WO2017002859A1 - Negative photosensitive resin composition, cured film, cured film production method and semiconductor device - Google Patents

Abstract

A negative photosensitive resin composition with a wide exposure latitude, a cured film, a cured film production method and a semiconductor device are provided. This negative photosensitive resin composition includes: a polyimide precursor; a radical polymerization initiator; at least one type of first polymerization inhibitor selected from compounds having an aromatic hydroxyl group; and at least one type of second polymerization inhibitor selected from a nitroso compound, an N-oxide compound, a quinone compound, an N-oxyl compound and a phenothiazine compound.

Description

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

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

Thermosetting resins that are cured by cyclization such as polyimide are excellent in heat resistance and insulation, and are therefore used for insulating layers of semiconductor devices.

（式（１）中、Ｘ_１は、４価の有機基であり、Ｙ_１は、２価の有機基であり、ｎは、２～１５０の整数であり、Ｒ_１及びＲ_２は、それぞれ独立に、水素原子、下記一般式（２）：

（式中、Ｒ_３、Ｒ_４及びＲ_５は、それぞれ独立に、水素原子又は炭素数１～３の有機基であり、そしてｍは、２～１０の整数である。）で表される１価の有機基、又は炭素数１～４の飽和脂肪族基である。但し、Ｒ_1１及びＲ_2２の両者が同時に水素原子であることはない。）で表される構造を有するポリイミド前駆体：１００質量部、
（Ｂ）光重合開始剤：１～２０質量部、並びに
（Ｃ）ヒドロキシル基、エーテル基及びエステル基からなる群より選ばれる官能基を１つ以上有する炭素数２～３０のモノカルボン酸化合物：０．０１～１０質量部、
を含有する、ネガ型感光性樹脂組成物が開示されている。 Here, since polyimide has low solubility in a solvent, it is used in the state of a precursor (heterocycle-containing polymer precursor) before the cyclization reaction, applied to a substrate, etc., and then heated to form a heterocycle-containing polymer. It has been practiced to form a cured film by cyclizing the precursor.
As a photosensitive resin composition using such a polyimide precursor, Patent Document 1 discloses (A) the following general formula (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 respectively Independently, a hydrogen atom, the following general formula (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). A valent organic group or a saturated aliphatic group having 1 to 4 carbon atoms. However, both R ₁₁ and R ₂₂ are not simultaneously hydrogen atoms. ) Polyimide precursor having a structure represented by: 100 parts by mass,
(B) Photopolymerization initiator: 1 to 20 parts by mass, and (C) a monocarboxylic acid compound having 2 to 30 carbon atoms having at least one functional group selected from the group consisting of a hydroxyl group, an ether group and an ester group: 0.01 to 10 parts by mass,
A negative-type photosensitive resin composition containing the above is disclosed.

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

JP 2011-191749 A International Publication WO2010 / 008514

Here, there is a demand for a negative photosensitive resin composition having a wide appropriate exposure range of the resolution of the negative photosensitive resin composition, that is, a wide exposure latitude, such as when used for an interlayer insulating film for a semiconductor rewiring layer. It has been. However, the negative photosensitive resin compositions described in Patent Document 1 and Patent Document 2 each have a narrow exposure latitude. Here, Patent Document 2 describes high image resolution, but neither describes nor suggests that an image having a good edge sharpness can be obtained with a wide range of exposure energy.
The present invention has been made to solve the above-described problems, and has an object to provide a negative photosensitive resin composition having a wide exposure latitude, a cured film, a method for producing the cured film, and a semiconductor device.

一般式（１）中、Ａ^１およびＡ^２は、それぞれ独立に、酸素原子または－ＮＨ－を表し、Ｒ^１１は、２価の有機基を表し、Ｒ^１２は、４価の有機基を表し、Ｒ^１３およびＲ^１４は、それぞれ独立に、水素原子または１価の有機基を表す。
＜３＞一般式（１）中、Ｒ^１３およびＲ^１４の少なくとも一方が、ラジカル重合性基を含む、＜２＞に記載のネガ型感光性樹脂組成物。
＜４＞さらに、ラジカル重合性化合物を含む、＜１＞～＜３＞のいずれかに記載のネガ型感光性樹脂組成物。
＜５＞ラジカル重合性化合物が、２つ以上のラジカル重合性基を有する、＜４＞に記載のネガ型感光性樹脂組成物。
＜６＞第２の重合禁止剤が、キノン化合物およびＮ－オキシル化合物から選択される、＜１＞～＜５＞のいずれかに記載のネガ型感光性樹脂組成物。
＜７＞第１の重合禁止剤と、第２の重合禁止剤との質量比率が、１０：９０～９０：１０である、＜１＞～＜６＞のいずれかに記載のネガ型感光性樹脂組成物。
＜８＞第１の重合禁止剤と、ラジカル重合開始剤との質量比率が、１：９９～１０：９０である、＜１＞～＜７＞のいずれかに記載のネガ型感光性樹脂組成物。
＜９＞一般式（１）中、Ｒ^１２が、芳香環を含む４価の基である、＜１＞～＜８＞のいずれかに記載のネガ型感光性樹脂組成物。
＜１０＞さらに、熱塩基発生剤を含む、＜１＞～＜９＞のいずれかに記載のネガ型感光性樹脂組成物。
＜１１＞熱塩基発生剤が、下記一般式（Ｙ）で表されるアンモニウムカチオンを有する、＜１０＞に記載のネガ型感光性樹脂組成物；

一般式（Ｙ）中、Ａｒ^１０は、芳香族基を表し、Ｒ^１１～Ｒ^１５は、それぞれ独立に、水素原子または炭化水素基を表し、Ｒ^１４とＲ^１５は互いに結合して環を形成していてもよく、ｎは、１以上の整数を表す。
＜１２＞再配線層用層間絶縁膜用である、＜１＞～＜１１＞のいずれかに記載のネガ型感光性樹脂組成物。
＜１３＞＜１＞～＜１２＞のいずれかに記載のネガ型感光性樹脂組成物を硬化してなる、硬化膜。
＜１４＞再配線層用層間絶縁膜である、＜１３＞に記載の硬化膜。
＜１５＞＜１＞～＜１２＞のいずれかに記載のネガ型感光性樹脂組成物を用いることを含む、硬化膜の製造方法。
＜１６＞ネガ型感光性樹脂組成物を基板に適用する工程と、
基板に適用されたネガ型感光性樹脂組成物に対して、活性光線または放射線を照射して露光する工程と、
露光されたネガ型感光性樹脂組成物に対して、現像処理を行う工程とを有する、＜１５＞に記載の硬化膜の製造方法。
＜１７＞現像処理を行う工程後に、現像されたネガ型感光性樹脂組成物を５０～５００℃の温度で加熱する工程を含む、＜１６＞に記載の硬化膜の製造方法。
＜１８＞硬化膜の膜厚が、３～３０μｍである、＜１５＞～＜１７＞のいずれかに記載の硬化膜の製造方法。
＜１９＞＜１３＞または＜１４＞に記載の硬化膜、または、＜１５＞～＜１８＞のいずれかに記載の方法で製造された硬化膜を有する、半導体デバイス。 As a result of investigations by the inventors under the above-mentioned problems, the exposure latitude of the negative photosensitive resin composition can be broadened by adopting a polyimide precursor having a predetermined structure in the negative photosensitive resin composition. It has been found that it is possible to solve this problem. Specifically, the above problem has been solved by <1> below, preferably <2> to <19>.
<1> polyimide precursor; radical polymerization initiator; at least one first polymerization inhibitor selected from compounds having an aromatic hydroxyl group; and nitroso compounds, N-oxide compounds, quinone compounds, N-oxyls A negative photosensitive resin composition comprising at least one second polymerization inhibitor selected from a compound and a phenothiazine compound.
<2> The negative photosensitive resin composition according to <1>, wherein the polyimide precursor includes a repeating unit represented by the following general formula (1);
General formula (1)

In general formula (1), A ¹ and A ² each independently represent an oxygen atom or —NH—, R ¹¹ represents a divalent organic group, and R ¹² represents a tetravalent organic group. , R ¹³ and R ¹⁴ each independently represents a hydrogen atom or a monovalent organic group.
<3> The negative photosensitive resin composition according to <2>, wherein in General Formula (1), at least one of R ¹³ and R ¹⁴ 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 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-oxyl compound.
<7> The negative photosensitivity 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 Resin composition.
<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. object.
<9> The negative photosensitive resin composition according to any one of <1> to <8>, wherein R ¹² in formula (1) 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 thermal base generator.
<11> The negative photosensitive resin composition according to <10>, wherein the thermal base generator has an ammonium cation represented by the following general formula (Y);

In general formula (Y), Ar ¹⁰ represents an aromatic group, R ¹¹ to R ¹⁵ each independently represents a hydrogen atom or a hydrocarbon group, and R ¹⁴ and R ¹⁵ are 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 rewiring 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 rewiring layer.
<15> A method for producing a cured film, comprising using the negative photosensitive resin composition according to any one of <1> to <12>.
<16> applying the negative photosensitive resin composition to the substrate;
A step of exposing the negative photosensitive resin composition applied to the substrate by irradiation with actinic rays or radiation, and
The manufacturing method of the cured film as described in <15> which has a process of developing with respect to the exposed negative photosensitive resin composition.
<17> The method for producing a cured film according to <16>, comprising a step of heating the developed negative photosensitive resin composition at a temperature of 50 to 500 ° C. after the step of performing the 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 to 30 μm.
<19> A semiconductor device having the cured film according to <13> or <14>, or the cured film manufactured by the method according to any one of <15> to <18>.

The present invention makes it possible to provide a negative photosensitive resin composition having a wide exposure latitude, a cured film, a method for producing a cured film, and a semiconductor device.

It is the schematic which shows the structure of one Embodiment of a semiconductor device.

The description of the components in the present invention described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, “active light” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation. In this specification, “exposure” means not only exposure using far ultraviolet rays, X-rays, EUV light typified by mercury lamps and excimer lasers, but also particle beams such as electron beams and ion beams, unless otherwise specified. Include drawing in the exposure.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present specification, “(meth) acrylate” represents both and / or “acrylate” and “methacrylate”, and “(meth) allyl” means both “allyl” and “methallyl”, or “(Meth) acryl” represents either “acryl” and “methacryl” or any one, and “(meth) acryloyl” represents both “acryloyl” and “methacryloyl”, or Represents either.
In this specification, the term “process” not only means an independent process, but also if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes, include.
In this specification, solid content concentration is the mass percentage of the mass of the other component except a solvent with respect to the gross mass of a composition. Moreover, solid content concentration says the density | concentration in 25 degreeC unless there is particular mention.
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene-converted values in gel permeation chromatography (GPC) measurement unless otherwise specified. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and guard columns HZ-L, TSKgel Super HZM-M, TSKgel. It can be determined by using Super HZ4000, TSKgel Super HZ3000, TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise stated, the eluent was measured using THF (tetrahydrofuran). In addition, unless otherwise stated, an ultraviolet (UV) 254 nm detector is used for detection.

Negative photosensitive resin composition The negative photosensitive resin composition of the present invention comprises at least one first polymerization inhibitor selected from a polyimide precursor; a radical polymerization initiator; and a compound having an aromatic hydroxyl group; And at least one second polymerization inhibitor selected from nitroso compounds, N-oxide compounds, quinone compounds, N-oxyl compounds and phenothiazine compounds. By adopting such a configuration, a negative photosensitive resin composition having a wide exposure latitude can be obtained.
The negative photosensitive resin composition containing the polyimide precursor is cured by exposure, but by blending two kinds of polymerization inhibitors, mainly the first polymerization inhibitor works on the side close to the surface layer. The second polymerization inhibitor works mainly on the side far from the surface layer of the film, and as a result, the polymerization inhibition effect works almost uniformly on the entire negative photosensitive resin composition layer, and the exposure latitude is widened. Will be possible. This is particularly advantageous when the difference in how light strikes is large and the film is thick.
In addition, the resin used in the examples of Patent Document 2 is an acrylic resin and has a problem from the viewpoint of heat resistance. However, in the present invention, a polyimide precursor is used, so that the resin has excellent heat resistance. It can be.

