds described in 34920, and compounds described in US Pat. No. 4,212,976.

Examples of the compounds described in the specification of US Patent No. 4212976 include compounds having an oxadiazole skeleton (for example, 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 Group) -1,3,4-oxadiazole, 2-tribromomethyl-5-styryl-1,3,4-oxadiazole, etc.).

Examples of the photoradical polymerization initiator other than the above include acridine derivatives (for example, 9-phenylacridine, 1,7-bis (9,9'-acridyl) heptane, etc.) , N-phenylglycine, etc., polyhalogen compounds (such as carbon tetrabromide, phenyltribromomethylphosphonium, phenyltrichloromethyl ketone, etc.), coumarins (such as 3- (2-benzene Benzofuranyl) -7-diethylaminocoumarin, 3- (2-benzofuranmethylfluorenyl) -7- (1-pyrrolidinyl) coumarin, 3-benzylfluorenyl- 7-diethylaminocoumarin, 3- (2-methoxybenzylidene) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzylidene) ) -7-diethylaminocoumarin, 3,3'-carbonylbis (5,7-di-n-propoxycoumarin), 3,3'-carbonylbis (7-diethylamine Base coumarin), 3-benzyl-7-methoxycoumarin, 3- (2-furanmethyl) -7-diethylaminocoumarin, 3- (4-di Ethylamino cinnamyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzyl-5,7- Dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, Japanese Patent Laid-Open No. 5-19475, Japanese Patent Laid-Open The fragrances described in JP 7-271028, JP 2002-363206, JP 2002-363207, JP 2002-363208, JP 2002-363209, etc. Legumin compounds, etc.), fluorenylphosphine oxides (such as bis (2,4,6-trimethylbenzylfluorenyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzylfluorenyl)) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.), metallocenes (eg, two described in paragraph 0076 of Japanese Patent Laid-Open No. 2011-13602) Titanocene compound, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium, η5- Cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.), Japanese Patent Laid-Open No. 53-133428, Japanese Patent Laid-Open No. 57-1819, Compounds described in Japanese Patent Publication No. 57-6096 and U.S. Patent No. 3615455.

Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenonetetracarboxylic acid Or its tetramethyl ester, 4,4'-bis (dialkylamino) benzophenones (e.g. 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (Dicyclohexylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (dihydroxyethylamino) benzophenone, 4 -Methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone), 4-dimethyl Amine acetophenone, benzophenone, anthraquinone, 2-tert-butylanthraquinone, 2-methylanthraquinone, phenanthrenequinone, xanthone, thiathrone, 2-chloro-thiathrone , 2,4-diethylthiaxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinylphenyl) -1-butanone, 2-methyl-1 -[4- (methylthio) phenyl] -2-morpholinyl-1-acetone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligo Substances, benzoin, benzoin ethers (such as benzoin methyl ether, benzoin ether, benzoin propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridinone, chloroacridone, N-methyl Acrylone, N-butylacridone, N-butyl-chloroacridone, and the like. Among commercially available products, Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be suitably used.

As the photo-radical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a fluorenylphosphine compound can also be suitably used. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Laid-Open No. 10-291969 and a fluorenylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used. As a hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IGACURE can be used. Solid (IRGACURE) -127 (trade name: all manufactured by BASF). As the amine acetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: both) (Manufactured by BASF). IRGACURE is a registered trademark. As the aminoacetophenone-based initiator, compounds described in Japanese Patent Laid-Open No. 2009-191179 whose absorption wavelength matches a light source such as 365 nm or 405 nm can also be used. As the fluorenylphosphine-based initiator, commercially available products such as IRGACURE-819 or DAROCUR-TPO (trade names: all manufactured by BASF) can be used.

The photoradical polymerization initiator is more preferably an oxime compound. As specific examples of the oxime-based initiator, compounds described in Japanese Patent Laid-Open No. 2001-233842, compounds described in Japanese Patent Laid-Open No. 2000-80068, and Japanese Patent Laid-Open No. 2006-342166 can be used. Documented compounds. Preferred oxime compounds include, for example, 3-benzyloxyiminobutane-2-one, 3-ethylamidooxyiminobutane-2-one, and 3-propanyloxy Iminobutane-2-one, 2-acetamidoiminopentane-3-one, 2-acetamidoimino-1-phenylpropane-1-one, 2-benzyl Ethoxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxyimino -1-phenylpropane-1-one and the like.

Examples of oxime compounds include: "The Journal of the British Chemical Society, JCS Perkin II" (1979) pp.1653-1660, "The Journal of the British Chemical Society, Perkin Journal II" (1979 Pp. 156-162, and "Journal of Photopolymer Science and Technology" (1995) pp. 202-232, and Japanese Patent Laid-Open No. 2000-66385, The compounds described in the respective publications of Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open No. 2004-534797, and Japanese Patent Laid-Open No. 2006-342166. Among commercially available products, IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), and N-1919 (Adi (ADEKA) company).

In addition, compounds described in Japanese Patent Publication No. 2009-519904 in which an oxime is linked to the N-position of a carbazole ring, and US Pat. No. 7,626,957 described in which a hetero substituent is introduced into a benzophenone moiety can also be used. Compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and U.S. Patent Publication No. 2009-292039, and ketooxime-based compounds described in International Publication No. WO2009 / 131189, in which a nitro group is introduced into a compound and a pigment portion, are the same. The compound described in U.S. Patent No. 7,565,910 containing a triazine skeleton and an oxime skeleton in the molecule, and a compound described in Japanese Patent Laid-Open No. 2009-221114, which has the maximum absorption at 405 nm and has good sensitivity to a g-ray light source Wait. In addition, cyclic oxime compounds described in Japanese Patent Laid-Open No. 2007-231000 and Japanese Patent Laid-Open No. 2007-322744 can also be suitably used. Among the cyclic oxime compounds, in particular, the cyclic oxime compound condensed in a carbazole pigment described in Japanese Patent Laid-Open No. 2010-32985 and Japanese Patent Laid-Open No. 2010-185072 has high light absorption, It is preferable from the viewpoint of high sensitivity. In addition, a compound described in Japanese Patent Laid-Open No. 2009-242469, which is a compound having an unsaturated bond at a specific site of an oxime compound, can also be suitably used. Alternatively, an oxime compound having a fluorine atom may be used. Specific examples of such initiators include compounds described in Japanese Patent Laid-Open No. 2010-262028, and compounds 24 and 36 described in Japanese Patent Laid-Open No. 2014-500852 in paragraph number 0345. ~ Compound 40, the compound (C-3) described in Japanese Patent Application Laid-Open No. 2013-164471, paragraph number 0101, and the like. Specific examples include the following compounds. [Chemical 14] Examples of the preferred oxime compound include an oxime compound having a specific substituent shown in Japanese Patent Laid-Open No. 2007-269779, or a thioaryl group shown in Japanese Patent Laid-Open No. 2009-191061. Oxime compounds and the like.

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, Fluorenyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallyl imidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentyl Compounds in the group consisting of diene-benzene-iron complexes and their salts, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds. More preferred are trihalomethyltriazine compounds, α-aminoketone compounds, fluorenylphosphine compounds, phosphine oxide compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzophenone compounds, and acetophenone compounds. In addition, a trihalomethyltriazine compound, an α-amino ketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound are more preferable, and an oxime compound is most preferable.

The content of the radical polymerization initiator is preferably 0.1% to 30% by mass, more preferably 0.1% to 20% by mass, and even more preferably 0.1% by mass relative to the total solid content of the negative photosensitive resin composition. % To 10% by mass. Moreover, it is preferable to contain 1 to 20 mass parts of radical polymerization initiators with respect to 100 mass parts, and it is more preferable to contain 3 to 10 mass parts. There may be only one type of radical polymerization initiator, or two or more types. When there are two or more kinds of radical polymerization initiators, it is preferable that the total thereof is within 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 compound having an aromatic hydroxyl group. Such a polymerization inhibitor has a strong polymerization inhibitory effect mainly on a compound having a radical polymerizable group in the presence of oxygen.

The compound having an aromatic hydroxyl group is preferably a compound represented by the formula (101). Formula (101) In formula (101), m represents an integer of 1 to 5, n represents an integer of 1 to 4, and n R ¹⁰¹ each independently represents a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a cyano group, Hydroxyl, branched alkyl having 1 to 20 carbons, cycloalkyl having 3 to 8 carbons, aryl having 6 to 12 carbons, alkenyl having 1 to 5 carbons, or 1 to 5 carbons Alkynyl groups, which may be bonded via a benzene ring represented by formula (101) and a linking group. Examples of the linking group include a carbonyl group, a carbonyloxy group (-COO-), and an oxycarbonyl group (-OCO-). , Sulfur, sulfofluorenyl, sulfenamidinyl, oxy, imino (-NH-), fluorenyl, alkylene having 1 to 6 carbon atoms, arylene having 6 to 12 carbon atoms, phosphine Polyester group, phosphate group, 3-membered ring to 8-membered ring formed by removing two or more hydrogen atoms from heterocycles such as triazine, dioxane and the like A polyvalent linking group from the combination of these linking groups. Furthermore, 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 that can be introduced. Examples of the introduceable substituent include 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, an iodine atom), an amine group, an alkylamino group, and an alkoxy group. And (meth) acrylfluorenyl.

X ¹⁰¹ does not exist when m is 1. When m is 2 or more, it represents an m-valent linking group. Specific examples include: a single bond, a carbonyl group, a carbonyloxy group, a thio group, a sulfofluorenyl group, and a sulfenylsulfenyl group. , Oxy, phosphonate group, alkylene group having 1 to 6 carbon atoms, arylene group having 6 to 12 carbon atoms, imine group, and aliphatic hydrocarbon group having 1 to 6 carbon atoms obtained by removing m hydrogen atoms , M-valent aromatic hydrocarbon groups having 6 to 12 carbon atoms obtained by removing m hydrogen atoms, and 6-membered to 12-membered ring heterocycles obtained by removing m hydrogen atoms from heterocyclic rings such as triazine and dioxane A ring group, a combination of these linking groups, and the like may have a substituent on a carbon atom that can be introduced. The substituent is preferably the same substituent as R ¹⁰¹ .

In formula (101), when m is 1, of course, there is no linking group X ¹⁰¹ . In this case, instead of X ¹⁰¹ may have a monovalent substituent as a monovalent substituent, may be exemplified the same groups as R ^101, it can also be substituted on the benzene ring and R ¹⁰¹ bonded 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-third-butyl-4-methylphenol, and pentaerythritol tetrakis [3- (3,5-di- Tributyl-4-hydroxyphenyl) propionate], thiodiethylidenebis [3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate], eighteen 3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate, N, N'-hexane-1,6-diylbis [3- (3,5-di -Third-butyl-4-hydroxyphenyl) propanamide), 3,3 ', 3' ', 5,5', 5 ''-Hexa-third-butyl-a, a ', a' ' -(Mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylidenebis (oxyethylidene) bis [ 3- (5-Third-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-third-butyl-4-hydroxyphenyl) propionic acid (Ester), 1,3,5-tris (3,5-di-third-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -Trione, 2,6-di-third-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol, catechol, Tertiary butyl-catechol, 4,4 ', 4' '-(1-methylpropanil-3-subunit) tris (6-third butyl-m-cresol), 6 , 6'-di-third-butyl-4,4'-butylene-m-cresol, 3 , 9-bis [2- [3- (3-Third-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4, 8,10-tetraoxaspiro [5,5] undecane, hydroquinone, methyl hydroquinone, third butyl hydroquinone, di-third butyl-p-cresol, gallic Phenol, 4,4-thiobis (3-methyl-6-third butylphenol), 2,2'-methylenebis (4-methyl-6-third butylphenol), phenol resin And cresol resins. In addition, 3- (3,5-di-third-butyl-4-hydroxyphenyl) propionic acid alkyl ester can also be cited as a preferable example. The number of carbon atoms in the alkyl chain portion of the alkyl ester herein is preferably 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 even more preferably 0.03% by mass or more. The upper limit is more preferably 3% by mass or less, and even more preferably 1% by mass or less. The first polymerization inhibitor may be only one kind, or two or more kinds. When there are two or more kinds of the first polymerization inhibitors, it is preferable that the total thereof falls within the above range.