一般式（１）中、Ａ^１およびＡ^２は、それぞれ独立に、酸素原子または－ＮＨ－を表し、Ｒ^１１は、２価の有機基を表し、Ｒ^１２は、４価の有機基を表し、Ｒ^１３およびＲ^１４は、それぞれ独立に、水素原子または１価の有機基を表す。 <Polyimide precursor>
The negative photosensitive resin composition of the present invention contains a polyimide precursor. Only one type of polyimide precursor may be used, or two or more types may be used.
It is preferable that a polyimide precursor is a polyimide precursor containing the repeating unit represented by General formula (1).
General formula (1)

In general formula (1), A ¹ and A ² each independently represent an oxygen atom or —NH—, R ¹¹ represents a divalent organic group, and R ¹² represents a tetravalent organic group. , R ¹³ and R ¹⁴ each independently represents a hydrogen atom or a monovalent organic group.

A ¹ and A ² each independently represents an oxygen atom or —NH—, 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 a carbon number of 6 A group consisting of a cyclic aliphatic group having 20 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a combination thereof is preferable, and a group consisting of an aryl group having 6 to 60 carbon atoms is more preferable. The following are mentioned as an example of an aryl group.

　式中、Ａは、単結合、または、フッ素原子で置換されていてもよい炭素数１～１０の炭化水素基、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ－、－Ｓ（＝Ｏ）_２－および－ＮＨＣＯ－、並びにこれらの組み合わせから選択される基であることが好ましく、単結合、フッ素原子で置換されていてもよい炭素数１～３のアルキレン基、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ－、－ＳＯ_２－から選択される基であることがより好ましく、－ＣＨ_２－、－Ｏ－、－Ｓ－、－ＳＯ_２－、－Ｃ（ＣＦ_３）_２－、－Ｃ（ＣＨ_３）_２－から選択される２価の基であることがさらに好ましい。

In the formula, A is a single bond or a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —C (═O) —, —S—, —S (= O) ₂ — and —NHCO—, and a group selected from these combinations are preferable. A single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, —O—, — It is more preferably a group selected from C (═O) —, —S—, —SO ₂ —, —CH ₂ —, —O—, —S—, —SO ₂ —, —C (CF _{3 ) 2 -, - C (CH} 3) 2 - and more preferably a divalent group selected from.

Specifically, examples of R ¹¹ include diamine residues remaining after removal of the amino group of the following diamine.
1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1, 2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4-aminocyclohexyl) methane, bis- (3 -Aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; m- and p-phenylenediamine, diaminotoluene, 4,4'- and 3,3'-diaminobiphenyl, 4,4'- and 3,3'-diaminodiphenyl ether, 4,4'- and 3,3'-diaminodiphenylmethane, 4, '-And 3,3'-diaminodiphenyl sulfone, 4,4'- and 3,3'-diaminodiphenyl sulfide, 4,4'- 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-aminophenyl) 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) hexafluoropropane, bis ( 3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 4,4′-diaminoparaterphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, bis [ 4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (2-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) ) Benzene, 9,10-bis (4-aminophenyl) anthracene, 3,3′-dimethyl-4,4′-diaminodiphenylsulfone, 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′-diaminodiphenylmethane, 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′-diaminodiphenylsulfone, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, 2,4- 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) tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diamino Pyridine, 1,2-bis (4-aminophenyl) ethane, diaminobenzanilide, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis (4-aminophenyl) hexafluoro Propane, 1,4-bis (4-aminophenyl) octafluorobutane, 1,5-bis (4-aminophenyl) Nyl) decafluoropentane, 1,7-bis (4-aminophenyl) tetradecafluoroheptane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (2-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] hexafluoropropane, 2,2-bis [4- (4-amino) Phenoxy) -3,5-bis (trifluoromethyl) phenyl] hexafluoropropane, p-bis (4-amino-2-trifluoromethylphenoxy) benzene, 4,4'-bis (4-amino-2-tri Fluoromethylphenoxy) biphenyl, 4,4′-bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4,4 '-Bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4,4'-bis (3-amino-5-trifluoromethylphenoxy) diphenylsulfone, 2,2-bis [4- (4- Amino-3-trifluoromethylphenoxy) phenyl] hexafluoropropane, 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′-hexafluorotriden and 4,4 ′ ″-diaminoqua At least one diamine selected from terphenyl;

Examples of R ¹¹ include diamine residues remaining after removal of the amino groups of diamines (DA-1) to (DA-18) shown below.

An example of R ¹¹ is a diamine residue remaining after removal of an amino group of a diamine having two or more alkylene glycol units in the main chain. Preferred is a diamine residue containing two or more ethylene glycol chains or propylene glycol chains in one molecule, and more preferred is a diamine residue containing no aromatic ring. Examples include Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 ( Trade names, manufactured by HUNTSMAN Co., Ltd.), 1- (2- (2- (2-aminopropoxy) ethoxy) propoxy) propan-2-amine, 1- (1- (1- (2-aminopropoxy) propane -2-yl) oxy) propan-2-amine, but is not limited thereto. The structures of Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, and EDR-176 are shown below.

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

In general formula (1), R ¹² represents a tetravalent organic group, preferably a tetravalent group containing an aromatic ring, represented by the following general formula (1-1) or general formula (1-2). More preferred are the groups

　一般式（１－１）中、Ｒ^１１２は、単結合、または、フッ素原子で置換されていてもよい炭素数１～１０の炭化水素基、－Ｏ－、－ＣＯ－、－Ｓ－、－ＳＯ₂－および－ＮＨＣＯ－、並びにこれらの組み合わせから選択される基であることが好ましく、単結合、または、フッ素原子で置換されていてもよい炭素数１～３のアルキレン基、－Ｏ－、－ＣＯ－、－Ｓ－および－ＳＯ_２－から選択される２価の基であることがより好ましく、－ＣＨ_２－、－Ｃ（ＣＦ_３）_２－、－Ｃ（ＣＨ_３）_２－、－Ｏ－、－ＣＯ－、－Ｓ－および－ＳＯ_２－からなる群から選択される２価の基がさらに好ましい。 General formula (1-1)

In the general formula (1-1), R ¹¹² represents a single bond or a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—, — It is preferably a group selected from SO ₂ — and —NHCO—, and combinations thereof. A single bond or an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, —O—, More preferably, it is a divalent group selected from —CO—, —S— and —SO ₂ —, —CH ₂ —, —C (CF ₃ ) ₂ —, —C (CH ₃ ) ₂ —, More preferred is a divalent group selected from the group consisting of —O—, —CO—, —S— and —SO ₂ —.

Formula (1-2)

Examples of R ¹² include a tetracarboxylic acid residue remaining after removal of the anhydride group from tetracarboxylic dianhydride.
Specific examples include tetracarboxylic acid residues remaining after the removal of anhydride groups from the following tetracarboxylic dianhydrides.
Pyromellitic dianhydride (PMDA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl sulfide tetracarboxylic dianhydride, 3,3 ′ , 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-diphenylmethane tetracarboxylic dianhydride 2,2 ′, 3,3′-diphenylmethanetetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenonetetracarboxylic Acid dianhydride, 4,4′-oxydiphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic dianhydride, 2, 2-bis (3,4-dicar Xylphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3 -Diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalene tetracarboxylic dianhydride, 2,2 ', 3,3'-diphenyltetracarboxylic Acid dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid Anhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyl) Phenyl) ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and at least one selected from alkyls having 1 to 6 carbons and alkoxy derivatives having 1 to 6 carbons Tetracarboxylic dianhydride.

Further, examples of R ¹² include tetracarboxylic acid residues remaining after removal of anhydride groups from tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below.

From the viewpoint of solubility in an alkali developer, R ¹² preferably has an OH group. More specifically, examples of R ¹² include tetracarboxylic acid residues remaining after removal of 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 that improves the solubility in a developer is preferably used.

From the viewpoint of solubility in an aqueous developer, R ¹³ and R ¹⁴ are a hydrogen atom or a monovalent organic group, and the monovalent organic group is a 1, 2 bonded to a carbon atom of an aryl group. Alternatively, an aryl group and an aralkyl group having three, preferably one, acid groups are exemplified. 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 specifically, a phenyl group having an acidic group and a benzyl group having an acidic group can be mentioned. The acidic group is preferably an OH group.
R ¹³ and R ¹⁴ are preferably a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl from the viewpoint of solubility in an aqueous developer.

From the viewpoint of solubility in an organic solvent, R ¹³ and R ¹⁴ are preferably monovalent organic groups. The monovalent organic group preferably includes an alkyl group, a cycloalkyl group, and an aryl group, and more preferably an alkyl group substituted with an aryl group.
The alkyl group preferably has 1 to 30 carbon atoms. The alkyl group may be linear, branched or cyclic. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, and an octadecyl group. Isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, and 2-ethylhexyl group. The cyclic alkyl group (cycloalkyl group) may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. Examples of the monocyclic cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic cycloalkyl group include an adamantyl group, a norbornyl group, a bornyl group, a camphenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group, and a pinenyl group. Can be mentioned. Among these, a cyclohexyl group is most preferable from the viewpoint of achieving high sensitivity. Moreover, as an alkyl group substituted by the aryl group, the linear alkyl group substituted by the aryl group mentioned later is preferable.
Specific examples of the aryl group include substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indecene ring, perylene ring, pentacene ring, acenaphthecene ring, phenanthrene ring, anthracene. Ring, naphthacene ring, chrysene 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, indolizine ring , Indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine , A phenanthroline ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxathiin ring, a phenothiazine ring or a phenazine ring. A benzene ring is most preferred.

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 blocked isocyanate group, an alkoxymethyl group, a methylol group, and an amino group.
In the present invention, a preferred embodiment of R ¹³ and R ^14, is exemplified embodiments comprising a radical polymerizable group, a group having an ethylenically unsaturated bond is more preferable. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, a group represented by the following formula (III), and the like.

In the formula (III), R ²⁰⁰ represents hydrogen or methyl, and methyl is more preferable.
In the formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, —CH ₂ CH (OH) CH ₂ — or a polyoxyalkylene group having 4 to 30 carbon atoms.
Examples of suitable R ²⁰¹ are ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene, octamethylene, dodecamethylene, —CH ₂ CH (OH) CH ₂ —, And ethylene, propylene, trimethylene, and —CH ₂ CH (OH) CH ₂ — are more preferable.
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 molar ratio of polymerizable group: no polymerizable group is 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, an ethylenically unsaturated bond is formed. The counter amine salt may be formed with the tertiary amine compound. Examples of such tertiary amine compounds having an ethylenically unsaturated bond include N, N-dimethylaminopropyl methacrylate.

In the case of alkali development, the polyimide precursor preferably has a fluorine atom in the structural unit from the viewpoint of improving resolution. The fluorine atom imparts water repellency to the surface of the film during alkali development, and soaking in from the surface can be suppressed. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less from the viewpoint of solubility in an alkaline aqueous solution.

Also, for the purpose of improving the adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane.

In addition, in order to improve the storage stability of the negative photosensitive resin composition, the polyimide precursor is end-capped with a main chain end such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound, etc. It is preferable to seal with an agent. Of these, it is more preferable to use a monoamine. Preferred examples of the monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene and 1-hydroxy-6-aminonaphthalene. 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy- 7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3- Minobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino- Examples include 4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

The polyimide precursor used by this invention may consist of the repeating unit represented by General formula (1), and the other repeating unit which is another imide precursor.
When other repeating units are included, the proportion of the other repeating units in the polyimide precursor is preferably 1 to 60 mol%, and more preferably 5 to 50 mol%.

The negative photosensitive resin composition of the present invention can also be configured to contain substantially no other polyimide precursor other than the polyimide precursor containing the repeating unit represented by the general formula (1). “Substantially free” means, for example, 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. Say.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 20000 to 28000, more preferably 22000 to 27000, and further preferably 23000 to 25000.
The degree of dispersion (Mw / Mn) of the polyimide precursor is not particularly defined, but is preferably 1.0 or more, more preferably 2.5 or more, and further preferably 2.8 or more. preferable. The upper limit of the degree of dispersion of the polyimide precursor is not particularly defined, but is preferably 4.5 or less, for example, or 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, more preferably 50 to 99% by mass, based on the total solid content of the negative photosensitive resin composition. 60 to 99% by mass is more preferable, and 70 to 99% by mass is particularly preferable.

<Other resin components>
The negative photosensitive resin composition of the present invention may contain other resin components without departing from the spirit of the present invention. Examples of 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. “Substantially free” means, for example, that the content of the resin other than the 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. .

<Radical polymerization initiator>
The negative photosensitive resin composition of the present invention contains a radical polymerization initiator. Negative development can be performed by initiating polymerization of a radical polymerizable group that the polyimide precursor may have or a radical polymerizable compound described later. The radical polymerization initiator may be a radical photopolymerization initiator or a thermal radical polymerization initiator, but is preferably a radical photopolymerization initiator. More specifically, after applying a negative photosensitive resin composition to a semiconductor wafer or the like to form a layered composition layer, irradiation with light causes curing by radicals, and solubility in the light irradiation part. Can be reduced. For this reason, there exists an advantage that the area | region from which solubility differs can be easily produced according to the pattern of an electrode by exposing the said composition layer through the photomask with the pattern which masked only the electrode part, for example.

The radical photopolymerization initiator is not particularly limited as long as it has the ability to initiate a polymerization reaction (crosslinking reaction) of a radically polymerizable compound or the like, and can be appropriately selected from known radical photopolymerization initiators. For example, those having photosensitivity to light in the ultraviolet region to the visible region are preferable. Further, it may be an activator that generates some active radicals by generating some action with the photoexcited sensitizer.
The radical photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 to 800 nm (preferably 330 to 500 nm). The molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.

As the radical photopolymerization initiator, known compounds can be used without limitation. For example, halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, those having a trihalomethyl group) , Acylphosphine compounds such as acylphosphine oxide, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo Compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, and the like.

Examples of halogenated hydrocarbon derivatives having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in GB 1388492, a compound described in JP-A-53-133428, a compound described in DE 3337024, F . C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, Examples thereof include compounds described in Japanese Patent No. 4221976.

Examples of the compounds described in US Pat. No. 4,221,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2-trichloro Methyl-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-butoxystyryl) -1,3,4-oxadiazole, 2-tribromomethyl-5-styryl-1,3,4-oxa And diazole).

Further, as photo radical polymerization initiators other than those described above, polyhalogen compounds (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine (for example, 9-phenylacridine, etc.) , Carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethylketone, etc.), coumarins (for example, 3- (2-benzofuranoyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- ( 1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonyl Bis (5,7-di-n-propoxycoumarin), 3, '-Carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7- Methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, JP-A-5-19475, JP-A-7-271028 JP-A 2002-363206, JP-A 2002-363207, JP-A 2002-363208, JP-A 2002-363209, etc.), acylphosphine oxides (for example, bis ( 2,4,6-trimethylbenzoyl) -fe Ruphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.), metallocenes (for example, described in paragraph No. 0076 of JP2011-13602A) Titanocene compound, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, η5-cyclopentadienyl- η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.), JP-A 53-133428, JP-B 57-1819, JP 57-6096, and US Pat. No. 3,615,455. And the compounds described in the book.

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, benzophenone tetracarboxylic acid or its tetramethyl ester, 4,4'-bis (dialkylamino) benzophenones (eg 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (dicyclohexyl) Amino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylaminobenzopheno 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro- Thioxanthone, 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- 1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl) Ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloro acridone, N- methyl acridone, N- butyl acridone, N- butyl - such as chloro acrylic pyrrolidone.
As a commercial product, Kaya Cure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

As the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used. IRGACURE is a registered trademark.
As the aminoacetophenone-based initiator, compounds described in JP-A-2009-191179 whose absorption wavelength is matched with a light source of 365 nm or 405 nm can also be used.
As the acylphosphine initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.

As the photo radical polymerization initiator, an oxime compound is more preferable. Specific examples of the oxime initiator include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166. .
Preferred oxime compounds include, for example, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxycarbonyloxy And imino-1-phenylpropan-1-one.

Examples of oxime compounds include J.M. C. S. Perkin II (1979) pp. 1653-1660, J.A. C. S. Perkin II (1979) pp. 156-162, and Journal of Photopolymer Science and Technology (1995) pp. And the compounds described in JP-A 2000-66385, JP-A 2000-80068, JP-T 2004-534797, and JP-A 2006-342166.
As commercially available products, IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), and N-1919 (manufactured by ADEKA) are also preferably used.

　最も好ましいオキシム化合物としては、特開２００７－２６９７７９号公報に示される、特定置換基を有するオキシム化合物や、特開２００９－１９１０６１号公報に示される、チオアリール基を有するオキシム化合物などが挙げられる。 Further, compounds described in JP-T 2009-519904, in which an oxime is linked to the N-position of the carbazole ring, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, and nitro groups in the dye moiety The compound described in JP 2010-15025 A and US Patent Publication No. 2009-292039 introduced, the ketoxime compound described in International Publication WO 2009/131189, the US containing a triazine skeleton and an oxime skeleton in the same molecule A compound described in Japanese Patent No. 7556910, a compound described in Japanese Patent Application Laid-Open No. 2009-221114, which has an absorption maximum at 405 nm, and has a good sensitivity to a g-ray light source may be used.
In addition, the cyclic oxime compounds described in JP-A-2007-231000 and JP-A-2007-322744 can also be suitably used. Among the cyclic oxime compounds, in particular, the cyclic oxime compounds fused to carbazole dyes described in JP2010-32985A and JP2010-185072A have high light absorption and high sensitivity. It is preferable from the viewpoint.
In addition, a compound described in JP-A-2009-242469, which is a compound having an unsaturated bond at a specific site of the oxime compound, can also be suitably used.
It is also possible to use an oxime compound having a fluorine atom. Specific examples of such an initiator include compounds described in JP 2010-262028 A, compounds 24, 36 to 40 described in paragraph No. 0345 of JP 2014-500852 A, JP Examples thereof include compound (C-3) described in paragraph No. 0101 of 2013-164471. Specific examples include the following compounds.

As the most preferred oxime compounds, there are oxime compounds having a specific substituent, as disclosed in JP 2007-267979 A, and oxime compounds having a thioaryl group, as disclosed in JP 2009-191061 A.

From the viewpoint of exposure sensitivity, the photo radical polymerization initiator is a trihalomethyltriazine compound, a benzyldimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, Selected from the group consisting of allylimidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound and derivatives thereof, cyclopentadiene-benzene-iron complex and salt thereof, halomethyloxadiazole compound, 3-aryl substituted coumarin compound Are preferred.
More preferred are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzophenone compounds, and acetophenone compounds, and more preferred are trihalomethyltriazine compounds. , Α-aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds, and most preferably oxime compounds.

The content of the radical polymerization initiator is preferably from 0.1 to 30% by mass, more preferably from 0.1 to 20% by mass, still more preferably from 0.1 to 20% by mass, based on the total solid content of the negative photosensitive resin composition. 1 to 10% by mass. Further, the radical polymerization initiator is preferably contained in an amount of 1 to 20 parts by mass, more preferably 3 to 10 parts by mass with respect to 100 parts by mass.
Only one type of radical polymerization initiator may be used, or two or more types may be used. When there are two or more radical polymerization initiators, the total is preferably in the above range.

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

　式（１０１）において、ｍは１～５の整数を表し、ｎは１～４の整数を表し、ｎ個のＲ^１０１は、それぞれ独立に、ハロゲン原子（フッ素原子、塩素原子、臭素原子、ヨウ素原子）、シアノ基、水酸基、炭素数１～２０の分岐を有していてもよいアルキル基、炭素数３～８のシクロアルキル基、炭素数６～１２のアリール基、炭素数１～５のアルケニル基、または、炭素数１～５のアルキニル基を表し、これらの基は式（１０１）に示すベンゼン環と連結基を介して結合していてもよく、連結基としては、カルボニル基、カルボニルオキシ基（－ＣＯＯ－）、オキシカルボニル基（－ＯＣＯ－）、チオ基、スルホニル基、スルフィニル基、オキシ基、イミノ基（－ＮＨ－）、アミド基、炭素数１～６のアルキレン基、炭素数６～１２のアリーレン基、ホスホン酸エステル基、リン酸エステル基、トリアジンおよびジオキサン等の複素環から２個以上の水素原子を除いた３～８員環の多価の複素環基、アルキルアミノ基並びにこれらの連結基の組合せから選択される多価の連結基が挙げられる。さらに、２つ以上のＲ^１０１で表される基が互いに結合して環構造を形成していてもよい。 The compound having an aromatic hydroxyl group is preferably a compound represented by the formula (101).
Formula (101)

In the formula (101), m represents an integer of 1 to 5, n represents an integer of 1 to 4, and each of the n R ¹⁰¹ independently represents a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom). Atom), a cyano group, a hydroxyl group, an alkyl group optionally having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. Represents an alkenyl group or an alkynyl group having 1 to 5 carbon atoms, and these groups may be bonded to the benzene ring represented by the formula (101) via a linking group. Oxy group (—COO—), oxycarbonyl group (—OCO—), thio group, sulfonyl group, sulfinyl group, oxy group, imino group (—NH—), amide group, alkylene group having 1 to 6 carbon atoms, carbon 6 to 12 allies A 3- to 8-membered polyvalent heterocyclic group in which two or more hydrogen atoms are removed from a heterocyclic ring such as a len group, a phosphonic acid ester group, a phosphoric acid ester group, a triazine or a dioxane, an alkylamino group, and a linkage thereof Examples include multivalent linking groups selected from a combination of 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 an introduceable carbon atom. Examples of the substituent that can be introduced include alkyl groups having 1 to 6 carbon atoms, hydroxyl groups, cyano groups, halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), amino groups, alkylamino groups, alkoxy groups, and A (meth) acryloyl group etc. can be illustrated.

X ¹⁰¹ does not exist when m is 1, and represents an m-valent linking group when m is 2 or more, specifically a single bond, a carbonyl group, a carbonyloxy group, a thio group, a sulfonyl group, Sulfinyl group, oxy group, phosphonic acid ester group, alkylene group having 1 to 6 carbon atoms, arylene group having 6 to 12 carbon atoms, imino group, aliphatic hydrocarbon group having 1 to 6 carbon atoms excluding m hydrogen atoms , An m-valent aromatic hydrocarbon group having 6 to 12 carbon atoms from which m hydrogen atoms have been removed, a 6 to 12-membered heterocyclic group by removing m hydrogen atoms from a heterocyclic ring such as triazine and dioxane, and Combinations of these linking groups and the like can be mentioned, and the carbon atom that can be introduced may have a substituent. The substituent is preferably the same as R ¹⁰¹ .

Needless to say, when m is 1 in the formula (101), the linking group X ¹⁰¹ is not present. In this case, it may have a monovalent substituent group in place of X ^101, as the monovalent substituent is exemplified the same groups as R ^101, combined with R ¹⁰¹ substituted on the benzene rings A structure may be formed and may be bonded to the benzene ring via a linking group.

Specific examples of the first polymerization inhibitor include 4-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4 -Hydroxyphenyl) propionate], thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxy Phenyl) propionate, N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], 3,3 ′, 3 ″, 5,5 ', 5 "-hexa-tert-butyl-a, a', a"-(mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (Octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di- -Tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 ( 1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol, catechol, tert-butyl -Catechol, 4,4 ', 4 "-(1-methylpropanyl-3-ylidene) tris (6-tert-butyl-m-cresol), 6,6'-di-te t-butyl-4,4′-butylidene-m-cresol, 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1- Dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, hydroquinone, methylhydroquinone, t-butylhydroquinone, di-t-butyl-p-cresol, pyrogallol, 4,4-thiobis ( Examples include 3-methyl-6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), phenol resins, and cresol resins.
A preferred example is 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid alkyl ester. The alkyl chain portion of the alkyl ester here preferably has 7 to 9 carbon atoms.
The content of the first polymerization inhibitor in the negative photosensitive resin composition is preferably 0.01 to 5% by mass with respect to 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 further preferably 0.03% by mass or more. As an upper limit, 3 mass% or less is more preferable, and 1 mass% or less is further more preferable.
Only 1 type may be sufficient as a 1st polymerization inhibitor, and 2 or more types may be sufficient as it. When there are two or more first polymerization inhibitors, the total is preferably in the above range.