<Second polymerization inhibitor> The negative photosensitive resin composition of the present invention includes a first photosensitive resin composition selected from the group consisting of a nitroso compound, an N-oxide compound, a quinone compound, an N-oxy compound, and a phenothiazine compound. 2 Polymerization inhibitor. Such a polymerization inhibitor has a strong polymerization inhibitory effect mainly on a compound having a radical polymerizable group in the presence of non-oxygen.

Examples of the nitroso compound as the second polymerization inhibitor include nitrosobenzene, 2-nitrosotoluene, 1,2,4,5-tetramethyl-3-nitrosobenzene, and 4-nitroso Phenol, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 4-nitroso-diphenylamine, 3,5-dibromo-4-nitrosobenzenesulfonic acid Acid, N-nitrosopyrrolidine, N-third butyl-N-nitrosoaniline, N-nitrosodimethylamine, N-nitrosodiethylamine, 1-nitrosopiperazine Pyridine, 4-nitrosomorpholine, N-nitroso-N-methylbutylamine, N-nitroso-N-ethylurea, N-nitrosohexamethyleneimine, N- Nitrosophenylhydroxylamine trivalent cerium salt and N-nitrosophenylhydroxylamine aluminum salt, 2,4,6-tri-third-butyl-nitrosobenzene, N-nitrosodiphenyl amine.

Examples of the N-oxide compound include phenyl-third butyl nitrone, 3,3,5,5-tetramethyl-1-pyrroline-N-oxide, and 5,5-dimethyl- 1-pyrroline N-oxide, 4-methylmorpholine N-oxide, pyridine N-oxide, 4-nitropyridine N-oxide, 3-hydroxypyridine N-oxide, picolinic acid N-oxidation Substances, nicotinic acid N-oxide, and isonicotinic acid N-oxide.

Examples of the quinone compound include p-benzoquinone, p-xyloquinone, p-methylquinone, 2,6-dimethyl-1,4-benzoquinone, tetramethyl-1,4-benzoquinone, 2-tert-butyl-p-benzoquinone, 2,5-di-tert-butyl-1,4-benzoquinone, 2,6-di-tertiary-1,4-benzoquinone, vanillin quinone, 2 , 5-Di-tertiarypentylbenzoquinone, 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 Quinone, 2,5-dimethoxy-1,4-benzoquinone, 2,6-dimethoxy-1,4-benzoquinone, 2,3-dimethoxy-5-methyl-1, 4-benzoquinone, tetrahydroxy-1,4-benzoquinone, 2,5-diphenyl-1,4-benzoquinone, 1,4-naphthoquinone, 1,4-anthraquinone, 2-methyl-1 4,4-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-nitroanthraquinone, anthraquinone, 1-aminoanthraquinone, 1,2-benzoanthraquinone, 1,4-diaminoanthraquinone, 2,3-dimethyl Anthraquinone, 2-ethylanthraquinone, 2-methylanthraquinone, 5,12-naphthonaphthoquinone.

Examples of the N-oxy compound include 2,2,6,6-tetramethylpiperidine 1-oxy, 4-cyano-2,2,6,6-tetramethylpiperidine 1-oxy 4-amino-2,2,6,6-tetramethylpiperidine 1-oxy, 4-carboxy-2,2,6,6-tetramethylpiperidine 1-oxy, 4-methoxy -2,2,6,6-tetramethylpiperidine 1-oxy, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxy, 4-methacryloxy -2,2,6,6-tetramethylpiperidine 1-oxyl, piperidine 1-oxyl radical, 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl Free radical, 4-acetamidin-2,2,6,6-tetramethylpiperidine 1-oxy radical, 4-cis-butenediamidoimine-2,2,6,6-tetramethyl Piperidine 1-oxy radical and 4-phosphinofluorenyl-2,2,6,6-tetramethylpiperidine 1-oxy radical, pyrrolidine 1-oxy radical compounds, 3- Carboxyl proxyl radical (3-carboxy-2,2,5,5-tetramethylpyrrolidine 1-oxy radical).

Examples of the phenothiazine compound include phenothiazine, 10-methyl phenothiazine, 2-methylthio phenothiazine, 2-chlorophenothiazine, 2-ethyl thiophenothiazine, and 2- (triphenylthiothiazine Fluoromethyl) phenothiazine, 2-methoxyphenothiazine.

In addition, since a compound belonging to either of the first polymerization inhibitor and the second polymerization inhibitor can exhibit polymerization inhibition near the surface layer of the film and anywhere inside the film, it is regarded as a second polymerization inhibitor.

The second polymerization inhibitor is preferably selected from quinone compounds and N-oxyl compounds. 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, and even more preferably 1% by mass or less. The second polymerization inhibitor may be only one kind, or two or more kinds. When there are two or more types of second polymerization inhibitors, it is preferable that the total thereof is within the above range.

<Ratio of polymerization inhibitor> The mass ratio of the first polymerization inhibitor and the second polymerization inhibitor is not particularly limited, but it is preferably 1:99 to 99: 1, more preferably 90:10 to 10:90, and further It is more preferably 70:30 to 30:70. By setting it as such a range, there exists a tendency for exposure latitude to become wider. The present invention may include a polymerization inhibitor other than the first polymerization inhibitor and the second polymerization inhibitor. Moreover, in this invention, it can also be set as the structure which does not substantially contain the polymerization inhibitor other than the said 1st polymerization inhibitor and the 2nd polymerization inhibitor. The term "substantially free" means that the amount of other polymerization inhibitors among the polymerization inhibitors contained in the photosensitive resin composition of the present invention is 5% by mass or less of the total amount of the polymerization inhibitors. The mass ratio of the first polymerization inhibitor to the radical polymerization initiator is preferably 0.01: 99.99 to 20:80, and more preferably 1:99 to 10:90. By setting it as such a range, there exists a tendency for exposure latitude to become wider.

<Radical Polymerizable Compound> The negative photosensitive resin composition of the present invention may contain a radical polymerizable compound other than the polyfluorene imide precursor. By containing a radical polymerizable compound, a cured film having more excellent heat resistance can be formed. Furthermore, pattern formation can be performed by a photolithography method. 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 chemical forms such as a monomer, a prepolymer, an oligomer, a mixture thereof, and a multimer thereof.

In the present invention, a monomeric radical polymerizable compound (hereinafter, also referred to as a radical polymerizable monomer) is a compound different from a polymer compound. The radical polymerizable monomer is typically a low-molecular compound, preferably a low-molecular compound having a molecular weight of 2,000 or less, more preferably a low-molecular compound having a molecular weight of 1500 or less, and even more preferably a low-molecular compound having a molecular weight of 900 or less. The molecular weight of the radical polymerizable monomer is usually 100 or more. The oligomer-type radically polymerizable compound is typically a polymer having a relatively low molecular weight, and is preferably a polymer in which 10 to 100 radically polymerizable monomers are bonded. As the molecular weight, the weight average molecular weight in terms of polystyrene obtained by gel permeation chromatography (GPC) is preferably 2,000 to 20,000, more preferably 2,000 to 15,000, and even more preferably 2,000 to 10,000.

The functional group number of the radically polymerizable compound in the present invention refers to the number of radically polymerizable groups in one molecule. From the standpoint of resolvability, the radical polymerizable compound preferably contains at least one type of difunctional or more radically polymerizable compound containing two or more radical polymerizable groups, and more preferably contains at least one type of difunctionality to tetrafunctionality. Functional radical polymerizable compounds.

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

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 amidines and these polymers are preferably esters of an unsaturated carboxylic acid and a polyol compound, and amidines of an unsaturated carboxylic acid and a polyamine compound, and these polymers. In addition, esters or amidines of unsaturated carboxylic acids having a nucleophilic substituent such as a hydroxyl group, an amine group, or a mercapto group, and addition reactions of monofunctional or polyfunctional isocyanates or epoxy compounds may also be suitably used. Or a dehydration condensation reactant with a monofunctional or polyfunctional carboxylic acid, and the like. In addition, an addition reaction product of an ester or unsaturated amine of an unsaturated carboxylic acid having an electrophilic substituent such as an isocyanate group or an epoxy group, and a monofunctional or polyfunctional alcohol, amine, or thiol, and further, Substituted reactants of esters or amidines of unsaturated carboxylic acids having a detachable substituent such as a halogen group or tosylsulfonyloxy group with monofunctional or polyfunctional alcohols, amines, or thiols are also suitable. In addition, as another example, a group of compounds substituted with an unsaturated phosphonic acid, a vinyl benzene derivative such as styrene, a vinyl ether, an allyl ether, or the like may be used instead of the unsaturated carboxylic acid.

Specific examples of the monomer of the ester of a polyol compound and an unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetracarboxylic acid. Methylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloxypropyl) ether, trimethylol Ethane 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 (acryloxyethyl) isotris Polycyanate, ethylene isocyanate modified triacrylate, polyester acrylate oligomer, etc.

Examples of methacrylates include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, Trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, Pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [ P- (3-Methacryloxy-2-hydroxypropoxy) phenyl] dimethylmethane, bis- [p- (methacryloxyethoxy) phenyl] dimethylmethane, etc. .

Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, and Methylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetraitaconate, and the like.

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

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

Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate Esters, etc.

As examples of other esters, for example, the aliphatic alcohol-based esters described in Japanese Patent Application Publication No. 46-27926, Japanese Patent Application Publication No. 51-47334, and Japanese Patent Application Publication No. 57-196231 can be suitably used. Or a compound having an aromatic skeleton described in Japanese Patent Laid-Open No. 59-5240, Japanese Patent Laid-Open No. 59-5241, and Japanese Patent Laid-Open No. 2-226149, Japanese Patent Laid-Open No. 1 An amine group-containing compound and the like described in JP-165613.

Specific examples of the monomer of a polyamine compound and amidamine of an unsaturated carboxylic acid include methylenebis-acrylamide, methylenebis-methacrylamide, and 1,6-hexamethylene Bis-acrylamide, 1,6-hexamethylenebis-methacrylamide, diethylenetriamine triacrylamide, xylylene bisacrylamine, xylylene bismethacrylamine, and the like.

As another example of a preferable amidine-based monomer, a monomer having a cyclohexyl structure described in Japanese Patent Publication No. 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. Examples of such a specific example include those described in Japanese Patent Publication No. 48-41708 A vinyl carbamate containing two or more polymerizable vinyl groups in one molecule 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, for example, the acrylic urethanes described in Japanese Patent Laid-Open No. 51-37193, Japanese Patent Laid-Open No. 2-32293, and Japanese Patent Laid-Open No. 2-16765, or Japanese Patent Laid-Open No. 58 No. -49860, Japanese Patent Laid-Open Publication No. 56-17654, Japanese Patent Laid-Open Publication No. 62-39417, and Japanese Patent Laid-Open Publication No. 62-39418. Ester compounds are also suitable.

In addition, in the present invention, as the compound having an ethylenically unsaturated bond, the compounds described in paragraphs 0095 to 0108 of Japanese Patent Laid-Open No. 2009-288705 can also be suitably used.

In addition, as the compound having an ethylenically unsaturated bond, a compound having a boiling point of 100 ° C. or higher under 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 tetra (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tris (acryloxypropyl) ) Ether, tris (propenyloxyethyl) isotricyanate, glycerol, or trimethylolethane, etc., are added to polyfunctional alcohols, followed by (meth) acrylic acid. Esterified, such as the (meth) acrylic acid urethanes described in various publications of Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034, and Japanese Patent Publication No. 51-37193. Categories, each of Japanese Patent Laid-Open No. 48-64183, Japanese Patent Laid-Open No. 49-43191, and Japanese Patent Laid-Open 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. In addition, the compounds described in Japanese Patent Laid-Open No. 2008-292970, paragraphs 0254 to 0257 are 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 can also be mentioned. In addition, as other preferred compounds having an ethylenically unsaturated bond, those described in Japanese Patent Laid-Open No. 2010-160418, Japanese Patent Laid-Open No. 2010-129825, and Japanese Patent No. 4364216 can be used. Cardo resin is a compound having a fluorene ring and having two or more groups containing an ethylenically unsaturated bond. Furthermore, as another example, Japanese Unexamined Patent Publication No. 46-43946, Japanese Patent Unexamined Patent Publication No. 1-40337, and Japanese Patent Unexamined Patent Publication No. 1-40336 can be cited as specific unsaturated compounds or Japanese patents. A vinylphosphonic acid compound and the like described in Japanese Patent Application Laid-Open No. 2-25493. In addition, in some cases, a structure containing a perfluoroalkyl group described in Japanese Patent Laid-Open No. 61-22048 is suitably used. Furthermore, those introduced as radical polymerizable monomers and oligomers in "Japanese Adhesive Association Journal" vol. 20, No. 7, pages 300 to 308 (1984) can also be used.