<Second polymerization inhibitor>
The negative photosensitive resin composition of the present invention contains at least one second polymerization inhibitor selected from nitroso compounds, N-oxide compounds, quinone compounds, N-oxyl compounds, and phenothiazine compounds. Such a polymerization inhibitor mainly has a strong polymerization inhibitory effect on a compound having a radical polymerizable group in the presence of non-oxygen.

The second polymerization inhibitor nitroso compounds include nitrosobenzene, 2-nitrosotoluene, 1,2,4,5-tetramethyl-3-nitrosobenzene, 4-nitrosophenol, 1-nitroso-2-naphthol, 2 -Nitroso-1-naphthol, 4-nitroso-diphenylamine, 3,5-dibromo-4-nitrosobenzenesulfonic acid, N-nitrosopyrrolidine, Nt-butyl-N-nitrosoaniline, N-nitrosodimethylamine, N- Nitrosodiethylamine, 1-nitrosopiperidine, 4-nitrosomorpholine, N-nitroso-N-methylbutylamine, N-nitroso-N-ethylurea, N-nitrosohexamethyleneimine, N-nitrosophenylhydroxyamine primary cerium salt and N- Nitrosophenylhydroxyamine Salt, 2,4,6-Tris-t- butyl - nitrosobenzene, N- nitrosodiphenylamine is exemplified.

Examples of N-oxide compounds include phenyl-t-butylnitrone, 3,3,5,5-tetramethyl-1-pyrroline-N-oxide, 5,5-dimethyl-1-pyrroline N-oxide, 4-methylmorpholine. Examples include N-oxide, pyridine N-oxide, 4-nitropyridine N-oxide, 3-hydroxypyridine N-oxide, picolinic acid N-oxide, nicotinic acid N-oxide, and isonicotinic acid N-oxide.

Examples of quinone compounds include p-benzoquinone, p-xyloquinone, p-toluquinone, 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-tert-1,4-benzoquinone, thymoquinone, 2,5-di-tert-amylbenzoquinone, 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, teto Chloro-1,4-benzoquinone, methoxy-1,4-benzoquinone, 2,5-dihydroxy-1,4-benzoquinone, 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-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-benzoant Quinone, 1,4-diamino-anthraquinone 2,3-dimethyl anthraquinone 2-ethylanthraquinone, 2-methyl anthraquinone, 5,12 Nafutasenkinon are exemplified.

Examples of N-oxyl compounds include 2,2,6,6-tetramethylpiperidine 1-oxyl, 4-cyano-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-amino-2,2,6. , 6-tetramethylpiperidine 1-oxyl, 4-carboxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4- Hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine 1-oxyl, piperidine 1-oxyl free radical, 4-oxo-2, 2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acetamido-2,2,6,6-tetramethylpiperidine 1- Xylyl free radical, 4-maleimido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, and 4-phosphonoxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, pyrrolidine 1- Examples include oxyl free radical compounds and 3-carboxyproxyl free radical (3-carboxy-2,2,5,5-tetramethylpyrrolidine 1-oxyl free radical).

Examples of the phenothiazine compound include phenothiazine, 10-methylphenothiazine, 2-methylthiophenothiazine, 2-chlorophenothiazine, 2-ethylthiophenothiazine, 2- (trifluoromethyl) phenothiazine, and 2-methoxyphenothiazine.

Since compounds belonging to either structure of the first polymerization inhibitor and the second polymerization inhibitor can inhibit polymerization in the vicinity of the surface layer of the film and inside the film, the second polymerization inhibition Considered an agent.

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 to 5% by mass with respect to the total solid content of the negative photosensitive resin composition. The lower limit value of the content of the second polymerization inhibitor is more preferably 0.02% by mass or more, and further preferably 0.03% by mass or more. As an upper limit, 3 mass% or less is more preferable, and 1 mass% or less is further more preferable.
The second polymerization inhibitor may be only one type or two or more types. When the number of second polymerization inhibitors is two or more, the total is preferably in the above range.

<Ratio of polymerization inhibitor>
The mass ratio between the first polymerization inhibitor and the second polymerization inhibitor is not particularly defined, but is preferably 1:99 to 99: 1, and preferably 90:10 to 10:90. More preferably, it is 70:30 to 30:70. By setting such a range, the exposure latitude tends to be wider.
In the present invention, a polymerization inhibitor other than the first polymerization inhibitor and the second polymerization inhibitor may be included. Moreover, in this invention, it can also be set as the structure which does not contain polymerization inhibitors other than the said 1st polymerization inhibitor and a 2nd polymerization inhibitor. “Substantially free” means that, among the polymerization inhibitors contained in the photosensitive resin composition of the present invention, the amount of other polymerization inhibitors is 5% by mass or less of the total amount of the polymerization inhibitor. Say.
The mass ratio of the first polymerization inhibitor to the radical polymerization initiator is preferably 0.01: 99.99 to 20:80, more preferably 1:99 to 10:90. By setting such a range, the exposure latitude tends to be wider.

<Radically polymerizable compound>
The negative photosensitive resin composition of the present invention may contain a radical polymerizable compound other than the polyimide precursor. By containing a radically polymerizable compound, a cured film having better heat resistance can be formed. Furthermore, pattern formation can also be performed by photolithography.
As the radical polymerizable compound, a compound having an ethylenically unsaturated bond is preferable, and a compound containing two or more ethylenically unsaturated groups is more preferable.
The radically polymerizable compound may be in any of chemical forms such as monomers, prepolymers, oligomers and mixtures thereof, and multimers thereof.

In the present invention, a monomer type 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 2000 or less, more preferably a low molecular compound having a molecular weight of 1500 or less, and a low molecular compound having a molecular weight of 900 or less. More preferably, it is a compound. The molecular weight of the radical polymerizable monomer is usually 100 or more.
The oligomer type radical polymerizable compound is typically a polymer having a relatively low molecular weight, and is preferably a polymer in which 10 to 100 radical polymerizable monomers are bonded. The molecular weight is preferably 2000 to 20000, more preferably 2000 to 15000, and still more preferably 2000 to 10000 in terms of polystyrene in gel permeation chromatography (GPC).

In the present invention, the number of functional groups of the radical polymerizable compound means the number of radical polymerizable groups in one molecule.
From the viewpoint of resolution, the radical polymerizable compound preferably contains at least one bifunctional or higher functional radical polymerizable compound containing two or more radical polymerizable groups, and preferably contains at least one bifunctional or tetrafunctional radical polymerizable compound. More preferably, one kind is included.

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

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, amides, and these Preferred are an ester of an unsaturated carboxylic acid and a polyhydric alcohol compound, an amide of an unsaturated carboxylic acid and a polyvalent amine compound, and a multimer thereof. In addition, an addition reaction product of an ester or amide of an unsaturated carboxylic acid having a nucleophilic substituent such as a hydroxyl group, an amino group, a mercapto group, and a monofunctional or polyfunctional isocyanate or epoxy, or a monofunctional or A dehydration condensation reaction product with a polyfunctional carboxylic acid is also preferably used. In addition, an addition reaction product of an ester or amide of an unsaturated carboxylic acid having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol; A substitution reaction product of an ester or amide of an unsaturated carboxylic acid having a leaving substituent such as a group or a tosyloxy group with a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a compound group in which an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like is used instead of the unsaturated carboxylic acid.

Specific examples of esters of polyhydric alcohol compounds and unsaturated carboxylic acids include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol diacrylate. , Propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetra Ethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Pentaerythritol diacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, isocyanuric acid ethylene oxide modified triacrylate, polyester acrylate There are oligomers and the like.

Methacrylic acid esters 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-hydroxyp Epoxy) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate.

Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.

Examples of isocrotonic acid esters 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.

Examples of other esters include aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, and JP-A-59-5240. The compounds having an aromatic skeleton described in JP-A No. 59-5241, JP-A-2-226149, compounds containing an amino group described in JP-A 1-165613, and the like are also preferably used. It is done.

Specific examples of amide monomers of polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis-methacrylic. Examples include amide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, and xylylene bismethacrylamide.

Examples of other preferable amide monomers include monomers having a cyclohexylene structure described in JP-B No. 54-21726.

In addition, urethane-based addition-polymerizable monomers produced using an addition reaction of isocyanate and hydroxyl group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. Examples thereof include a vinylurethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group to a polyisocyanate compound having two or more isocyanate groups.
Further, urethane acrylates as described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56- Urethane compounds having an ethylene oxide skeleton described in Japanese Patent No. 17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 are also suitable.

As the compound having an ethylenically unsaturated bond, the compounds described in paragraph numbers 0095 to 0108 of JP-A-2009-288705 can also be suitably used in the present invention.

Moreover, as a compound which has an ethylenically unsaturated bond, the compound which has a boiling point of 100 degreeC or more under a normal pressure is also preferable. Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri ( (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 tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) Polyfunctional alcohols such as sosocyanurate, glycerin and trimethylolethane added with ethylene oxide or propylene oxide and then (meth) acrylated. Urethane (meth) acrylates as described in JP-B-37193, polyester acrylates described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490 And polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof. Further, the compounds described in paragraph numbers 0254 to 0257 of JP-A-2008-292970 are also suitable. Moreover, the polyfunctional (meth) acrylate obtained by making the compound which has cyclic ether groups, such as glycidyl (meth) acrylate, and an ethylenically unsaturated group, react with polyfunctional carboxylic acid etc. can be mentioned.
Further, as other preferable compounds having an ethylenically unsaturated bond, those having a fluorene ring described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, etc. A compound having two or more groups having an unsaturated bond, a cardo resin can also be used.
Other examples include specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and JP-A-2-25493. The vinyl phosphonic acid-type compound of these can also be mentioned. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as radically polymerizable monomers and oligomers, can also be used.

In addition to the above, compounds having an ethylenically unsaturated bond represented by the following general formulas (MO-1) to (MO-5) can also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

In the general formula, n is an integer of 0 to 14, and m is an integer of 1 to 8. A plurality of R and T present in one molecule may be the same or different.
In each of the polymerizable compounds represented by the general formulas (MO-1) to (MO-5), at least one of the plurality of R is —OC (═O) CH═CH ₂ , or — represents a _{OC (= O) C (CH} 3) = groups represented by CH _2.
Specific examples of the compound having an ethylenically unsaturated bond represented by the general formulas (MO-1) to (MO-5) are described in paragraph numbers 0248 to 0251 of JP-A-2007-267979. The compound can be suitably used in the present invention.

Further, in JP-A-10-62986, compounds represented by general formulas (1) and (2) together with specific examples thereof, which are (meth) acrylated after addition of ethylene oxide or propylene oxide to a polyfunctional alcohol are also included. Can be used as a polymerizable compound.

Examples of the compound having an ethylenically unsaturated bond include dipentaerythritol triacrylate (as a commercially available product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercially available product, KAYARAD D-320). Manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and a structure in which these (meth) acryloyl groups are bonded via ethylene glycol and propylene glycol residues are preferred. 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 phosphoric acid group. The polyfunctional monomer having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound to form an acid group. More preferred are polyfunctional monomers, particularly preferably those in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include M-510 and M-520, which are polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
As the polyfunctional monomer having an acid group, one kind may be used alone, or two or more kinds may be mixed and used. Moreover, you may use together the polyfunctional monomer which does not have an acid group, and the polyfunctional monomer which has an acid group as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When the acid value of the polyfunctional monomer is in the above range, the production and handling properties are excellent, and further, the developability is excellent. Moreover, radical polymerizability is favorable.

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. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, Polyfunctional alcohol such as pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylol melamine, ε-caprolactone modified polyfunctionality obtained by esterifying (meth) acrylic acid and ε-caprolactone Mention may be made of (meth) acrylates. Among these, a polymerizable compound having a caprolactone structure represented by the following general formula (C) is preferable.

General formula (C)

(In the formula, all six Rs are groups represented by the following general formula (D), or 1 to 5 of the six 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 bond.)

General formula (E)

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

Such a polymerizable compound having a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and DPCA-20 (m = 1 in the above general formulas (C) to (E), Number of groups represented by formula (D) = 2, a compound in which R ¹ is all hydrogen atoms, DPCA-30 (formula, m = 1, number of groups represented by formula (D) = 3 , Compounds in which R ¹ is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (D) = 6, compounds in which R ¹ is all hydrogen atoms), DPCA -120 (a compound in which m = 2 in the formula, the number of groups represented by the general formula (D) = 6, and all R ¹ are hydrogen atoms).
In the present invention, the compounds having a caprolactone structure and an ethylenically unsaturated bond can be used alone or in admixture of two or more.