In addition to the above, a compound having an ethylenically unsaturated bond represented by the following general formula (MO-1) to general formula (MO-5) may be suitably used. In the formula, when T is an oxyalkylene group, a carbon atom-side end is bonded to R.

[Chemical 16]

[Chemical 17]

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

In addition, the following compounds described in Japanese Patent Application Laid-Open No. 10-62986 as general formulae (1) and (2), together with specific examples thereof, can also be used as polymerizable compounds. The compounds are used in polyfunctional alcohols. A compound obtained by addition of ethylene oxide or propylene oxide, followed by (meth) acrylic acid esterification.

As the compound having an ethylenically unsaturated bond, dipentaerythritol triacrylate (commercially available product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), and dipentaerythritol tetraacrylate (commercially available product) The products sold are KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., and dipentaerythritol penta (meth) acrylate (commercially sold as KAYARAD D-310; made in Japan) Pharma Corporation), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.), and these (meth) acryl fluorenyl groups Structure bonded via an ethylene glycol residue and a propylene glycol residue. These oligomer types can also be used.

The compound having an ethylenically unsaturated bond may be a polyfunctional monomer having an acid group such as a carboxyl group, a sulfonic acid group, or a phosphate group. The polyfunctional monomer having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a non-aromatic carboxylic anhydride and an unreacted hydroxyl group of the aliphatic polyhydroxy compound to react to have an acid group. The polyfunctional monomer is particularly preferably one in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include M-510 and M-520, which are polyacid-modified acrylic oligomers produced by Toa Synthesis Co., Ltd. The polyfunctional monomer having an acid group may be used alone or in combination of two or more. In addition, if necessary, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination. The preferred acid value of the polyfunctional monomer having an acid group is 0.1 mgKOH / g to 40 mgKOH / g, particularly preferably 5 mgKOH / g to 30 mgKOH / g. When the polyvalent monomer has an acid value within the above range, it is excellent in manufacturing or handling properties, and further, it is excellent in developability. In addition, 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 trimethylolethane and di-trimethylolethyl. Polyols such as alkane, trimethylolpropane, di-trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerol, diglycerol, trimethylolmelamine, and (meth) acrylic acid and ε-caprolactone Ε-caprolactone obtained by esterification is a modified polyfunctional (meth) acrylate. Among these, a polymerizable compound having a caprolactone structure represented by the following general formula (C) is preferable.

Formula (C)

(In the formula, 6 Rs are all groups represented by the following general formula (D), or 1 to 5 of the 6 Rs are groups represented by the following general formula (D), and the remainder is A group represented by the following general formula (E))

Formula (D)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and "*" represents a bonding bond.)

General formula (E)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and "*" represents a bonding bond.)

Such a polymerizable compound having a caprolactone structure is commercially available as a KAYARAD DPCA series from Nippon Kayakusho, and examples include DPCA-20 (the general formula (C) to the general formula In (E), m = 1, the number of groups represented by the general formula (D) = 2, and compounds in which R ¹ is a hydrogen atom), DPCA-30 (the general formula (C) to the general formula (E) ), M = 1, the number of groups represented by the general formula (D) = 3, compounds in which R ¹ is a hydrogen atom), DPCA-60 (in the general formula (C) to general formula (E) , M = 1, the number of groups represented by the general formula (D) = 6, compounds in which R ¹ is a hydrogen atom), DPCA-120 (in the general formula (C) to general formula (E), m = 2, the number of groups represented by the general formula (D) = 6, compounds 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 alone or as a mixture of two or more.

It is also preferable that the compound having an ethylenically unsaturated bond is at least one selected from the group of compounds represented by the following general formula (i) or general formula (ii).

[Chemical 21]

In the general formula (i) and the general formula (ii), E each independently represents-((CH ₂ ) _y CH ₂ O)-, or-((CH ₂ ) _y CH (CH ₃ ) O)-, y, respectively Each independently represents an integer of 0 to 10, and X each independently represents a (meth) acrylfluorenyl group, a hydrogen atom, or a carboxyl group. In the general formula (i), the total number of (meth) acrylfluorenyl groups is three or four, m each independently represents an integer of 0 to 10, and the total of each m is an integer of 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 number of (meth) acrylfluorenyl groups is five or six, 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 general formula (i), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. In addition, 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 general formula (ii), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. In addition, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12. -((CH ₂ ) _y CH ₂ O)-or-((CH ₂ ) _y CH (CH ₃ ) O)-in the general formula (i) or (ii) is preferably a terminal bond on the oxygen atom side Knot form on X. In particular, in the general formula (ii), it is preferable that all six X's are acrylfluorenyl groups.

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

Among the compounds represented by the general formulae (i) and (ii), pentaerythritol derivatives and dipentaerythritol derivatives are more preferred. Specific examples include compounds represented by the following formulae (a) to (f) (hereinafter, also referred to as "exemplary compounds (a) to (f)"). Among them, exemplary compounds are preferred. (A), exemplified compound (b), exemplified compound (e), exemplified compound (f).

[Chemical 22]

[Chemical 23]

Examples of commercially available polymerizable compounds represented by the general formulae (i) and (ii) include, for example, tetrafunctional acrylic acid having four ethoxyl chains manufactured by Sartomer Corporation. SR-494 of ester, DPCA-60 as a hexafunctional acrylate having 6 pentyloxy chains, and TPA as a trifunctional acrylate having 3 butyloxy groups -330 etc.

Examples of compounds having ethylenically unsaturated bonds include Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765. Acrylic urethanes described in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418. The urethane compounds having an ethylene oxide-based skeleton described in the publication are also suitable. Furthermore, as the polymerizable compound, an amine in the molecule described in Japanese Patent Laid-Open No. 63-277653, Japanese Patent Laid-Open No. 63-260909, and Japanese Patent Laid-Open No. 1-105238 can also be used. Addition polymerizable monomers having a base structure or a thioether group structure. Examples of commercially available compounds having an ethylenically unsaturated bond include urethane oligomers UAS-10 and UAB-140 (manufactured by Sanyo Kokusaku Pulp), and NK ester (NK ESTER ) M-40G, NK ester (NK ESTER) 4G, NK ester (NK ESTER) M-9300, NK ester (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 (manufactured by Nippon Oil Co., Ltd.), etc.

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

[Chemical 24]

Specific examples of the compound having an ethylenically unsaturated bond having the partial structure include, for example, trimethylolpropane tri (meth) acrylate, ethylene isocyanate modified bis (methyl) ) Acrylate, ethylene isocyanate modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dimethylolpropane tetra (methyl) ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, etc. In the present invention, these can be used particularly preferably Polymerizable compound.

In the negative photosensitive resin composition, the content of the radical polymerizable compound is preferably 1 with respect to the total solid content of the negative photosensitive resin composition in terms 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 radical polymerizable compound may be used singly or in combination of two or more kinds. In addition, the mass ratio of the polyfluorene imide precursor to the compound having a radical polymerizable compound (polyimide precursor / radical polymerizable compound) is preferably 98/2 to 10/90, and more preferably 95 / 5 to 30/70, and more preferably 90/10 to 50/50. When the mass ratio of a polyimide precursor and a radically polymerizable compound is the said range, a cured film which is more excellent in hardenability and heat resistance can be formed. Only one type of radical polymerizable compound may be used, or two or more types may be used. When two or more kinds are used, the total amount is preferably in the range.

<Photobase generator> The negative photosensitive resin composition of this invention may contain a photobase generator. The so-called photo-alkali generator is one that generates alkali by exposure and does not show activity under normal conditions of normal temperature and pressure. As long as it generates alkali (alkaline substance) when irradiated with electromagnetic waves and heated as an external stimulus, It is not particularly limited. Since the alkali generated by exposure functions as a catalyst when the polyimide precursor is hardened by heating, it can be suitably used in a negative type.

The content of the photobase generator is not particularly limited as long as a desired pattern can be formed, and it can be set to a normal content. The content of the photobase generator is preferably in a range of 0.01 parts by mass or more and less than 30 parts by mass, more preferably in a range of 0.05 parts by mass to 25 parts by mass, with respect to 100 parts by mass of the negative photosensitive resin composition. Still more preferably, it is in the range of 0.1 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 Y. Kaneko, A. Sarker, and D. Neckers, "Chemistry of Materials (Chem. Mater.)", 11, 170 (1999); H . Tachi and M. Shirai and M. Tsunooka, "Journal of Photopolymer Science and Technology, J. Photopolym. Sci. Technol . "", 13, 153 (2000); M. Winkle and and Graziano, "J. Photopolym. Sci. Technol.", 3, 419 (1990); M. Tsunooka, H. Tachi, and S. Yoshitaka, "Journal of Photopolymer Science and Technology (J. Photopolym. Sc i. Technol.) ", 9, 13 (1996); K. Suyama and H. Araki and M. Shirai (K. Suyama, H. Araki, M. Shirai)," Journal of Photopolymer Science and Technology (J. Photopolym. Sci. Technol.) ", 19, 81 (2006), transition metal compound complexes, those with structures such as ammonium salts, or potential formation by forming a salt of a phosphonium moiety with a carboxylic acid In general, an ionic compound that is neutralized by forming a salt with an alkali component, or a carbamate derivative, an oxime ester derivative, a fluorenyl compound, etc., is potentially latent with an alkali component through a urethane bond or an oxime bond Non-ionic compounds. The photobase generator that can be used in the present invention can be used without any particular limitation, and examples thereof include carbamate derivatives, amidine derivatives, amidine derivatives, α-cobalt complexes, and imidazole derivatives. Compounds, ammonium cinnamate derivatives, oxime derivatives, and the like.

The basic substance generated from the photobase generator is not particularly limited, and examples thereof include compounds having an amine group, particularly polyamines such as monoamines or diamines, or amidines. The generated basic substance is preferably a compound having an amino group having a higher basicity. The reason is that the catalyst has a strong catalytic effect such as dehydration condensation reaction in the fluorene imidization of the polyfluorene imide precursor, and it is added in a smaller amount, and the dehydration condensation reaction can be exhibited at a lower temperature. Catalyst effect. 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 catalyst effect, fluorene and aliphatic amines are preferred.

The photobase generator is preferably a photobase generator having no salt in the structure. In the photobase generator, it is preferable that there is no charge on the nitrogen atom of the generated alkali portion. The photobase generator preferably uses a covalent bond for potential generation of the generated base, and more preferably, the base generation mechanism is such that the covalent bond between the nitrogen atom of the generated alkali portion and the adjacent atom is cleaved, Base-producing compounds. If the photobase generator does not contain salt in the structure, the photobase generator can be made neutral, so the solvent solubility is good, and the pot life is improved. For this reason, the amine generated from the photobase generator used in the present invention is preferably a primary amine or a secondary amine.

In addition, for the reasons as described above, it is preferable that the base generated in the manner described above is used as a base for potential generation using a covalent bond. In addition, it is more preferable that the generated base is made latent using a amide bond, a urethane bond, and an oxime bond. Examples of the alkali generator in the present invention include alkali generators having an ammonium cinnamate structure as disclosed in Japanese Patent Laid-Open No. 2009-80452 and International Publication WO2009 / 123122, such as Japanese Patent The alkali generator having a urethane structure as disclosed in JP-A-2006-189591 and JP-A-2008-247747, such as JP-A-2007-249013 and JP-A-2008- A base generator having an oxime structure and a carbamoyl oxime structure as disclosed in 003581 is not limited to these, and other known base generator structures may be used.

Hereinafter, a specific example is given and the photobase generator which can be used for this invention is demonstrated. As an ionic compound, the following structural formula is mentioned, for example.

[Chemical 25]

Examples of the fluorenyl compound include compounds represented by the following formula.

[Chemical 26]

Examples of the photobase generator include compounds represented by the following general formula (PB-1).

[Chemical 27] (PB-1)

(In the general 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. Among them, 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 include a heteroatom bond; R ⁴³ and R ⁴⁴ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a silane group, and a silane Alcohol, nitro, nitroso, sulfinyl, sulfo, sulfonate, phosphine, phosphine, phosphino, phosphonate, or organic groups, 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 mercapto group, a thioether group, a silane group, a silanol group, a nitro group, a nitroso group, a sulfinate group, a sulfo group, or a sulfonic acid group. The radicals, phosphino, phosphinyl, phosphino, phosphino, amine, ammonium or organic groups may be the same or different; or among 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.

[Chemical 28]

[Chemical 29]

[Chemical 30]

In addition, examples of the photobase generator include compounds described in paragraphs 0185 to 0188, paragraphs 0199 to 0200, and paragraph 0202 in Japanese Patent Laid-Open Publication No. 2012-93746. Compounds described in paragraph numbers 0022 to 0069 of Japanese Patent Publication No. 2013-194205, compounds described in paragraph numbers 0026 to 0074 of Japanese Patent Laid-Open Publication No. 2013-204019, and paragraph numbers of Japanese Patent Publication No. WO2010 / 064631 The compounds described in 0052 are examples.

<Thermal Alkali Generator> The negative photosensitive resin composition of the present invention may contain a thermal alkali generator. The type of the thermal alkali generator is not particularly limited, but preferably includes at least one selected from the group consisting of an acidic compound that generates an alkali when heated to 40 ° C or higher, and an ammonium salt having an anion and an ammonium cation having a pKa1 of 0 to 4 Hot alkali generator. Here, pKa1 represents a logarithmic label (-Log ₁₀ Ka) of the dissociation constant (Ka) of the first proton of the polyacid. By compounding such a compound, a cyclization reaction of a polyimide precursor can be performed at a low temperature, and a negative photosensitive resin composition having more excellent stability can be formed. In addition, the hot alkali generator does not generate an alkali as long as it is not heated, so even if it coexists with a polyimide precursor, it can suppress the cyclization of the polyimide precursor during storage, and is excellent in storage stability.

The hot alkali generator in the present invention contains at least one selected from the group consisting of an acidic compound (A1) which generates an alkali when heated to 40 ° C or higher, and an ammonium salt (A2) having an anion and an ammonium cation having a pKa1 of 0 to 4. The acidic compound (A1) and the ammonium salt (A2) generate a base if heated. Therefore, the base generated from these compounds can promote the cyclization reaction of the polyimide precursor and can be used in Cyclization of polyfluorene imide precursors is performed at low temperatures. In addition, even if these compounds are coexisted with a polyimide precursor that is cyclized and hardened by a base, the cyclization of the polyimide precursor is hardly performed unless heating is performed. A negative-type photosensitive resin composition having excellent stability is prepared. In addition, in the present specification, the term "acidic compound" refers to a compound in which 1 g of the compound is extracted into a container, and a mixed solution of ion-exchanged water and tetrahydrofuran (mass ratio of water / tetrahydrofuran = 1/4) 50 mL is added. , And stirred at room temperature for 1 hour, using a pH (potential hydrogen, pH) meter to measure the obtained solution at 20 ° C is less than 7.

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

In the present invention, the base generated by the hot base generator is preferably a secondary amine or a tertiary amine, and more preferably a tertiary amine. Because tertiary amines are highly basic, the cyclization temperature of polyimide precursors can be further reduced. The boiling point of the alkali generated by the hot alkali generator is preferably 80 ° C or higher, more preferably 100 ° C or higher, and most preferably 140 ° C or higher. The molecular weight of the generated base is preferably 80 to 2,000. The lower limit is more preferably 100 or more. The upper limit is more preferably 500 or less. In addition, the molecular weight value is a theoretical value calculated | required from a 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 general formula (A1) described later.

In the present invention, the ammonium salt (A2) is preferably an acidic compound. In addition, the ammonium salt (A2) may be a compound containing an acidic compound that generates a base when heated to 40 ° C or higher (preferably 120 ° C to 200 ° C), or it may be a compound except for heating to 40 ° C or higher (more It is preferably 120 ° C to 200 ° C), and compounds other than the acidic compounds of the base are generated.

<<< Ammonium salt> In the present invention, the ammonium salt refers to a salt of an ammonium cation and an anion represented by the following general formula (1) or general formula (2). The anion may be bonded to any part of the ammonium cation through a covalent bond, and may also exist outside the molecule of the ammonium cation, and preferably exists outside the molecule of the ammonium cation. The term “anion exists outside the molecule of the ammonium cation” means that the ammonium cation and the anion are not bonded by a covalent bond. Hereinafter, the anion outside the molecule of the cation part is also called a counter anion. [Chemical 31] In the general formula (1) and the general 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 , R ⁵ and R ⁷ may be bonded to form a ring, respectively.

In the present invention, the ammonium salt is preferably an anion and an ammonium cation having a pKa1 of 0 to 4. The upper limit of the pKa1 of the anion is more preferably 3.5 or less, and even more preferably 3.2 or less. The lower limit is more preferably 0.5 or more, and even more preferably 1.0 or more. When the pKa1 of the anion is within the above range, the polyfluorene imide 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 hot alkali generator is good, the generation of alkali without heating can be suppressed, and the stability of the negative photosensitive resin composition is good. When pKa1 is 0 or more, the generated base is difficult to be neutralized, and the cyclization efficiency of the polyfluorene imide 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. A carboxylate anion is more preferable for the reason that the stability of the salt and the thermal decomposability can coexist. . 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, and more preferably an anion of a divalent carboxylic acid. According to this aspect, a thermal alkali generator which can further improve the stability, hardenability, and developability of the negative photosensitive resin composition can be produced. In particular, by using an anion of a divalent carboxylic acid, the stability, hardenability, 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. pKa1 is more preferably 3.5 or less, and even more preferably 3.2 or less. According to this aspect, the stability of the negative photosensitive resin composition can be further improved. Here, the so-called pKa1 represents the logarithm of the inverse of the first dissociation constant of the acid, and can be referred to "Determination of Organic Structures by Physical Methods" (Author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; Editors: Braude, EA, Nachod, FC; Academic Press, New York, 1955), or "Data for Biochemical Research" (Author: Dawson , RMC, etc .; Oxford, Clarendon Press, 1959). For compounds not described in these documents, values calculated from the structural formula using software using ACD / pKa (manufactured by ACD / Labs) were used.

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

In the present invention, the electron-withdrawing group refers to a Hammett's substituent constant σm showing a positive value. Here, σm is explained in detail in Tono's general comment, "Journal of the Society of Organic Synthetic Chemistry", Vol. 23 No. 8 (1965) P.631-642. The electron-withdrawing group of the present invention is not limited to the substituents described in the literature. Examples of the substituent having a positive value for σm include, for example, 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. . In addition, Me represents methyl, Ac represents ethenyl, and Ph represents phenyl.

In the present invention, the EWG preferably represents a group represented by the following general formula (EWG-1) to (EWG-6). [Chemical 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 carbon number of the alkyl group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. The alkyl group may be any of linear, branched, and cyclic, preferably linear or branched, and more preferably linear. The alkyl group may have a substituent or may be unsubstituted. Examples of the substituent include those described for the substituent which the organic group represented by A ¹ described later may have. The substituent is preferably a carboxyl group. The carbon number of the alkenyl group is preferably 2 to 30, more preferably 2 to 20, and even more preferably 2 to 10. The alkenyl group may be any of linear, branched, and cyclic, preferably linear or branched, and more preferably linear. The alkenyl group may have a substituent or may be unsubstituted. Examples of the substituent include those described for the substituent which the organic group represented by A ¹ described later may have. The substituent is preferably a carboxyl group. The carbon number of the aryl group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include those described for the substituent which the organic group represented by A ¹ described later may have. The substituent is preferably a carboxyl group.

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

The carbon number of the alkylene group represented by L ¹⁰ is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. The alkylene group may be any of linear, branched, and cyclic, preferably linear or branched, and more preferably linear. The alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include those described for the substituent which the organic group represented by A ¹ described later may have. The carbon number of the alkenyl group represented by L ¹⁰ is preferably 2 to 30, more preferably 2 to 20, and even more preferably 2 to 10. The alkenyl group may be any of linear, branched, and cyclic, preferably linear or branched, and more preferably linear. The alkenyl group may have a substituent or may be unsubstituted. Examples of the substituent include those described for the substituent which the organic group represented by A ¹ described later may have. The carbon number of the arylene group represented by L ¹⁰ is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. The arylene group may have a substituent or may be unsubstituted. Examples of the substituent include those described for the substituent which the organic group represented by A ¹ described later may have.

The carbon number of the alkyl group represented by R ^X is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. The alkyl group may be any of linear, branched, and cyclic, preferably linear or branched, and more preferably linear. The alkyl group may have a substituent or may be unsubstituted. Examples of the substituent include those described for the substituent which the organic group represented by A ¹ described later may have. The carbon number of the alkenyl group represented by R ^X is preferably 2 to 30, more preferably 2 to 20, and even more preferably 2 to 10. The alkenyl group may be any of linear, branched, and cyclic, preferably linear or branched, and more preferably linear. The alkenyl group may have a substituent or may be unsubstituted. Examples of the substituent include those described for the substituent which the organic group represented by A ¹ described later may have. The carbon number of the aryl group represented by R ^X is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include those described for the substituent which the organic group represented by A ¹ described later may have.

Specific examples of the carboxylate anion include a maleate anion, a phthalate anion, an N-phenylimide diacetate 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). [Chemical 35]

In the general formula, R ¹⁰¹ represents an n-valent organic group, R ¹⁰² to R ¹¹¹ each independently represent a hydrogen atom or a hydrocarbon group, R ¹⁵⁰ and R ¹⁵¹ each independently represent a hydrocarbon group, and R ¹⁰⁴ and R ¹⁰⁵ and 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. 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. Examples of the monovalent organic group include an alkyl group, an alkylene group, and an aryl group. Examples of the divalent or higher organic group include a group obtained by removing one or more hydrogen atoms from a monovalent organic group and forming an n-valent group. R ^{101 is} preferably aryl. Specific examples of the aryl group include those described in Ar ¹⁰ 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, alkenyl group, and aryl group may further have a substituent. Examples of the substituent include those described for the substituent which the organic group represented by A ¹ described later may have.

The carbon number of the alkyl group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. The alkyl group may be any of linear, branched, and cyclic, preferably linear or branched, and more preferably linear. The alkyl group may have a substituent or may be unsubstituted. The carbon number of the alkenyl group is preferably 2 to 30, more preferably 2 to 20, and even more preferably 2 to 10. The alkenyl group may be any of linear, branched, and cyclic, preferably linear or branched, and more preferably linear. The alkenyl group may have a substituent or may be unsubstituted. The carbon number of the aryl group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 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 6 to 30, more preferably 6 to 20, and even more preferably 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 heterocyclic ring. The ring may be a single ring or a complex ring. Examples of the linking group when the groups are bonded to form a ring include a group selected from the group consisting of -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aryl group, and combinations thereof. Divalent linking group in the group. Specific examples of the formed ring include, for example, 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 thiazole. Azine ring, indole ring, isoindole ring, benzimidazole ring, purine ring, quinoline ring, isoquinoline ring, quinoxaline ring, Porphyrin ring, carbazole ring, etc.

In the present invention, the ammonium cation preferably has a structure represented by the general formula (Y1-1) or the general formula (Y1-2), more preferably the general formula (Y1-1) or the general formula (Y1-2) And R ¹⁰¹ is a structure having an aryl group, and particularly preferably a structure represented by the general 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 general formula (Y). [Chemical 36] In the general formula (Y), Ar ¹⁰ represents an aromatic group, R ¹¹ to R ¹⁵ each independently represent a hydrogen atom or a hydrocarbon group, R ¹⁴ and R ¹⁵ may be bonded to 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 pentenene ring, an indene ring, a fluorene ring, a heptene ring, an indenene ring, a fluorene ring, and a condensed pentabenzene. Ring, ethane naphthalene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring, Ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indoxazine Ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinazine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, iso A quinoline ring, a carbazole ring, a pyridine ring, an acridine ring, a phenanthroline ring, a thiathracene ring, a benzopyran ring, a xanthene ring, a phenothiazine ring, a phenothiazine ring, and a phenazine ring. Among them, from the viewpoints of storage stability and high sensitivity, a benzene ring, a naphthalene ring, an anthracene ring, a phenothiazine ring, or a carbazole ring is preferable, and a benzene ring or a naphthalene ring is most preferable. Examples of the substituent which the aryl group may have include those described for the substituent which the organic group represented by A ¹ described later may have.