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

In the general formulas (i) and (ii), each E independently represents — ((CH ₂ ) _y CH ₂ O) — or — ((CH ₂ ) _y CH (CH ₃ ) O) — Each y independently represents an integer of 0 to 10, and each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxyl group.
In the general formula (i), the total number of (meth) acryloyl groups is 3 or 4, each m 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) acryloyl groups is 5 or 6, each n 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 general formula (i), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
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 general formula (ii), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.
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.
In general formula (i) or general formula (ii), — ((CH ₂ ) _y CH ₂ O) — or — ((CH ₂ ) _y CH (CH ₃ ) O) — The form which couple | bonds with is preferable. In particular, in the general formula (ii), a form in which all six Xs are acryloyl groups is preferable.

The compound represented by the general formula (i) or (ii) is a conventionally known process in which a ring-opening skeleton is bonded by a ring-opening addition reaction of ethylene oxide or propylene oxide with pentaerythritol or dipentaerythritol. And a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with the terminal hydroxyl group of the ring-opening skeleton. 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 (ii).

Among the compounds represented by the general formulas (i) and (ii), pentaerythritol derivatives and dipentaerythritol derivatives are more preferable.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”). Among them, exemplary compounds (a), (f) b), (e) and (f) are preferred.

Examples of commercially available polymerizable compounds represented by general formulas (i) and (ii) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

Examples of the compound having an ethylenically unsaturated bond include those described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. Urethane acrylates and urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. It is. Furthermore, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are described as polymerizable compounds. Monomers can also be used.
Commercially available compounds having an ethylenically unsaturated bond include urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A -9300, UA-7200 (manufactured by Shin-Nakamura Chemical 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.), Bremer PME400 (manufactured by NOF Corporation) and the like can be mentioned.

The compound having an ethylenically unsaturated bond preferably has a partial structure represented by the following formula from the viewpoint of heat resistance. However, * in the formula is a connecting hand.

Specific examples of the compound having an ethylenically unsaturated bond having the above partial structure include, for example, trimethylolpropane tri (meth) acrylate, isocyanuric acid ethylene oxide-modified di (meth) acrylate, and isocyanuric acid ethylene oxide-modified tri (meth). Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tetramethylol methane tetra ( (Meth) acrylate etc. are mentioned, and these polymerizable compounds can be particularly preferably used in the present invention.

In the negative photosensitive resin composition, the content of the radical polymerizable compound is 1 to 50% by mass with respect to the total solid content of the negative photosensitive resin composition from the viewpoint of good radical polymerizability and heat resistance. Is preferred. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 30% by mass or less. A radically polymerizable compound may be used alone or in combination of two or more.
The mass ratio of the polyimide precursor to the compound having a radical polymerizable compound (polyimide precursor / radical polymerizable compound) is preferably 98/2 to 10/90, more preferably 95/5 to 30/70, 90/10 to 50/50 is more preferable. If the mass ratio of a polyimide precursor and a radically polymerizable compound is the said range, the cured film excellent in sclerosis | hardenability and heat resistance can be formed.
The radical polymerizable compound may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes the said range.

<Photobase generator>
The negative photosensitive resin composition of the present invention may contain a photobase generator. A photobase generator generates a base upon exposure and does not exhibit activity under normal conditions of normal temperature and pressure. However, when an electromagnetic wave is irradiated and heated as an external stimulus, the base (basic substance) is generated. ) Is not particularly limited as long as it generates. Since the base generated by the exposure works as a catalyst for curing the polyimide precursor by heating, it can be suitably used in the negative type.

The content of the photobase generator is not particularly limited as long as it can form a desired pattern, and can be a general content. The content of the photobase generator is preferably in the range of 0.01 parts by weight or more and less than 30 parts by weight with respect to 100 parts by weight of the negative photosensitive resin composition, and 0.05 parts by weight to 25 parts by weight. More preferably, it is in the range of 0.1 parts by mass to 20 parts by mass.

In the present invention, known photobase generators can be used. For example, the Shirai, and M.M. Tsunooka, Prog. Polym. Sci. , 21, 1 (1996); Masahiro Kadooka, polymer processing, 46, 2 (1997); Kutal, Coord. Chem. Rev. , 211, 353 (2001); Kaneko, A .; Sarker, and D.C. Neckers, Chem. Mater. 11, 170 (1999); Tachi, M .; Shirai, and M.M. Tsunooka, J. et al. Photopolym. Sci. Technol. , 13, 153 (2000); Winkle, and K.K. Graziano, J. et al. Photopolym. Sci. Technol. 3,419 (1990); Tsunooka, H .; Tachi, and S.M. Yoshitaka, J. et al. Photopolym. Sci. Technol. , 9, 13 (1996); Suyama, H .; Araki, M .; Shirai, J. et al. Photopolym. Sci. Technol. , 19, 81 (2006), such as those having a structure such as a transition metal compound complex, an ammonium salt, or the like that is latentized by forming a salt with a carboxylic acid in the amidine moiety. An ionic compound neutralized by forming a salt with a base component, or a nonionic compound in which the base component is made latent by a urethane bond or an oxime bond such as a carbamate derivative, an oxime ester derivative, or an acyl compound Can be mentioned.
The photobase generator that can be used in the present invention is not particularly limited and known ones can be used. For example, carbamate derivatives, amide derivatives, imide derivatives, α-cobalt complexes, imidazole derivatives, cinnamic acid amide derivatives, Examples thereof include oxime derivatives.

The basic substance generated from the photobase generator is not particularly limited, and examples thereof include compounds having an amino group, particularly monoamines, polyamines such as diamines, and amidines.
The generated basic substance is preferably a compound having an amino group having a higher basicity. This is because the catalytic action for the dehydration condensation reaction or the like in the imidization of the polyimide precursor is strong, and the catalytic effect in the dehydration condensation reaction or the like at a lower temperature can be expressed with a smaller amount of addition. That is, since the catalytic effect of the generated basic substance is large, the apparent sensitivity as a negative photosensitive resin composition is improved.
From the viewpoint of the catalytic effect, an amidine and an aliphatic amine are preferable.

The photobase generator is preferably a photobase generator that does not contain salt in the structure. It is preferred that there is no charge on the nitrogen atom of the base moiety generated in the photobase generator. In the photobase generator, the generated base is preferably latentized using a covalent bond, and the base generation mechanism is such that the covalent bond between the nitrogen atom of the generated base moiety and the adjacent atom is cleaved. More preferably, the compound generates a base. When the photobase generator does not contain a salt in the structure, the photobase generator can be neutralized, so that the solvent solubility is good and the pot life is improved. For these reasons, the amine generated from the photobase generator used in the present invention is preferably a primary amine or a secondary amine.

For the reasons described above, the photobase generator preferably has a latent base generated using a covalent bond as described above. More preferably, the generated base is latentized using an amide bond, carbamate bond, or oxime bond.
Examples of the base generator according to the present invention include a base generator having a cinnamic acid amide structure as disclosed in Japanese Patent Application Laid-Open No. 2009-80452 and International Publication No. WO 2009/123122, and Japanese Patent Application Laid-Open No. 2006-189591. And a base generator having a carbamate structure as disclosed in Japanese Patent Application Laid-Open No. 2008-247747, an oxime structure and a carbamoyloxime structure as disclosed in Japanese Patent Application Laid-Open Nos. 2007-249013 and 2008-003581. Examples thereof include, but are not limited to, a base generator having a known structure.

Hereinafter, the photobase generator that can be used in the present invention will be described with specific examples.
Examples of the ionic compound include those having the following structural formula.

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

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

（ＰＢ－１）

(PB-1)

(In the general formula (PB-1), R ⁴¹ and R ⁴² each independently represent a hydrogen atom or an organic group, and may be the same or different, provided that at least one of R ⁴¹ and R ⁴² is present. R ⁴¹ and R ⁴² may be bonded to each other to form a ring structure and may contain a heteroatom bond, and R ⁴³ and R ⁴⁴ are each an organic group. Independently, hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, or an organic group, may be different even in the same ^{.R 45, R 46,} R ⁴⁷ and ^{R 48} are each independently a hydrogen atom, halogen atom , Hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, ammonio group or organic group R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ may be a combination of two or more of them to form a ring structure, and a hetero atom R ⁴⁹ is a hydrogen atom or a protective group that can be deprotected by heating and / or irradiation with electromagnetic waves.)

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

In addition, examples of the photobase generator include compounds described in paragraph numbers 0185 to 0188, 0199 to 0200 and 0202 of JP2012-93746A, compounds described in paragraph numbers 0022 to 0069 of JP2013-194205A. Examples thereof include compounds described in JP-A-2013-204019, paragraphs 0026 to 0074, and compounds described in paragraph No. 0052 of WO2010 / 064631.

<Heat base generator>
The negative photosensitive resin composition of the present invention may contain a thermal base generator.
The type of the thermal base generator is not particularly defined, but is selected from an acidic compound that generates a base when heated to 40 ° C. or higher, and an ammonium salt having an anion having an pKa1 of 0 to 4 and an ammonium cation. It is preferable to include a thermal base generator containing at least one kind. Here, pKa1 represents a logarithmic representation (−Log ₁₀ Ka) of the dissociation constant (Ka) of the first proton of the polyvalent acid.
By mix | blending such a compound, the cyclization reaction of a polyimide precursor can be performed at low temperature, and it can be set as the negative photosensitive resin composition excellent in stability more. Moreover, since the base is not generated unless heated, the thermal base generator can suppress cyclization of the polyimide precursor during storage even if it coexists with the polyimide precursor, and is excellent in storage stability.

The thermal base generator in the present invention is at least one selected from an acidic compound (A1) that generates a base when heated to 40 ° C. or higher, and an ammonium salt (A2) having an anion having a pKa1 of 0 to 4 and an ammonium cation. including.
Since the acidic compound (A1) and the ammonium salt (A2) generate a base when heated, the base generated from these compounds can accelerate the cyclization reaction of the polyimide precursor, thereby cyclizing the polyimide precursor. Can be performed at low temperatures. In addition, even if these compounds coexist with a polyimide precursor that is cured by cyclization with a base, since the cyclization of the polyimide precursor hardly proceeds unless heated, a negative photosensitive resin composition having excellent stability. Product can be prepared.
In the present specification, an acidic compound means that 1 g of a compound is collected in a container, and 50 mL of a mixed solution of ion-exchanged water and tetrahydrofuran (mass ratio is water / tetrahydrofuran = 1/4) is added to the mixture at room temperature for 1 hour. It means a compound having a value measured by stirring at 20 ° C. using a pH (potential hydrogen) meter and 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, more preferably 120 to 200 ° C. The upper limit of the base generation temperature is more preferably 190 ° C or lower, further preferably 180 ° C or lower, and further preferably 165 ° C or lower. The lower limit of the base generation temperature is more preferably 130 ° C or higher, and still more preferably 135 ° C or higher.
If the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 120 ° C. or higher, it is difficult to generate a base during storage. Therefore, it is possible to prepare a negative photosensitive resin composition having excellent stability. it can. When the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 200 ° C. or lower, the cyclization temperature of the polyimide precursor can be lowered. The base generation temperature is measured, for example, by using differential scanning calorimetry, heating the compound to 250 ° C. at 5 ° C./min in a pressure capsule, reading the peak temperature of the lowest exothermic peak, and measuring the peak temperature as the base generation temperature. can do.

In the present invention, the base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, more preferably a tertiary amine. Since tertiary amine has high basicity, the cyclization temperature of a polyimide precursor can be made lower. Further, the boiling point of the base generated by the thermal base 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 2000. The lower limit is more preferably 100 or more. The upper limit is more preferably 500 or less. The molecular weight value is a theoretical value obtained from the structural formula.

In the present invention, the acidic compound (A1) preferably contains one or more selected from 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. 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 to 200 ° C.), or 40 ° C. or higher (preferably 120 to 200 ° C.). ) May be a compound other than an acidic compound that generates a base when heated.