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

The carbon number of the alkyl group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. The alkyl group may be any of linear, branched, and cyclic. Examples of the linear or branched alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, Octadecyl, isopropyl, isobutyl, second butyl, third butyl, 1-ethylpentyl, and 2-ethylhexyl. The cyclic alkyl (cycloalkyl) may be a monocyclic cycloalkyl or a polycyclic cycloalkyl. Examples of the monocyclic cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of the polycyclic cycloalkyl group include adamantyl, norbornyl, norbornyl, pinenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, fluorenedifluorenyl, and Cyclohexyl and pinenyl. Among them, from the viewpoint of coexistence with high sensitivity, cyclohexyl is the best. The carbon number of the alkenyl group is preferably 2 to 30, more preferably 2 to 20, and even more preferably 2 to 10. The alkenyl group may be any of linear, branched, and cyclic, preferably linear or branched, and more preferably linear. The carbon number of the aryl group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12.

R ¹³ to R ^{15 each} represent a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include the hydrocarbon groups described for R ¹¹ and R ¹² . R ¹³ to R ^{15 are} particularly preferably an alkyl group, and the preferred forms are 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 (non-aromatic hydrocarbon ring), an aromatic ring, and a heterocyclic ring. The ring may be a single ring or a complex ring. Examples of the linking group when R ⁴ and R ⁵ are bonded to form a ring include a group selected from the group consisting of -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aryl group, and combinations thereof. A bivalent linking group in the group. Specific examples of the formed ring include, for example, 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 thiazole. Azine ring, indole ring, isoindole ring, benzimidazole ring, purine ring, quinoline ring, isoquinoline ring, quinoxaline ring, Porphyrin ring, carbazole ring, etc.

R ¹³ to R ^{15 are} preferably R ¹⁴ and R ¹⁵ 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 generated. Further, it is boiling amines or basic species generated viewpoint, R ¹³ ~ R ¹⁵ R ¹³ is preferably the total number of carbon atoms in R ¹⁴ and R ¹⁵ is 7 to 30, more preferably 10 to 20 . In addition, for the reason that amine species having a high boiling point are liable to be generated, the amount of the chemical formula of "-NR ¹³ R ¹⁴ R ¹⁵ " in the general formula (Y) is preferably 80 to 2000, and more preferably 100 to 500.

On the other hand, as an embodiment for further improving the adhesion with the copper wiring, the following aspects may be mentioned: In the general formula (Y), R ¹³ and R ¹⁴ are methyl groups or ethyl groups, and R ¹⁵ is a carbon number 5 or more straight-chain, branched or cyclic alkyl groups, or aryl groups. In this embodiment, it is preferable that R ¹³ and R ¹⁴ are methyl groups, R ¹⁵ is a linear alkyl group having 5 to 20 carbon atoms, a branched alkyl group having 6 to 17 carbon atoms, and a ring having 6 to 10 carbon atoms. Alkyl group or phenyl group, more preferably: R ¹³ and R ¹⁴ are methyl groups, R ¹⁵ is a linear alkyl group having 5 to 10 carbon atoms, a branched alkyl group having 6 to 10 carbon atoms, and 6 to 8 carbon atoms Cyclic alkyl or phenyl. By reducing the hydrophobicity of the amine species as described above, even when the amine is attached to the copper wiring, it is possible to more effectively suppress the decrease in the affinity between the copper surface and the polyimide. In this embodiment, the preferable ranges of Ar ¹⁰ , R ¹¹ , R ^12, and n are the same as those described above.

<The compound represented by General formula (A1)> In this invention, it is also preferable that an acidic compound is a compound represented by the following general formula (A1). This compound is acidic at room temperature, but disappears by heating, decarboxylation or dehydration cyclization of the carboxyl group, thereby neutralizing and deactivating the amine site which has been previously made active, thereby becoming alkaline. The general formula (A1) will be described below.

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

In the general formula (A1), A ¹ represents a p-valent organic group. Examples of the organic group include an aliphatic group and an aryl group, and an aryl group is preferred. When A ^{1 is an} aryl group, a base having a high boiling point can be easily produced at a lower temperature. By increasing the boiling point of the generated base, volatilization or decomposition caused by heating during the curing of the polyfluorene imide precursor can be suppressed, and the cyclization of the polyfluorene imide precursor can be performed more efficiently. Examples of the monovalent aliphatic group include an alkyl group and an alkenyl group. The carbon number of the alkyl group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. The alkyl group may be any of linear, branched, and cyclic. The alkyl group may have a substituent or may be unsubstituted. Specific examples of the alkyl group include methyl, ethyl, third butyl, dodecyl, cyclopentyl, cyclohexyl, cycloheptyl, and adamantyl. The carbon number of the alkenyl group is preferably 2 to 30, more preferably 2 to 20, and even more preferably 2 to 10. The alkenyl group may be any of linear, branched, and cyclic. 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 obtained by removing one or more hydrogen atoms from the monovalent aliphatic group. Aryl may be monocyclic or polycyclic. 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 pentalene ring, an indene ring, a fluorene ring, a heptene ring, an indenene ring, a fluorene ring, a pentacene ring, an ethane naphthalene ring, Phenanthrene ring, anthracene ring, fused tetraphenyl ring, Ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indoxazine Ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinazine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, iso Quinoline ring, carbazole ring, morphine ring, acridine ring, morpholine ring, thiathracene ring, benzopyran ring, xanthene ring, phenoxaline ring, phenothiazine ring, and morphazine ring, most It is preferably a benzene ring. The aryl group may have a plurality of aromatic rings connected through a single bond or a linking group described later. As the linking group, for example, an alkylene group is preferred. It is also preferable that the alkylene group is any of linear and branched. Specific examples of the aryl group in which a plurality of aromatic rings are connected through a single bond or a linking group include biphenyl, diphenylmethane, diphenylpropane, diphenylisopropane, triphenylmethane, and tetrabenzene. Methane, etc.

Examples of the substituent which the organic group represented by A ¹ may have include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; an alkane such as a methoxy group, an ethoxy group, and a third butoxy group Aryloxy groups such as phenoxy and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl and butoxycarbonyl; aryloxycarbonyl groups such as phenoxycarbonyl; ethoxyl and propionyloxy And fluorenyl groups such as benzamyloxy; fluorenyl groups such as ethenyl, benzamyl, isobutylfluorenyl, acrylfluorenyl, methacrylfluorenyl, and methoxyoxalyl; methylmercapto and tertiary butyl Alkyl mercapto groups such as mercapto; aryl mercapto groups such as phenyl mercapto and p-tolyl mercapto; alkyl groups such as methyl, ethyl, third butyl, and dodecyl; halogenated alkyl groups such as fluorinated alkyl; cyclopentyl, Cycloalkyl groups such as cyclohexyl, cycloheptyl, and adamantyl; aryl groups such as phenyl, p-tolyl, xylyl, cumenyl, naphthyl, anthracenyl, and phenanthryl; hydroxyl; carboxyl; formamyl; Sulfo; cyano; alkylaminocarbonyl; arylaminocarbonyl; sulfoamido; silyl; amino; monoalkylamino; dialkylamino; 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 alkylene (preferably a carbon number) 1 to 10 straight chain alkylene or branched alkylene), cycloalkylene (preferably a cycloalkylene having 3 to 10 carbon atoms), and alkenyl (preferably a straight chain alkylene having 210 carbon atoms) An alkenyl group or a branched alkenyl group), or a linking group in which a plurality of these are connected. The total carbon number of the linking group is preferably 3 or less. The linking group is preferably an alkylene group, a cycloalkylene group, an alkylene group, more preferably a linear alkylene group or a branched alkylene group, and even more preferably a linear alkylene group, and particularly preferably an alkylene group or an alkylene group. Methyl, most preferably methylene.

R ¹ represents a monovalent organic group. Examples of the monovalent organic group include an aliphatic group and an aryl group. About aliphatic group, an aryl group, the A ¹ include those as described. The monovalent organic group represented by R ¹ may have a substituent. Examples of the substituent include those mentioned 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. Examples of the linking group represented by L ² include the groups described in L ¹ described above. The preferred ranges are also the same. Particularly preferred is ethylene or methylene, and most preferred is methylene. n represents an integer of 1 or more, preferably 1 or 2, and 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, a tertiary amine having a high boiling point is easily generated by heating at 200 ° C or lower. Furthermore, the stability of the negative photosensitive resin composition can be improved.

m represents an integer of 1 or more, preferably 1 or 2, and 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, a tertiary amine having a high boiling point is easily generated by heating at 200 ° C or lower. Furthermore, the stability of the negative photosensitive resin composition can be improved. p represents an integer of 1 or more, preferably 1 or 2, and more preferably 1. The upper limit of p is the maximum number of substituents that can be used for the organic group represented by A ¹ . When p is 1, a tertiary amine having a high boiling point is easily generated by heating at 200 ° C or lower.

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

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

Specific examples of the hot alkali generator in the present invention are described below, but the present invention is not limited to these specific examples. These can be used individually or in mixture of 2 or more types. 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 formula (A1). Among the compounds shown below, (A-1) to (A-11), (A-18) to (A-26) are more preferable, and (A-1) to (A-9) are more preferable. , (A-18) to (A-21), (A-23), (A-24). In addition, from the viewpoint of improving the adhesion with copper, (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 hot alkali generator used in the present invention, the compounds described in paragraph No. 0015 to paragraph 0055 of Japanese Patent Application No. 2015-034388 can be preferably used, and these contents are incorporated in this specification.

When a hot alkali generator is used, the content of the hot alkali generator 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 even more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and even more preferably 20% by mass or less. The hot alkali generator may be used alone or in combination of two or more. When two or more kinds are used, the total amount is preferably in the range.

<Thermal radical polymerization initiator> The negative photosensitive resin composition of this invention may contain a thermal radical polymerization initiator. As the thermal radical polymerization initiator, a known thermal radical polymerization initiator can be used. A thermal radical polymerization initiator is a compound that generates radicals by the energy of heat and starts or accelerates the polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, when the cyclization reaction of a polyimide precursor is advanced, the polymerization reaction of a polymerizable compound can be advanced. In addition, when the polyfluorene imide precursor contains an ethylenically unsaturated bond, the cyclization of the polyfluorene imide precursor and the polymerization reaction of the polyfluorene imide precursor can be performed together, so that higher heat resistance can be achieved . Examples of the thermal radical polymerization initiator include aromatic ketones, onium salt compounds, peroxides, sulfur compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azineium compounds, and methylene Metal compounds, active ester compounds, compounds having a carbon halogen bond, azo compounds, and the like. Among these, a peroxide or an azo compound is more preferable, and a peroxide is particularly preferable. The 10-hour half-aging temperature of the thermal radical polymerization initiator used in the present invention is preferably 90 ° C to 130 ° C, and more preferably 100 ° C to 120 ° C. Specifically, the compounds described in paragraphs 0074 to 0118 of Japanese Patent Laid-Open No. 2008-63554 can be mentioned. Among 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% to 50% by mass relative to the total solid content of the negative photosensitive resin composition. %, More preferably 0.1% to 30% by mass, and particularly preferably 0.1% to 20% by mass. Moreover, it is preferable to contain 0.1-50 mass parts with respect to 100 mass parts of polymerizable compounds, and it is more preferable to contain 0.5-30 mass parts. According to this aspect, a cured film having more excellent heat resistance is easily formed. There may be only one thermal radical polymerization initiator, or two or more. When there are two or more types of thermal radical polymerization initiators, it is preferable that the total thereof is within the above range.