　上記一般式（１）、（２）中、Ｒ^１～Ｒ^６は、それぞれ独立に、水素原子または炭化水素基を表し、式Ｒ^７は炭化水素基を表す。Ｒ^１とＲ^２、Ｒ^３とＲ^４、Ｒ^５とＲ^６、Ｒ^５とＲ^７はそれぞれ結合して環を形成してもよい。 << Ammonium salt >>
In the present invention, the ammonium salt means a salt of an ammonium cation represented by the following general formula (1) or general formula (2) and an anion. The anion may be bonded to any part of the ammonium cation via a covalent bond, and may be outside the molecule of the ammonium cation, but is preferably outside the molecule of the ammonium cation. In addition, that an anion exists outside the molecule | numerator of an ammonium cation means the case where an ammonium cation and an anion are not couple | bonded through a covalent bond. Hereinafter, the anion outside the molecule of the cation moiety is also referred to as a counter anion.

In the general formulas (1) and (2), R ¹ to R ⁶ each independently represents 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.

In the present invention, the ammonium salt preferably has an anion having an pKa1 of 0 to 4 and an ammonium cation. The upper limit of the anion pKa1 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 further preferably 1.0 or more. If the pKa1 of the anion is in the above range, the polyimide precursor can be cyclized at a low temperature, and further, the stability of the negative photosensitive resin composition can be improved. If pKa1 is 4 or less, the stability of the thermal base generator is good, the generation of a base without heating can be suppressed, and the stability of the negative photosensitive resin composition is good. If pKa1 is 0 or more, the generated base is hardly neutralized, and the cyclization efficiency of the polyimide precursor is good.
The kind of anion is preferably one selected from a carboxylate anion, a phenol anion, a phosphate anion, and a sulfate anion, and a carboxylate anion is more preferable because both the stability of the salt and the thermal decomposability can be achieved. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion.
The carboxylic acid anion is preferably a divalent or higher carboxylic acid anion having two or more carboxyl groups, and more preferably a divalent carboxylic acid anion. According to this aspect, it is possible to provide a thermal base generator that can further improve the stability, curability and developability of the negative photosensitive resin composition. In particular, the stability, curability and developability of the negative photosensitive resin composition can be further improved by using an anion of a divalent carboxylic acid.
In the present invention, the carboxylic acid anion is preferably a carboxylic acid anion 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, pKa1 represents the logarithm of the reciprocal of the first dissociation constant of the acid. Determination of Organic Structures by Physical Methods (Author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; Compilation: Braude, EA, Nachod, FC; Academic Press, New York, 1955) and Data for Biochemical Research (author: Dawson, RMC et al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, values calculated from the structural formula using software of ACD / pKa (manufactured by ACD / Labs) are used.

　一般式（Ｘ１）において、ＥＷＧは、電子吸引性基を表す。 In the present invention, the carboxylate anion is preferably represented by the following general formula (X1).

In General Formula (X1), EWG represents an electron-withdrawing group.

In the present invention, the electron-withdrawing group means a group having a positive Hammett's substituent constant σm. Here, σm is a review by Yugo Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965) P.I. 631-642. The electron-withdrawing group of the present invention is not limited to the substituents described in the above documents.
Examples of substituents in which σm has a positive value include, for example, CF ₃ group (σm = 0.43), CF ₃ CO group (σm = 0.63), HC≡C group (σm = 0.21) 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), and the like. Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group.

　式中、Ｒ^ｘ１～Ｒ^ｘ３は、それぞれ独立に、水素原子、アルキル基、アルケニル基、アリール基、水酸基またはカルボキシル基を表し、Ａｒはアリール基を表す。
　アルキル基の炭素数は、１～３０が好ましく、１～２０がより好ましく、１～１０がさらに好ましい。アルキル基は直鎖、分岐、環状のいずれであってもよく、直鎖または分岐が好ましく、直鎖がより好ましい。アルキル基は、置換基を有していてもよく、無置換であってもよい。置換基としては、後述するＡ^１が表す有機基が有していてもよい置換基で説明したものが挙げられる。置換基としては、カルボキシル基が好ましい。
　アルケニル基の炭素数は、２～３０が好ましく、２～２０がより好ましく、２～１０がさらに好ましい。アルケニル基は直鎖、分岐、環状のいずれであってもよく、直鎖または分岐が好ましく、直鎖がより好ましい。アルケニル基は、置換基を有していてもよく、無置換であってもよい。置換基としては、後述するＡ^１が表す有機基が有していてもよい置換基で説明したものが挙げられる。置換基としては、カルボキシル基が好ましい。
　アリール基の炭素数は、６～３０が好ましく、６～２０がより好ましく、６～１２がさらに好ましい。アリール基は、置換基を有していてもよく、無置換であってもよい。置換基としては、後述するＡ^１が表す有機基が有していてもよい置換基で説明したものが挙げられる。置換基としては、カルボキシル基が好ましい。 In the present invention, EWG preferably represents a group represented by the following general formulas (EWG-1) to (EWG-6).

In the formula, R ^x1 to R ^x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group, or a carboxyl group, and Ar represents an aryl group.
The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 10 carbon atoms. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched, more preferably linear. The alkyl group may have a substituent or may be unsubstituted. Examples of the substituent include those described for the organic group has optionally may substituent represented by A ¹ to be described later. As the substituent, a carboxyl group is preferable.
The alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and still more preferably 2 to 10 carbon atoms. The alkenyl group may be linear, branched or cyclic, and is preferably linear or branched, more preferably linear. The alkenyl group may have a substituent or may be unsubstituted. Examples of the substituent include those described for the organic group has optionally may substituent represented by A ¹ to be described later. As the substituent, a carboxyl group is preferable.
The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms. The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include those described for the organic group has optionally may substituent represented by A ¹ to be described later. As the substituent, a carboxyl group is preferable.

　一般式（Ｘ）において、Ｌ^１０は、単結合、または、アルキレン基、アルケニレン基、アリーレン基、－ＮＲ^Ｘ－およびこれらの組み合わせから選ばれる２価の連結基を表し、Ｒ^Ｘは、水素原子、アルキル基、アルケニル基またはアリール基を表す。 In the present invention, the carboxylate anion is also preferably represented by the following general formula (X).

In the general formula (X), L ¹⁰ represents a single bond or a divalent linking group selected from an alkylene group, an alkenylene group, an arylene group, —NR ^X —, and a combination thereof, and R ^X represents a hydrogen atom Represents an alkyl group, an alkenyl group or an aryl group.

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

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

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

The ammonium cation is preferably represented by any one of the following general formulas (Y1-1) to (Y1-6).

In the above general formula, R ¹⁰¹ represents an n-valent organic group,
R ¹⁰² to R ¹¹¹ each independently represents a hydrogen atom or a hydrocarbon group,
R ¹⁵⁰ and R ¹⁵¹ each independently represent a hydrocarbon group,
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,
Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group,
n represents an integer of 1 or more,
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 valent organic group include those obtained by removing one or more hydrogen atoms from a monovalent organic group to form an n valent group.
R ¹⁰¹ is preferably an aryl group. Specific examples of the aryl group include those described for Ar ¹⁰ described later.

R ¹⁰² ~ ^{R 111} each independently represent a hydrogen atom, or a hydrocarbon ^{group, R 0.99} 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 organic group has optionally may substituent represented by A ¹ to be described later.

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

Ar ¹⁰¹ and Ar ¹⁰² each independently represents an aryl group.
The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms. 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, a heterocyclic ring, and the like. The ring may be monocyclic or multicyclic. In the case where the above groups are bonded to form a ring, the linking group is selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aryl group, and combinations thereof. The bivalent coupling group chosen is mentioned. Specific examples of the ring formed include, for example, pyrrolidine ring, pyrrole ring, piperidine ring, pyridine ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, pyrazine ring, morpholine ring, thiazine ring, indole ring, isoindole. Ring, benzimidazole ring, purine ring, quinoline ring, isoquinoline ring, quinoxaline ring, cinnoline ring, carbazole ring and the like.

一般式（Ｙ）中、Ａｒ^１０は、芳香族基を表し、Ｒ^１１～Ｒ^１５は、それぞれ独立に、水素原子または炭化水素基を表し、Ｒ^１４とＲ^１５は互いに結合して環を形成していてもよく、ｎは、１以上の整数を表す。 In the present invention, the ammonium cation preferably has a structure represented by the general formula (Y1-1) or (Y1-2), represented by the general formula (Y1-1) or (Y1-2), and R ¹⁰¹ is aryl. A structure that is a group is more preferable, and a structure represented by the general formula (Y1-1), in which R ¹⁰¹ is an aryl group, is particularly preferable. That is, in the present invention, the ammonium cation is more preferably represented by the following general formula (Y).

In general formula (Y), Ar ¹⁰ represents an aromatic group, R ¹¹ to R ¹⁵ each independently represents a hydrogen atom or a hydrocarbon group, and R ¹⁴ and R ¹⁵ are 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, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indecene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring. Naphthacene ring, chrysene 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, indolizine ring, Indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, Enantororin ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring, and a phenazine ring. Among these, from the viewpoint 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 aryl groups the substituents which may have, include those described in the organic group has optionally may substituent represented by A ¹ to be described later.

R ¹¹ and R ¹² each independently represents 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 alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 10 carbon atoms. The alkyl group may be linear, branched or cyclic.
Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, and an octadecyl group. Isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, and 2-ethylhexyl group.
The cyclic alkyl group (cycloalkyl group) may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. Examples of the monocyclic cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic cycloalkyl group include an adamantyl group, a norbornyl group, a bornyl group, a camphenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group, and a pinenyl group. Can be mentioned. Among these, a cyclohexyl group is most preferable from the viewpoint of achieving high sensitivity.
The alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and still more preferably 2 to 10 carbon atoms. The alkenyl group may be linear, branched or cyclic, and is preferably linear or branched, more preferably linear.
The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms.

R ¹³ to R ^{15 each} represents a hydrogen atom or a hydrocarbon group.
Examples of the hydrocarbon group include the hydrocarbon groups described above for R ¹¹ and R ¹² . R ¹³ to R ¹⁵ are particularly preferably alkyl groups, and preferred embodiments 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 cycloaliphatic (non-aromatic hydrocarbon ring), aromatic ring, heterocyclic ring and the like. The ring may be monocyclic or multicyclic. When R ⁴ and R ⁵ are combined to form a ring, the linking group is composed of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aryl group, and combinations thereof. And divalent linking groups selected from the group. Specific examples of the ring formed include, for example, pyrrolidine ring, pyrrole ring, piperidine ring, pyridine ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, pyrazine ring, morpholine ring, thiazine ring, indole ring, isoindole. Ring, benzimidazole ring, purine ring, quinoline ring, isoquinoline ring, quinoxaline ring, cinnoline ring, carbazole ring and the like.

R ¹³ to R ¹⁵ are a group in which R ¹⁴ and R ¹⁵ are bonded to each other to form a ring, or R ¹³ is a linear alkyl group having 5 to 30 carbon atoms (more preferably 6 to 18 carbon atoms). R ¹⁴ and R ¹⁵ are preferably each independently an alkyl group having 1 to 3 carbon atoms (more preferably 1 or 2 carbon atoms). According to this aspect, it is possible to easily generate amine species having a high boiling point.
R ¹³ to R ¹⁵ are preferably 7 to 30 in terms of the total number of carbon atoms of R ¹³ , R ¹⁴ and R ¹⁵ from the viewpoint of the basicity and boiling point of the generated amine species. It is more preferable.
In addition, the amount of the chemical formula “—NR ¹³ R ¹⁴ R ¹⁵ ” in the general formula (Y) is preferably 80 to 2000, and more preferably 100 to 500, because an amine species having a high boiling point is likely to be generated.

On the other hand, as an embodiment for further improving the adhesion to the copper wiring, in the general formula (Y), R ¹³ and R ¹⁴ are a methyl group or an ethyl group, and R ¹⁵ is a straight chain having 5 or more carbon atoms, Examples include a branched or cyclic alkyl group or an aryl group. In this embodiment, R ¹³ and R ¹⁴ are methyl groups, and R ¹⁵ is a linear alkyl group having 5 to 20 carbon atoms, a branched alkyl group having 6 to 17 carbon atoms, or a cyclic alkyl group having 6 to 10 carbon atoms. Or a phenyl group, 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, or 6 to 8 carbon atoms. A cyclic alkyl group or a phenyl group is more preferable. By reducing the hydrophobicity of the amine species in this way, it is possible to more effectively prevent the affinity between the copper surface and the polyimide from being lowered even when the amine adheres on the copper wiring. In the present embodiment, preferred ranges of Ar ¹⁰ , R ¹¹ , R ¹² and n are the same as described above.