<Anticorrosive agent> It is preferable to add an anticorrosive agent to the negative photosensitive resin composition of this invention. The anticorrosive agent is added for the purpose of preventing ions from flowing out of the metal wiring. As a compound, for example, a rust preventive agent described in Japanese Patent Laid-Open No. 2013-15701, paragraph number 0094, and Japanese Patent Laid-open No. 2009-283711 can be used. Compounds described in paragraph numbers 0073 to 0076 of Japanese Patent Publication, compounds described in paragraph number 0052 of Japanese Patent Laid-Open No. 2011-59656, paragraph numbers 0114 and 0116 of Japanese Patent Laid-Open No. 2012-194520 And the compounds described in paragraph number 0118 and the like. Among them, a compound having a triazole ring or a compound having a tetrazole ring can be preferably used, and 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 an anticorrosive agent is added, the blending amount of the anticorrosive agent is preferably in the range of 0.1 to 10 parts by mass, and more preferably in the range of 0.2 to 5 parts by mass, with respect to 100 parts by mass of the polyimide precursor. The anticorrosive agent may be only one kind, or two or more kinds. When two or more kinds are used, it is preferable that the total thereof is within the above range.

<Metal Adhesive Improver> The negative photosensitive resin composition of the present invention preferably contains a metal adhesive improver for improving adhesiveness with a metal material used for an electrode, wiring, or the like. Examples of the metal adhesion improver include those described in paragraphs 0046 to 0049 of Japanese Patent Laid-Open No. 2014-186186 or paragraphs 0032 to 0043 of Japanese Patent Laid-Open No. 2013-072935. A thioether compound. Moreover, as a metal adhesive improvement agent, the following compounds can be illustrated. [Chemical 39] When a metal adhesion improving agent is used, the blending amount of the metal adhesion improving agent is preferably in the range of 0.1 to 30 parts by mass, and more preferably 0.5 to 15 parts by mass based on 100 parts by mass of the polyimide precursor. Range of parts by mass. When it is 0.1 parts by mass or more, the adhesiveness between the film and the metal after thermal curing becomes good, and when it is 30 parts by mass or less, the heat resistance and mechanical properties of the film after curing become good. The metal adhesion improver may be only one type, or two or more types. When two or more kinds are used, it is preferable that the total thereof is within the above range.

<Silane coupling agent> The negative photosensitive resin composition of the present invention preferably contains a silane coupling agent in terms of improving the adhesion to the substrate. Examples of the silane coupling agent include compounds described in Japanese Patent Laid-Open No. 2014-191002, paragraphs 0061 to 0073, compounds described in WO2011 / 080992A1, paragraphs 0063 to 0071, and Compounds described in paragraphs 0060 to 0061 of Japanese Patent Laid-Open No. 2014-191252, compounds described in paragraphs 0045 to 0052 of Japanese Patent Laid-open No. 2014-41264, and compounds of WO2014 / 097594 The compound described in paragraph number 0055. In addition, it is also preferable to use two or more different silane coupling agents as described in Japanese Patent Application Laid-Open No. 2011-128358, paragraph numbers 0050 to 0058. When a silane coupling agent is used, the blending amount of the silane coupling agent is preferably in the range of 0.1 to 20 parts by mass, and more preferably in the range of 1 to 10 parts by mass, based on 100 parts by mass of the polyimide precursor. . When it is 0.1 parts by mass or more, sufficient adhesion to the substrate can be provided, and when it is 20 parts by mass or less, problems such as an increase in viscosity during storage at room temperature can be further suppressed. The silane coupling agent may be only one kind, or two or more kinds. When two or more kinds are used, it is preferable that the total thereof is within the above range.

<Sensitizing dye> The negative photosensitive resin composition of this invention may contain a sensitizing dye. The sensitizing dye absorbs a specific active radiation and becomes an electronically excited state. The sensitized dye in an electronically excited state comes into contact with a thermal alkali generator, a thermal radical polymerization initiator, a photoradical polymerization initiator, and the like, and causes the effects of electron movement, energy movement, and heat generation. As a result, the thermal base generator, thermal radical polymerization initiator, and photoradical polymerization initiator undergo chemical changes to decompose, and generate radicals, acids, or bases.

Examples of preferred sensitizing dyes include those belonging to the following compounds and those having an absorption wavelength in the region of 300 nm to 450 nm. Examples include: polynuclear aromatics (such as phenanthrene, anthracene, pyrene, pyrene, triphenylene, 9,10-dialkoxyanthracene), xanthene (such as fluorescein, eosin, red fluorescein, fluorene Tannin B, Bengal rose red), thiaxanthone (such as 2,4-diethylthioxanthone), cyanine (such as thiocarbonyl cyanine, oxocyanine), merocyanine (Such as merocyanine, carbonyl merocyanine), thiazines (such as thiamine, methylene blue, toluidine blue), acridines (such as acridine orange, chloroflavin, acridine flavin), anthracene Quinones (such as anthraquinones), succinates (such as squarates), coumarins (such as 7-diethylamino-4-methylcoumarin), benzene Vinylbenzenes, distyrylbenzenes, carbazoles, etc.

Among them, in the present invention, from the standpoint of starting efficiency, it is preferable to use polynuclear aromatics (for example, phenanthrene, anthracene, fluorene, pyrene, triphenylene), thioanthrones, and distyrylbenzene And styrylbenzenes, and more preferably a compound having an anthracene skeleton. Particularly preferred specific compounds 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, relative to the total solid content of the negative photosensitive resin composition. 15 mass%, more preferably 0.5 mass% to 10 mass%. The sensitizing dye may be used alone or in combination of two or more.

<Chain transfer agent> The negative photosensitive resin composition of this invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by the Polymer Society, 2005) pages 683-684. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule can be used. These chain transfer agents provide hydrogen to low-activity free radical species to generate free radicals, or are deprotonated after being oxidized, thereby generating free radicals. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles) can be preferably used. Wait).

When the negative photosensitive resin composition contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the total solid content of the negative photosensitive resin composition, and more preferably 1 to 10 parts by mass, and more preferably 1 to 5 parts by mass. The chain transfer agent may be only one kind, or two or more kinds. When there are two or more kinds of chain transfer agents, it is preferable that the total thereof is within the above range.

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

The fluorine content of the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content ratio within this range is effective in terms of thickness uniformity or liquid saving of the coating film, and also has good solubility. 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, manufactured by DIC (stock)), Fluorad FC430 Fluorad FC431, Fluorad FC171 (above, manufactured by Sumitomo 3M (Shares)), 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, Surflon KH-40 (above, manufactured by Asahi Glass), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA), etc. As the fluorine-based surfactant, a block polymer may also be used. As a specific example, for example, a compound described in Japanese Patent Laid-Open No. 2011-89090 may be mentioned. In addition, the following compounds can be exemplified as the fluorine-based surfactant used in the present invention. [Chemical 40] The weight average molecular weight of the compound is, for example, 14,000.

Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates (such as glycerol propoxylate, Glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylen Glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters (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), Solusperse 20000 (Lubo, Japan) Run (Lubrizol) ( Parts)) and the like. In addition, Pionin D-6112-W manufactured by Takemoto Oil (Stock), and NCW-101, NCW-1001, NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. can also be used.

Specific examples of the cationic surfactant include a phthalocyanine derivative (trade name: EFKA-745, manufactured by Morishita Industries, Ltd.), and an organosiloxane polymer KP341 (Shin-Etsu Chemical Industry) (Manufactured)), (meth) acrylic (co) polymers Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 ( Kyoeisha Chemical Co., Ltd.), W001 (Yushang Co., Ltd.), etc.

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

Examples of the silicone-based surfactants include "Toray Silicone DC3PA", "Toray Silicone SH7PA", and "Toray Silicone" manufactured by Toray Dow Corning Corporation. (Toray Silicone DC11PA "," Toray Silicone SH21PA "," Toray Silicone SH28PA "," Toray Silicone SH29PA "," Toray Silicone 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 Shinetsu Silicone Co., Ltd.," BYK307 "," BYK323 "manufactured by BYK Chemie , "BYK330", etc.

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, relative to the total solid content of the negative photosensitive resin composition. To 1.0% by mass. The surfactant may be only one kind, or two or more kinds. When two or more surfactants are contained, it is preferable that the total thereof is within the above 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 behenamine may be added. Etc., and it is made to exist on the surface of a negative photosensitive resin composition in the process of drying after coating. When the negative photosensitive resin composition contains a higher fatty acid derivative and the like, the content of the higher fatty acid derivative and the like with respect to the total solid content of the negative photosensitive resin composition is preferably 0.1% by mass to 10% by mass. The higher fatty acid derivative and the like may be only one kind, or two or more kinds. When two or more types of higher fatty acid derivatives are contained, it is preferable that the total is within the above range.

<Solvent> When the negative-type photosensitive resin composition of the present invention is formed into a layer by coating, it is preferable to prepare a solvent. As long as the negative-type photosensitive resin composition can be formed in a layered form, known solvents can be used without limitation. As the solvent used in the negative photosensitive resin composition of the present invention, as the esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, oxyacetic acid Alkyl esters (e.g. methyloxyacetate, ethyloxyacetate, butyloxyacetate (e.g. methylmethoxyacetate, ethylmethoxyacetate, butylmethoxyacetate, methylethoxyacetate) Ester, ethyl ethoxyacetate, etc.)), alkyl 3-oxypropionate (eg methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg 3-methoxypropionate Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-oxypropionates (e.g. 2 -Methyloxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (e.g. methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2- Propyl methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionic acid (Ester)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (e.g. methyl 2-methoxy-2-methylpropionate, 2- Ethyl ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, methyl 2-oxobutanoate And ethyl 2-oxobutanoate, and examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and methyl cellulose. Agent 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, Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like, and examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptane. Ketones, N-methyl-2-pyrrolidone, and the like, and as the aromatic hydrocarbons, for example, toluene, xylene, anisole, and limonene can be suitably exemplified, and as the fluorenes, suitably, List dimethyl sulfene.

From the viewpoint of improving the coating surface state and the like, a form in which two or more solvents are mixed is also preferable. Among them, the following mixed solution is preferred, which comprises methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol Dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfene, ethyl carbitol ethyl Esters, butylcarbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate. Particularly preferred is the combined use of dimethyl sulfene and γ-butyrolactone.

When the negative photosensitive resin composition contains a solvent, from the viewpoint of coating properties, the content of the solvent is preferably such that the total solid content concentration of the negative photosensitive resin composition becomes 5 to 80% by mass. The amount is more preferably 5 to 70% by mass, and even more preferably 10 to 60% by mass. The solvent may be only one kind, or two or more kinds. When two or more solvents are contained, it is preferable that the total thereof is within the above range. From the viewpoint of film strength, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N, N-diamine are relative to the total mass of the negative photosensitive resin composition. The content of methylacetamide and N, N-dimethylformamide is preferably less than 5% by mass, more preferably less than 1% by mass, even more preferably less than 0.5% by mass, and particularly preferably not more than 0.5% by mass. At least 0.1% by mass.

<Other additives> As long as the effect of the present invention is not impaired, the negative photosensitive resin composition of the present invention may be formulated with various additives, such as inorganic particles, hardeners, hardening catalysts, fillers, antioxidants, and ultraviolet rays, as necessary. Absorbent, anticoagulant, etc. When these additives are blended, the total blended amount is preferably 3% by mass or less of the solid content of the negative photosensitive resin composition.

From the viewpoint of coating surface state, 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, and particularly preferably less than 0.6% by mass.

From the viewpoint of insulation, the metal content of the negative photosensitive resin composition of the present invention is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and particularly preferably less than 0.5 mass ppm. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, and nickel. When a plurality of metals are included, the total of these metals is preferably in the above range. In addition, as a method for reducing unintentional metal impurities contained in the negative-type photosensitive resin composition, methods such as selecting a raw material with a low metal content as a raw material constituting the negative-type photosensitive resin composition and The raw materials of the photosensitive resin composition are filtered by a filter, and lined with polytetrafluoroethylene or the like in the apparatus, and distillation is performed under conditions that minimize contamination.

From the viewpoint of wiring corrosivity, the content of halogen atoms in the negative photosensitive resin composition of the present invention is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass. ppm. Among them, those present in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and particularly preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of a chlorine atom and a bromine atom, or a chloride ion and a bromide ion is the said range, respectively.