<Compound represented by formula (A1)>
In the present invention, the acidic compound is also preferably a compound represented by the following general formula (A1). This compound is acidic at room temperature, but by heating, the carboxyl group is lost by decarboxylation or dehydration cyclization, and the amine site that has been neutralized and inactivated becomes active. It becomes sex. Hereinafter, general formula (A1) is demonstrated.

　一般式（Ａ１）において、Ａ^１はｐ価の有機基を表し、Ｒ^１は１価の有機基を表し、Ｌ^１は（ｍ＋１）価の有機基を表し、ｍは１以上の整数を表し、ｐは１以上の整数を表す。

In General Formula (A1), A ¹ represents a p-valent organic group, R ¹ represents a monovalent organic group, L ¹ represents an (m + 1) -valent organic group, and m represents an integer of 1 or more. , P represents an integer of 1 or more.

In 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 preferable. By the A ¹ and aryl group, at lower temperatures, often invites a base having a boiling point higher. By increasing the boiling point of the generated base, volatilization or decomposition due to heating at the time of curing of the polyimide precursor can be suppressed, and cyclization of the polyimide precursor can proceed more effectively.
Examples of the monovalent aliphatic group include an alkyl group and an alkenyl group.
The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 10 carbon atoms. The alkyl group may be linear, branched or cyclic. The alkyl group may have a substituent or may be unsubstituted. Specific examples of the alkyl group include a methyl group, an ethyl group, a tert-butyl group, a dodecyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and an adamantyl group.
The alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and still more preferably 2 to 10 carbon atoms. The alkenyl group may be linear, branched or 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 groups obtained by removing one or more hydrogen atoms from the above monovalent aliphatic group.
The aryl group may be monocyclic or polycyclic. The aryl group may be a heteroaryl group containing a heteroatom. The aryl group may have a substituent or may be unsubstituted. Unsubstituted is preferred. Specific examples of the aryl group include benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indecene ring, perylene ring, pentacene ring, acenaphthalene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene ring. , Triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, thiazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, Benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, Antoren ring, chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring, and include phenazine ring, a benzene ring is most preferred.
In the aryl group, a plurality of aromatic rings may be linked through a single bond or a linking group described later. As the linking group, for example, an alkylene group is preferable. The alkylene group is preferably linear or branched. Specific examples of the aryl group in which a plurality of aromatic rings are linked through a single bond or a linking group include biphenyl, diphenylmethane, diphenylpropane, diphenylisopropane, triphenylmethane, and tetraphenylmethane.

Examples of the substituent that the organic group represented by A ¹ may have include, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a methoxy group, an ethoxy group and a tert-butoxy group. Alkoxy groups; aryloxy groups such as phenoxy group and p-tolyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group and butoxycarbonyl group; aryloxycarbonyl groups such as phenoxycarbonyl group; acetoxy group, propionyloxy group and benzoyloxy group An acyloxy group such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group and a methoxalyl group; an alkylsulfanyl group such as a methylsulfanyl group and a tert-butylsulfanyl group; And arylsulfanyl groups such as p-tolylsulfanyl group; alkyl groups such as methyl group, ethyl group, tert-butyl group and dodecyl group; halogenated alkyl groups such as fluorinated alkyl group; cyclopentyl group, cyclohexyl group, cycloheptyl Group and cycloalkyl group such as adamantyl group; aryl group such as phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group and phenanthryl group; hydroxyl group; carboxyl group; formyl group; sulfo group; Alkylaminocarbonyl group; arylaminocarbonyl group; sulfonamido group; silyl group; amino group; monoalkylamino group; dialkylamino group; arylamino group; diarylamino group;

L ¹ represents a (m + 1) -valent linking group. The linking group is not particularly limited, and is —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, an alkylene group (preferably a straight chain having 1 to 10 carbon atoms). A chain or branched alkylene group), a cycloalkylene group (preferably a cycloalkylene group having 3 to 10 carbon atoms), an alkenylene group (preferably a linear or branched alkenylene group having 210 carbon atoms), or a linking group in which a plurality of these are linked And so on. The total carbon number of the linking group is preferably 3 or less. The linking group is preferably an alkylene group, a cycloalkylene group, or an alkenylene group, more preferably a linear or branched alkylene group, still more preferably a linear alkylene group, particularly preferably an ethylene group or a methylene group, and most preferably a methylene group.

R ¹ represents a monovalent organic group. Examples of the monovalent organic group include an aliphatic group and an aryl group. Aliphatic group, for the aryl group include those described in A ¹ described above. The monovalent organic group represented by R ¹ may have a substituent. Examples of the substituent include those described 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 an (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 above for L ¹ , and the preferred ranges are also the same, an ethylene group or a methylene group is particularly preferred, and a methylene group is most preferred.
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 that can take the linking group L ² represents. If n is 1, a tertiary amine having a high boiling point is likely to be 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 that the linking group represented by L ¹ can take. When m is 1, a tertiary amine having a high boiling point is likely to be 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 take the organic group A ¹ represents. When p is 1, a tertiary amine having a high boiling point is likely to be generated by heating at 200 ° C. or lower.

　一般式（１ａ）中、Ａ^１はｐ価の有機基を表し、Ｌ^１は（ｍ＋１）価の連結基を表し、Ｌ^２は（ｎ＋１）価の連結基を表し、ｍは１以上の整数を表し、ｎは１以上の整数を表し、ｐは１以上の整数を表す。
　一般式（１ａ）のＡ^１、Ｌ^１、Ｌ^２、ｍ、ｎおよびｐは、一般式（Ａ１）で説明した範囲と同義であり、好ましい範囲も同様である。 In the present invention, the compound represented by the general formula (A1) is preferably a compound represented by the following general formula (1a).

In General Formula (1a), A ¹ represents a p-valent organic group, L ¹ represents an (m + 1) -valent linking group, L ² represents an (n + 1) -valent linking group, and m is an integer of 1 or more. , N represents an integer of 1 or more, and p represents an integer of 1 or more.
A ¹ , L ¹ , L ² , m, n, and p in the general formula (1a) have the same meanings as the ranges 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. In N-aryliminodiacetic acid, A ¹ in the general formula (A1) is an aryl group, L ¹ and L ² are methylene groups, m is 1, n is 1, and p is 1. A compound. N-aryliminodiacetic acid tends to generate a tertiary amine having a high boiling point at 120 to 200 ° C.

Although the specific example of the thermal base generator in this invention is described below, this invention is not limited to these. These can be used alone or in admixture of two or more. Me in the following formulas represents a methyl group. Among the compounds shown below, (A-1) to (A-11), (A-18), and (A-19) are compounds represented by the above formula (A1). Of the compounds shown below, (A-1) to (A-11), (A-18) to (A-26) are more preferred, and (A-1) to (A-9), (A-18) ) To (A-21), (A-23), and (A-24) are more preferable.
From the viewpoint of improving the adhesion to copper, (A-18) to (A-26) and (A-38) to (A-43) are preferable, and (A-26) and (A-38) are preferable. ) To (A-43) are more preferable.

As the thermal base generator used in the present invention, compounds described in paragraph Nos. 0015 to 0055 of Japanese Patent Application No. 2015-034388 are also preferably used, the contents of which are incorporated herein.

When the thermal base generator is used, the content of the thermal base generator in the negative photosensitive resin composition is preferably 0.1 to 50% by mass with respect to the total solid content of the negative photosensitive resin composition. The lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and further preferably 20% by mass or less.
1 type (s) or 2 or more types can be used for a thermal base generator. When using 2 or more types, it is preferable that a total amount is the said range.

<Thermal radical polymerization initiator>
The negative photosensitive resin composition of the present invention may contain a thermal radical polymerization initiator. As the thermal radical polymerization initiator, a known thermal radical polymerization initiator can be used.
The thermal radical polymerization initiator is a compound that generates radicals by heat energy and initiates or accelerates the polymerization reaction of the polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the polymerizable compound can be advanced when the cyclization reaction of the polyimide precursor is advanced. Moreover, when a polyimide precursor contains an ethylenically unsaturated bond, since the polymerization reaction of a polyimide precursor can also be advanced with the cyclization of a polyimide precursor, higher heat resistance can be achieved.
Thermal radical polymerization initiators include aromatic ketones, onium salt compounds, peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, carbon halogens. Examples thereof include a compound having a bond and an azo compound. Among these, a peroxide or an azo compound is more preferable, and a peroxide is particularly preferable.
The thermal radical polymerization initiator used in the present invention preferably has a 10-hour half-life temperature of 90 to 130 ° C, more preferably 100 to 120 ° C.
Specific examples include compounds described in paragraph numbers 0074 to 0118 of JP-A-2008-63554.
In a commercial item, perbutyl Z and park mill D (made by NOF Corporation) can be used conveniently.

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 with respect to the total solid content of the negative photosensitive resin composition. 0.1 to 30% by mass is more preferable, and 0.1 to 20% by mass is particularly preferable. Further, the thermal radical polymerization initiator is preferably contained in an amount of 0.1 to 50 parts by mass, and more preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the polymerizable compound. According to this aspect, it is easy to form a cured film having more excellent heat resistance.
Only one type of thermal radical polymerization initiator may be used, or two or more types may be used. When there are two or more thermal radical polymerization initiators, the total is preferably in the above range.

<Corrosion inhibitor>
It is preferable to add a corrosion inhibitor to the negative photosensitive resin composition of the present invention. The corrosion inhibitor is added for the purpose of preventing the outflow of ions from the metal wiring. Examples of the compound include a rust inhibitor described in paragraph No. 0094 of JP2013-15701A, and JP2009-283711A. The compounds described in Paragraph Nos. 0073 to 0076, the compound described in Paragraph No. 0052 of JP 2011-59656 A, the compounds described in Paragraph Nos. 0114, 0116, and 0118 of JP 2012-194520 A are used. be able to. Among them, a compound having a triazole ring or a compound having a tetrazole ring can be preferably used. 1,2,4-triazole, 1,2,3-benzotriazole, 5-methyl-1H-benzotriazole, 1H-tetrazole 5-methyl-1H-tetrazole is more preferred, and 1H-tetrazole is most preferred.
When the corrosion inhibitor is added, the amount of the corrosion inhibitor is preferably in the range of 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight with respect to 100 parts by weight of the polyimide precursor. It is a range.
Only one type of corrosion inhibitor may be used, or two or more types may be used. When using 2 or more types, it is preferable that the sum total is the said range.

　金属接着性改良剤を用いる場合、金属接着性改良剤の配合量は、ポリイミド前駆体１００質量部に対して好ましくは０．１～３０質量部の範囲であり、より好ましくは０．５～１５質量部の範囲である。０．１質量部以上とすることで熱硬化後の膜と金属との接着性が良好となり、３０質量部以下とすることで硬化後の膜の耐熱性、機械特性が良好となる。
　金属接着性改良剤は１種のみでもよいし、２種以上であってもよい。２種以上用いる場合、その合計が上記範囲であることが好ましい。 <Metal adhesion improver>
The negative photosensitive resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to a metal material used for electrodes, wirings and the like. Examples of metal adhesion improvers include sulfide compounds described in paragraph numbers 0046 to 0049 of JP-A-2014-186186 and paragraph numbers 0032 to 0043 of JP-A-2013-072935. Examples of the metal adhesion improver also include the following compounds.

When using a metal adhesion improver, the compounding amount of the metal adhesion improver is preferably in the range of 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts per 100 parts by mass of the polyimide precursor. It is the range of mass parts. By setting it as 0.1 mass part or more, the adhesiveness of the film | membrane and metal after thermosetting becomes favorable, and the heat resistance of the film | membrane after hardening and mechanical characteristics become favorable by setting it as 30 mass parts or less.
Only one type of metal adhesion improver may be used, or two or more types may be used. When using 2 or more types, it is preferable that the sum total is the said 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 paragraphs 0062 to 0073 of JP2014-191002, compounds described in paragraphs 0063 to 0071 of WO2011 / 080992A1, and JP2014-191252A. And the compounds described in paragraph Nos. 0060 to 0061 of JP-A No. 2014-41264, the compounds described in paragraph Nos. 0045 to 0052 of JP 2014-41264 A, and the compounds described in paragraph No. 0055 of WO 2014/097594. It is also preferable to use two or more different silane coupling agents as described in paragraph numbers 0050 to 0058 of JP2011-128358A.
When a silane coupling agent is used, the amount of the silane coupling agent is preferably in the range of 0.1 to 20 parts by mass, more preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the polyimide precursor. It is. When it is 0.1 part by mass or more, sufficient adhesion to the substrate can be imparted, 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.
Only one type of silane coupling agent may be used, or two or more types may be used. When using 2 or more types, it is preferable that the sum total is the said range.