<Preparation of a negative-type photosensitive resin composition> The negative-type photosensitive resin composition of this invention can be prepared by mixing the said components. The mixing method is not particularly limited, and can be performed by a conventionally known method. In addition, it is preferable to perform filtration using a filter for the purpose of removing foreign matters such as dust, particulates, and the like 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 even more preferably 0.1 μm or less. The material of the filter is preferably a filter made of polytetrafluoroethylene, polyethylene, or nylon. The filter may be a person who has been washed with an organic solvent in advance. In the filter filtration step, a plurality of filters can be used in series or in parallel. When multiple filters are used, filters with different pore sizes and / or materials can also be used in combination. In addition, various materials can be filtered multiple times, and the step of multiple filtering can also be a cyclic filtering step. It is also possible to perform filtration by pressurizing, and the pressurizing pressure is preferably 0.05 MPa or more and 0.3 MPa or less. In addition to filtration using a filter, impurities can also be removed using an adsorbent. In addition, regarding the removal of impurities, a filter filtration and an adsorption material may be combined. As the adsorbent, known adsorbents can be used, and for example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents 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 excellent in heat resistance and insulation, it can be preferably used for an insulating film for a semiconductor element, an interlayer insulating film for a redistribution layer, and the like. In particular, it can be preferably used for an interlayer insulating film or the like for a redistribution layer in a three-dimensional mounting element. In addition, it can also be used for photoresists (galvanic resist, etching resist, solder top resist) and the like for electronics. In addition, it can also be used for the production of lithographic layouts or screen layouts, etching of formed parts, electronics, especially protective coatings in microelectronics, and the manufacture of dielectric layers.

<The manufacturing method of a cured film> Next, the manufacturing method of the cured film of this invention is demonstrated. The manufacturing method of a cured film is not specifically limited if it is formed using the negative photosensitive resin composition of this 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 corresponding to the substrate.

<<< Procedure for Applying Negative Photosensitive Resin Composition to Substrate >> Examples of the application method of the negative photosensitive resin composition to the substrate include spinning, dipping, doctor blade coating, and overcast ( Suspended casting), coating, spraying, electrostatic spraying, reverse roll coating, and the like are preferably applied by spin coating, electrostatic spraying, and reverse roll coating for the reason that they can be uniformly applied to a substrate.

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 silicon substrate, a silicon nitride substrate, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such substrates. Examples of the resin substrate include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, and poly Fluorene, polyether fluorene, polyarylate, allyl diethylene glycol carbonate, polyfluorene, polyfluorene imine, polyfluorene fluorene, imine, polyether fluorene, polybenzoxazole, polyphenylene sulfide Fluorine resins such as polycyclic olefins, norbornene resins, polychlorotrifluoroethylene, liquid crystal polymers, acrylic resins, epoxy resins, silicone resins, ionic polymer resins, cyanate resins, crosslinked butadiene Substrates for synthetic resins such as acid diesters, cyclic polyolefins, aromatic ethers, maleimide, imine, olefins, cellulose, and episulfide compounds. These substrates are rarely used directly in the above-mentioned form. Usually, depending on the form of the final product, for example, a multilayer build-up structure such as a thin film transistor (TFT) device can be formed.

The amount of application of the negative photosensitive resin composition (the thickness of the layer) and the type of substrate (the carrier of the layer) depend on the field of the intended application. It is particularly advantageous that the negative-type photosensitive resin composition can be used in a wide range of layer thicknesses. The thickness of the layer is preferably in the range of 0.5 μm to 100 μm. In the method of the present invention, it is more effective when the thickness is 3 μm to 30 μm, and then 5 μm to 30 μm. After the negative photosensitive resin composition is applied to the substrate, it is preferably dried. The drying is preferably performed at 60 ° C. to 150 ° C. for 10 seconds to 2 minutes.

<<< Heating Step >> The polyimide precursor is subjected to a cyclization reaction by heating a negative photosensitive resin composition applied on a substrate to form a cured film having excellent heat resistance. The heating temperature is preferably 50 ° C to 300 ° C, and more preferably 100 ° C to 250 ° C. According to the present invention, since a large amount of isomers containing a faster cyclization rate are included, the cyclization reaction of the polyfluorene imide precursor can also be performed at a lower temperature.

From the viewpoint of reducing the internal stress of the cured film or suppressing warpage, it is preferable to adjust at least one selected from the group consisting of a heating rate, a heating time, and a cooling rate. The heating start temperature is 20 ° C to 150 ° C, 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 preferably 240 minutes or less, for example. When the heating temperature is 240 ° C to 300 ° C, the heating time is preferably 90 minutes or more. The upper limit is preferably 180 minutes or less, for example. When the heating temperature is 300 to 380, the heating time is preferably 60 minutes or more. The upper limit is preferably 120 minutes or less, for example. The cooling rate is preferably 1 ° C / min to 5 ° C / min. Heating can be performed in stages. As an example, the following steps can be mentioned: heating from 20 ° C to 150 ° C at 5 ° C / min, standing at 150 ° C for 30 minutes, and then heating from 150 ° C to 230 ° C at 5 ° C / min, and at 230 ° C Let stand for 180 minutes.

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

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

<< Exposure Step >> In the exposure step, actinic rays or radiation are irradiated in a predetermined pattern in accordance with a negative photosensitive resin composition used on a substrate. The wavelength of actinic rays or radiation varies depending on the composition of the negative photosensitive resin composition, but it is preferably 200 nm to 600 nm, and 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 (Light Emitting Diode, LED) light source, an excimer laser generating device, etc. can be used, and an i-ray (365 nm) can be preferably used , H-rays (405 nm), g-rays (436 nm) and other actinic rays with wavelengths above 300 nm and below 450 nm. In addition, the irradiated light may be adjusted by a spectroscopic filter such as a long-wavelength cut-off filter, a short-wavelength cut-off filter, or a band-pass filter, if necessary. The exposure amount is preferably 1 mJ / cm ² to 1000 mJ / cm ² , and more preferably 200 mJ / cm ² to 800 mJ / cm ² . The value of the present invention is high in that the development can be performed in a wide range in this manner with high developability. As the exposure device, various methods such as mirror projection aligner, stepper, scanner, proximity, contact, micro lens array, lens scanner, and laser exposure can be used. Exposure machine. Furthermore, when (meth) acrylates and similar olefinically unsaturated compounds are used, these photopolymerizations are known, especially in thin layers due to oxygen in the air. This effect can be mitigated, for example, by a known prior method such as temporary introduction of a film layer of polyvinyl alcohol, or front exposure or front adjustment in an inert gas.

<<< Step of Performing Development Process> In the step of performing the development process, an unexposed portion of the negative photosensitive resin composition is developed using a developing solution. As the developing solution, an aqueous alkaline developing solution, an organic solvent, or the like can be used. Examples of the alkaline compound used in the aqueous alkaline developer include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, and metasilicon. Sodium, potassium metasilicate, ammonia or amines. 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 these, a metal-free basic compound is preferred. A suitable aqueous alkaline developer is usually alkali to 0.5 N, but it may be appropriately diluted before 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 only one kind, or two or more kinds. When two or more kinds of basic compounds are used, the total thereof is preferably in the above range. As an organic solvent, the same thing as the solvent which can be used for the said negative photosensitive resin composition can be used. For example, acetic acid-n-butyl ester, γ-butyrolactone, cyclopentanone, and a mixture of these are suitably mentioned. Further, it is also preferable that after the step of performing the development treatment, a step of heating the developed negative photosensitive resin composition at a temperature of 50 ° C to 500 ° C is included. By going through such a step, there is an advantage that heat resistance or adhesion to a substrate is improved.

As a field to which the manufacturing method of the cured film of this invention can be applied, it can be used suitably for the insulation film of a semiconductor element, the interlayer insulation film for redistribution layers, etc. In particular, since it has good resolvability, it can be preferably used for an interlayer insulating film for a redistribution layer in a three-dimensional mounting element. In addition, it can also be used for photoresists (galvanic resist, etching resist, solder top resist) and the like for electronics. In addition, it can also be used for the production of lithographic layouts or screen layouts, etching of formed parts, electronics, especially protective coatings in microelectronics, and the manufacture of dielectric layers.

<Semiconductor Element> Next, an embodiment of a semiconductor element using a negative photosensitive resin composition for an interlayer insulating film for a redistribution layer will be described. The semiconductor element 100 shown in FIG. 1 is a so-called three-dimensional mounting element, and a multilayer body 101 in which a plurality of semiconductor devices (semiconductor wafers) 101 a to 101 d are stacked is arranged on a wiring substrate 120. Furthermore, in this embodiment, a case where the number of stacked layers of a semiconductor device (semiconductor wafer) is four will be described, but the number of stacked layers of a semiconductor device (semiconductor wafer) is not particularly limited. 8 layers, 16 layers, 32 layers, etc. Alternatively, it may be a single layer.

Each of the plurality of semiconductor devices 101a to 101d includes a semiconductor wafer such as a silicon 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 devices 101b to 101d include penetration electrodes 102b to 102d, and connection pads (not shown) integrally provided on the penetration electrodes are provided on both surfaces of each semiconductor device.

The laminated body 101 has a structure in which a semiconductor device 101a not having a penetrating electrode and a semiconductor device 101b to a semiconductor device 101d having a penetrating electrode 102b to a penetrating electrode 102d are connected by flip-chip bonding. That is, the electrode pads of the semiconductor device 101a without the penetration electrode and the connection pads on the semiconductor device 101a side of the semiconductor device 101b with the penetration electrode 102b adjacent thereto are connected by metal bumps 103a such as solder bumps and have penetrations. The connection pad on the other side of the semiconductor device 101b of the electrode 102b and the connection pad on the semiconductor device 101b side 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 penetrating electrode 102c and the connection pad on the semiconductor device 101c side of the semiconductor device 101d having the penetrating electrode 102d adjacent thereto are connected to a metal bump 103c such as a solder bump. To connect.

An 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 substrate using an insulating substrate such as a resin substrate, a ceramic substrate, or a glass substrate as a base material is used. Examples of the wiring substrate 120 using a resin substrate include a multilayer copper-clad laminated board (multilayer printed wiring board) and the like.

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

Hereinafter, the present invention will be described more specifically with reference to the examples. However, the present invention is not limited to the following examples as long as the present invention does not exceed the gist thereof. In addition, unless otherwise specified in advance, "%" and "part" are quality standards. NMR is an abbreviation for nuclear magnetic resonance.

(Synthesis Example 1) [Polyimide precursor derived from pyromellitic dianhydride, 4,4'-oxydiphenylamine, and benzyl alcohol (A-1: polyfluorene imide having no radical polymerizable group (Precursor)] 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C for 12 hours), suspended with 14.22 g (131.58 mmol) of benzyl alcohol in 50 ml of N -In methylpyrrolidone, it is dried using 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, and while maintaining the temperature at -10 ° C ± 4 ° C, 16.12 g (135.5 mmol) of SOCl _{2 was} added over 10 minutes. During the addition of SOCl ₂ , the viscosity increased. After dilution with 50 ml of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, a solution prepared by dissolving 11.08 g (58.7 mmol) of 4,4'-oxydiphenylamine in 100 ml of N-methylpyrrolidone at 20 ° C to 23 ° C for 20 minutes. Add dropwise to the reaction mixture. Then, the reaction mixture was stirred at room temperature for 1 night. Then, the polyamidine precursor was precipitated in 5 liters of water, and the water-polyimide precursor mixture was stirred at 5000 rpm for 15 minutes. The polyimide precursor was filtered, put into 4 liters of water again, stirred for 30 minutes, and filtered again. Then, the obtained polyimide precursor was dried at 45 ° C. for 3 days under a reduced pressure to obtain a polyimide precursor (A-1) having a structure represented by the following formula. [Chemical 41]

(Synthesis Example 2) [Polyimide precursor derived from pyromellitic dianhydride, 4,4'-oxydiphenylamine, and 2-hydroxyethyl methacrylate (A-2: radical polymerizable Polyimide 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 diglyme were mixed and stirred at 60 ° C for 18 hours to produce homobenzene The diester of tetracarboxylic acid and 2-hydroxyethyl methacrylate. Next, the obtained diester was chlorinated by SOCl ₂ and then converted to a polyfluorene imine precursor by 4,4'-oxydiphenylamine by the same method as in Synthesis Example 1. In the same manner, a polyfluorene imide precursor (A-2) containing a structure represented by the following formula was obtained. [Chemical 42]

(Synthesis Example 3) [Polyimide precursor derived from 4,4'-oxydiphthalic anhydride, 4,4'-oxydiphenylamine, and 2-hydroxyethyl methacrylate (A- 3: Synthesis of a polyfluorene imide 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 mix at 60 After stirring at a temperature of 18 ° C. for 18 hours, a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate was produced. Next, the obtained diester was chlorinated by SOCl ₂ and then converted to a polyfluorene imine precursor by 4,4'-oxydiphenylamine by the same method as in Synthesis Example 1. In the same manner, a polyfluorene imide precursor (A-3) containing a structure represented by the following formula was obtained. [Chemical 43]

(Synthesis Example 4) [Polyimide precursor derived from 4,4'-oxydiphthalic anhydride and 4,4'-oxydiphenylamine (A-4: polyfluorene imide 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- Pyrrolidone (N-methyl-2-pyrrolidone, NMP) was further added with 21.43 g (270.9 mmol) of pyridine, and the reaction solution 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 the reaction mixture was stirred at room temperature for 1 night. Then, it was poured into 5 liters of water to precipitate the polyimide precursor, and the water-polyimide precursor mixture was stirred at 5000 rpm for 15 minutes. The polyfluorene imide precursor was filtered, put into 4 liters of water again, stirred for 30 minutes, and filtered again. Then, the obtained polyfluorene imide precursor was dried at 45 ° C. for 3 days under reduced pressure to obtain a polyfluorene imide precursor (A-4) containing a structure represented by the following formula. [Chemical 44]

(Synthesis Example 5) [Synthesis of Polymer (RA-1) for Comparative Example] 27.0 g (153.2 mmol) of benzyl methacrylate and 20 g (157.3 mmol) of N-isopropylmethyl Methacrylamide, 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) 3.55 g (15.4 mmol) and 300 g of 3-methoxy-2-propanol. Under a nitrogen atmosphere, the mixed liquid was added dropwise to 300 g of 3-methoxy-2-propanol heated to 75 ° C. over 2 hours. After completion of the dropwise addition, the mixture was further stirred at 75 ° C. for 2 hours under a nitrogen atmosphere. After completion of the reaction, the polymer was poured into 5 liters of water to precipitate a polymer, and the mixture was stirred at 5000 rpm for 15 minutes. The acrylic resin was collected by filtration, poured into 4 liters of water and stirred for 30 minutes, and then 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. [Chemical 45]

<Examples and Comparative Examples> The components described below were mixed to make a uniform solution, and a coating solution for a photosensitive resin composition was prepared. <<< Composition of Photosensitive Resin Composition >> Polyimide precursor: part by mass shown in Table 6 radical polymerization initiator: part by mass described in Table 6 First polymerization inhibitor: part by mass described in Table 6 2 Polymerization inhibitor: Mass parts of the radical polymerizable compound described in Table 6: Mass parts of the hot alkali generator described in Table 6: Mass parts (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) Polyimide precursor or resin for comparison 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 (manufactured by BASF)

(C) First polymerization inhibitor C-1: 4-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) C-2: 2,6-di-third-butyl-4-methylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) C-3: Pentaerythritol tetrakis [3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate] (manufactured by BASF, Irganox 1010) C- 4: Thiodiethyl bis [3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate] (manufactured by BASF, Irganox 1035 ) C-5: Octadecyl-3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate (manufactured by BASF, Irganox 1076) C -6: N, N'-hexane-1,6-diylbis [3- (3,5-di-third-butyl-4-hydroxyphenyl) propanamide] (manufactured by BASF) , Irganox 1098) C-7: 3,3 ', 3' ', 5,5', 5 ''-hexa-third-butyl-a, a ', a' '-(all Xylene-2,4,6-triyl) tri-p-cresol (manufactured by BASF, Irganox 1330) C-8: ethylidenebis (oxyethylidene) bis [ 3- (5-Third-butyl-4-hydroxy-m-tolyl) propionate] (BASF) Manufactured, Irganox 245) C-9: Hexamethylenebis [3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate] (BASF) Manufactured by the company, Irganox 259) C-10: 1,3,5-tris (3,5-di-third-butyl-4-hydroxybenzyl) -1,3,5-triazine -2,4,6 (1H, 3H, 5H) -trione (manufactured by BASF, Irganox 3114) C-11: catechol (manufactured by Tokyo Chemical Industry) C-12: Tertiary butyl-catechol (manufactured by Tokyo Chemical Industry)

(D) Second polymerization inhibitor D-1: 2,4,6-tri-third-butyl-nitrosobenzene (manufactured by Tokyo Chemical Industry) D-2: phenyl-third-butyl nitrone (Tokyo (Manufactured by Chemical Industry) D-3: 3,3,5,5-tetramethyl-1-pyrroline-N-oxide (manufactured by Tokyo Chemical Industry) D-4: p-benzoquinone (manufactured by Tokyo Chemical Industry) D- 5: p-toluone (manufactured by Tokyo Chemical Industry) D-6: 2-tert-butyl-p-benzoquinone (manufactured by Tokyo Chemical Industry) D-7: 2,2,6,6-tetramethylpiperidine 1- Oxygen (manufactured by Tokyo Chemical Industry) D-8: 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (manufactured by Tokyo Chemical Industry) D-9: 4-methacrylic acid -2,2,6,6-tetramethylpiperidine 1-oxyl (manufactured by Tokyo Chemical Industry) D-10: N-nitroso diphenylamine (manufactured by Tokyo Chemical Industry) D-11: phenanthrene Azine (manufactured by Tokyo Chemical Industry)

(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 (NK ESTER) 4G (manufactured by Shin Nakamura Chemical Industry Co., Ltd .; difunctional methacrylate; the following structure) [Chem. 47] E-3: NK Ester (NK ESTER) A-9300 (manufactured by Shin Nakamura Chemical Industry Co., Ltd .; trifunctional acrylate; the following structure) [Chem. 48]

(F) Hot alkali generator [Chem. 49] F-1: F-2:

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

Each negative photosensitive resin composition was subjected to pressure filtration by passing through a filter having a pore width of 0.8 μm, and then applied by spin coating on a silicon wafer. The silicon wafer to which the negative photosensitive resin composition was applied was dried on a hot plate at 100 ° C. for 5 minutes, and a uniform polymer layer having the thickness described in Table 6 was formed on the silicon wafer.

<Evaluation> [Exposure latitude] A stepper (Nikon NSR2005i9C) was used to expose the photosensitive resin composition layer on the silicon wafer. Exposure was 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 mask with a line and space in units of 1 μm from 5 μm to 25 μm.

The exposed photosensitive resin composition layer was developed with cyclopentanone for 60 seconds. The following criteria are used to evaluate line widths that can have good edge sharpness. The smaller the line width of the photosensitive resin composition layer, the larger the difference between the solubility of the light-irradiated portion and the non-light-irradiated portion in the developing solution becomes, and a better result is obtained. In addition, the smaller the change in line width with respect to the change in exposure energy, the wider the exposure latitude and the better the 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: 8 μm or more and 10 μm or less C: 10 μm or more and 15 μm or less D: 15 μm or more and 20 μm or less E: 20 μm or more

[Heat resistance] After exposing the exposed photosensitive resin composition layer at 300 ° C for 3 hours under a nitrogen environment, the exposed photosensitive resin composition layer was peeled off, and the temperature was increased at a rate of 10 ° C / min in nitrogen. The thermal mass analysis was performed under the conditions described above, 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 below 300 ° C

[TABLE 7]

The numerical values of the exposure latitude in Table 7 indicate the exposure energy (unit: mJ / cm ² ). In Comparative Example 4, since all components were dissolved in the development treatment with cyclopentanone, it was impossible to measure.

<Example 100> The negative-type 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 having a thin copper layer (3500 rpm). , 30 seconds) to apply. After the negative photosensitive resin composition applied to the resin substrate was dried at 100 ° C. for 5 minutes, it was exposed using an aligner (Karl-Suss MA150). The exposure was performed using a high-pressure mercury lamp, and the exposure energy at a wavelength of 365 nm was measured. After exposure, the image was developed with cyclopentanone for 75 seconds. Then, it heated at 180 degreeC for 20 minutes. In this manner, an interlayer insulating film for a redistribution layer is formed. This interlayer insulating film for a redistribution layer has excellent insulation properties. In addition, a semiconductor element was manufactured using the interlayer insulating film for a redistribution layer, and as a result, it was confirmed that the semiconductor element was operated without problems.

100‧‧‧Semiconductor element

101‧‧‧Laminated body

101a ～ 101d‧‧‧Semiconductor device (semiconductor wafer)

102b ～ 102d‧‧‧through electrode

103a ～ 103e‧‧‧ metal bump

105‧‧‧ redistribution layer

110, 110a, 110b‧‧‧ Underfill

115‧‧‧ Insulation

120‧‧‧ wiring board

120a‧‧‧ surface electrode

FIG. 1 is a schematic diagram showing a configuration of an embodiment of a semiconductor element.

Claims (19)

A negative-type photosensitive resin composition comprising: a polyimide precursor; a radical polymerization initiator; a first polymerization inhibitor selected from at least one compound having an aromatic hydroxyl group; and a second polymerization The inhibitor is at least one selected from the group consisting of an N-oxide compound, a quinone compound, and an N-oxy compound. The negative photosensitive resin composition according to item 1 of the scope of application for a patent, wherein the polyfluorene imide precursor includes a repeating unit represented by the following general formula (1); In the general 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 each independently represent A hydrogen atom or a monovalent organic group. The negative photosensitive resin composition according to item 2 of the scope of patent application, wherein in the general formula (1), at least one of R ¹³ and R ¹⁴ includes a radical polymerizable group. The negative-type photosensitive resin composition according to item 1 or item 2 of the scope of patent application, further comprising a radical polymerizable compound. The negative-type photosensitive resin composition according to item 4 of the scope of patent application, wherein the radical polymerizable compound has two or more radical polymerizable groups. The negative-type photosensitive resin composition according to item 1 or item 2 of the scope of patent application, wherein the second polymerization inhibitor is selected from a quinone compound and an N-oxy compound. The negative photosensitive resin composition according to item 1 or item 2 of the scope of application for a patent, wherein a mass ratio of the first polymerization inhibitor to the second polymerization inhibitor is 10:90 to 90:10. The negative photosensitive resin composition according to item 1 or item 2 of the scope of the patent application, wherein the mass ratio of the first polymerization inhibitor to the radical polymerization initiator is 1:99 to 10:90 . The negative-type photosensitive resin composition according to item 1 or 2 of the scope of application for a patent, wherein in the general formula (1), R ¹² is a tetravalent group containing an aromatic ring. The negative photosensitive resin composition according to item 1 or 2 of the scope of patent application, further comprising a thermal alkali generator. The negative photosensitive resin composition according to item 10 of the scope of application for a patent, wherein the thermal alkali generator has an ammonium cation represented by the following general formula (Y); In the general formula (Y), Ar ¹⁰ represents an aromatic group, R ¹¹ to R ¹⁵ each independently represent a hydrogen atom or a hydrocarbon group, R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring, and n represents an integer of 1 or more. The negative-type photosensitive resin composition according to claim 1 or claim 2, which is used for an interlayer insulating film for a redistribution layer. A cured film obtained by curing the negative-type photosensitive resin composition according to any one of claims 1 to 12 of the scope of patent application. The cured film according to item 13 of the scope of patent application, which is an interlayer insulating film for a redistribution layer. A method for producing a cured film, comprising using the negative photosensitive resin composition according to any one of claims 1 to 12 of a patent application scope. The method for manufacturing a cured film according to item 15 of the scope of patent application, comprising: a step of applying the negative photosensitive resin composition to a substrate; corresponding to the negative photosensitive used on the substrate A step of exposing the resin composition to actinic rays or radiation to perform exposure; and a step of subjecting the exposed photosensitive resin composition to a development process. The method for manufacturing a cured film according to item 16 of the scope of patent application, which comprises performing the developing treatment step, and comprises developing the negative photosensitive resin composition developed at a temperature of 50 ° C to 500 ° C. Perform the heating step. The method for manufacturing a cured film according to item 15 or 16 of the scope of application for a patent, wherein the film thickness of the cured film is 3 μm to 30 μm. A semiconductor device having a cured film as described in claim 13 or 14 of the scope of patent application.