<Sensitizing dye>
The negative photosensitive resin composition of the present invention may contain a sensitizing dye. A sensitizing dye absorbs specific actinic radiation and enters an electronically excited state. The sensitizing dye in an electronically excited state is brought into contact with a thermal base generator, a thermal radical polymerization initiator, a photo radical polymerization initiator or the like, and causes actions such as electron transfer, energy transfer, and heat generation. Thereby, a thermal base generator, a thermal radical polymerization initiator, and a photo radical polymerization initiator cause a chemical change and are decomposed to generate radicals, acids, or bases.

Examples of preferable sensitizing dyes include those belonging to the following compounds and having an absorption wavelength in the range of 300 nm to 450 nm. For example, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9.10-dialkoxyanthracene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), thioxanthones (For example, 2,4-diethylthioxanthone), cyanines (for example thiacarbocyanine, oxacarbocyanine), merocyanines (for example merocyanine, carbomerocyanine), thiazines (for example thionine, methylene blue, toluidine blue), acridines (Eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squaryliums (eg, squarylium), coumarins (eg, 7-di-) Chiruamino 4-methylcoumarin), styryl benzenes, distyryl benzenes, carbazoles, and the like.

Among them, in the present invention, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene), thioxanthones, distyrylbenzenes, and styrylbenzenes are preferably used from the viewpoint of starting efficiency, and the anthracene skeleton is used. It is more preferable to use the compound which has. Particularly preferred specific compounds include 9,10-diethoxyanthracene and 9,10-dibutoxyanthracene.

When the negative photosensitive resin composition contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01 to 20% by mass, based on the total solid content of the negative photosensitive resin composition, 0.1 Is more preferably 15 to 15% by mass, and further preferably 0.5 to 10% by mass. A sensitizing dye may be used individually by 1 type, and may use 2 or more types together.

<Chain transfer agent>
The negative photosensitive resin composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in Polymer Dictionary 3rd Edition (edited by the Polymer Society, 2005) pages 683-684. As the chain transfer agent, for example, a compound group having SH, PH, SiH, GeH in the molecule is used. These can donate hydrogen to low-activity radical species to generate radicals, or can be oxidized and then deprotonated to generate radicals. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.) can be preferably used.

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 with respect to 100 parts by mass of the total solid content of the negative photosensitive resin composition. More preferably, it is 1 to 10 parts by mass, and still more preferably 1 to 5 parts by mass.
Only one type of chain transfer agent may be used, or two or more types may be used. When there are two or more chain transfer agents, the total is preferably in the above range.

<Surfactant>
Various surfactants may be added to the negative photosensitive resin composition of the present invention from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
In particular, by including a fluorosurfactant, liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, so that the uniformity of coating thickness and liquid-saving properties can be further improved. .
In the case of forming a film using a coating liquid containing a fluorosurfactant, the wettability to the coated surface is improved by reducing the interfacial tension between the coated surface and the coating liquid, and the coated surface The coating property of is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

　上記の化合物の重量平均分子量は、例えば、１４，０００である。 The fluorine content of the fluorosurfactant 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 within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility.
Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320 PF6520, PF7002 (manufactured by OMNOVA), and the like.
A block polymer can also be used as the fluorosurfactant, and specific examples thereof include compounds described in JP-A-2011-89090.
The following compounds are also exemplified as the fluorosurfactant used in the present invention.

The weight average molecular weight of the above compound is, for example, 14,000.

Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1) Solsperse 20000 (Lubrizol Japan Co., Ltd.), and the like. Alternatively, Pionein D-6112-W manufactured by Takemoto Yushi Co., Ltd., NCW-101, NCW-1001, NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. may be used.

Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.

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

Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Tore Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400, Momentive Performance Materials TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by BYK Chemie.

When the negative photosensitive resin composition contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass with respect to the total solid content of the negative photosensitive resin composition. More preferably, the content is 0.005 to 1.0% by mass.
Only one surfactant may be used, or two or more surfactants may be used. When two or more surfactants are contained, the total is preferably in the above range.

<Higher fatty acid derivatives, etc.>
In order to prevent polymerization inhibition due to oxygen, a negative fatty acid derivative such as behenic acid or behenamide is added to the negative photosensitive resin composition of the present invention, and the negative photosensitive resin composition in the drying process after coating. It may be unevenly distributed on the surface of the photosensitive resin composition.
When the negative photosensitive resin composition contains a higher fatty acid derivative or the like, the content of the higher fatty acid derivative or the like is preferably 0.1 to 10% by mass with respect to the total solid content of the negative photosensitive resin composition. .
Only one type of higher fatty acid derivative or the like may be used. When two or more higher fatty acid derivatives are contained, the total is preferably within the above range.

<Solvent>
When the negative photosensitive resin composition of the present invention is layered by coating, it is preferable to blend a solvent. If a negative photosensitive resin composition can be formed in a layer form, a well-known thing can be used for a solvent without a restriction | limiting.
Examples of the solvent used in the negative photosensitive resin composition of the present invention include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, and ethyl butyrate. Butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone δ-valerolactone, alkyl oxyacetate (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, Butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate etc.)), 3-oxypropionic acid alkyl esters (eg methyl 3-oxypropionate, ethyl 3-oxypropionate etc. (eg methyl 3-methoxypropionate, 3-methoxypropio Acid ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-oxypropionic acid alkyl esters (for example, methyl 2-oxypropionate, ethyl 2-oxypropionate, 2-oxypropionic acid) Propyl etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-oxy-2-methylpropion Methyl acid and ethyl 2-oxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, pyruvic acid Propyl, methyl acetoacetate, ace Ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like, and ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve 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 as ketones, for example, methyl ethyl ketone , Cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and aromatic hydrocarbons such as toluene, xylene, anisole and limonene, and sulfoxides Preferred examples include dimethyl sulfoxide.

The solvent is preferably in the form of a mixture of two or more types from the viewpoint of improving the coated surface. Among them, 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 A mixed solution composed of two or more selected from dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable. The combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

When the negative photosensitive resin composition contains a solvent, the content of the solvent should be such that the total solid content concentration of the negative photosensitive resin composition is 5 to 80% by mass from the viewpoint of applicability. It is preferably 5 to 70% by mass, more preferably 10 to 60% by mass.
One type of solvent may be sufficient and 2 or more types may be sufficient as it. When two or more solvents are contained, the total is preferably within the above range.
In addition, the content of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide and N, N-dimethylformamide is such that the negative photosensitive resin composition can be used from the viewpoint of film strength. It is preferably less than 5% by mass, more preferably less than 1% by mass, further preferably less than 0.5% by mass, and particularly preferably less than 0.1% by mass with respect to the total mass.

<Other additives>
The negative photosensitive resin composition of the present invention is various additives, for example, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet rays, as necessary, as long as the effects of the present invention are not impaired. Absorbers, anti-aggregation agents and the like can be blended. When mix | blending these additives, it is preferable that the total compounding quantity shall be 3 mass% or less of solid content of a negative photosensitive resin composition.

The water 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 the coated surface.

From the viewpoint of insulation, the metal content of the negative photosensitive resin composition of the present invention is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and particularly preferably less than 0.5 ppm by mass. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. 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 metal impurities unintentionally contained in the negative photosensitive resin composition, a negative photosensitive resin composition in which a raw material having a low metal content is selected as a raw material constituting the negative photosensitive resin composition. Filter the raw material constituting the conductive resin composition, and line the inside of the apparatus with polytetrafluoroethylene or the like, and perform distillation under the conditions that suppress contamination as much as possible. .

In the negative photosensitive resin composition of the present invention, the halogen atom content is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass from the viewpoint of wiring corrosion. Especially, what exists in the state of a halogen ion is less than 5 mass ppm, more preferably less than 1 mass ppm, and especially less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. The total of chlorine atoms and bromine atoms, or chloride ions and bromide ions is preferably in the above range.

<Preparation of negative photosensitive resin composition>
The negative photosensitive resin composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited, and can be performed by a conventionally known method.
Moreover, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the negative photosensitive resin composition. The pore size 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 filter material is preferably a polytetrafluoroethylene, polyethylene, or nylon filter. A filter that has been washed in advance with an organic solvent may be used. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different pore diameters and / or materials may be used in combination. Moreover, various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step. Moreover, you may pressurize and filter and the pressure to pressurize is 0.05 MPa or more and 0.3 MPa or less.
In addition to filtration using a filter, impurities may be removed using an adsorbent. Moreover, you may combine a filter filtration and an adsorbent for the removal of an impurity. As the adsorbent, known adsorbents can be used. 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 having excellent heat resistance and insulation, it can be preferably used for an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, and the like. In particular, it can be preferably used for an interlayer insulating film for a rewiring layer in a three-dimensional mounting device.
It can also be used as a photoresist for electronics (galvanic resist, galvanic resist, etching resist, solder top resist).
It can also be used for the production of printing plates such as offset printing plates or screen printing plates, the etching of molded parts, the production of protective lacquers and dielectric layers in electronics, in particular microelectronics.

<Method for producing cured film>
Next, the manufacturing method of the cured film of this invention is demonstrated. The method for producing a cured film is not particularly defined as long as it is formed using the negative photosensitive resin composition of the present invention. The method for producing a cured film of the present invention preferably includes a step of applying the negative photosensitive resin composition of the present invention to a substrate and a step of curing the negative photosensitive resin composition applied to the substrate. .

<< Step of applying negative photosensitive resin composition to substrate >>
Examples of the method for applying the negative photosensitive resin composition to the substrate include spinning, dipping, doctor blade coating, suspension casting, coating, spraying, electrostatic spraying, reverse roll coating, and the like. Electrostatic spraying and reverse roll coating are preferred because they can be applied uniformly on the substrate.

Examples of the substrate include inorganic substrates, resins, and resin composite materials.
Examples of the inorganic substrate include a glass substrate, a quartz substrate, a silicon substrate, a silicon nitride substrate, and a composite substrate obtained by depositing molybdenum, titanium, aluminum, copper, or the like on such a substrate.
As the resin substrate, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, Fluorine resin such as polybenzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, Groups consisting of synthetic resins such as aromatic ethers, maleimide-olefins, cellulose, episulfide compounds And the like. These substrates are rarely used in the above-described form, and usually have a multilayer structure such as a thin film transistor (TFT) element, depending on the form of the final product.

The amount (layer thickness) and type of substrate (layer carrier) to which the negative photosensitive resin composition is applied depends on the field of application desired. It is particularly advantageous that the photosensitive resin composition can be used in layer thicknesses that can be varied over a wide range. The range of the layer thickness is preferably 0.5 to 100 μm, and in the method of the present invention, it is more effective when the thickness is 3 to 30 μm, further 5 to 30 μm.
It is preferable to dry the negative photosensitive resin composition after applying it to the substrate. The drying is preferably performed at 60 to 150 ° C. for 10 seconds to 2 minutes, for example.

<< Step of heating >>
By heating the negative photosensitive resin composition applied to the substrate, the cyclization reaction of the polyimide precursor proceeds and a cured film having excellent heat resistance can be formed.
The heating temperature is preferably 50 to 300 ° C, more preferably 100 to 250 ° C.
According to the present invention, since many isomers with a faster cyclization rate are contained, the cyclization reaction of the polyimide precursor can be performed at a lower temperature.

It is preferable to adjust at least one selected from a heating rate, a heating time, and a cooling rate from the viewpoint of reducing internal stress and suppressing warpage of the cured film.
The heating rate is preferably 3 to 5 ° C./min, with 20 to 150 ° C. being the heating start temperature.
When the heating temperature is 200 to 240 ° C., the heating time is preferably 180 minutes or more. For example, the upper limit is preferably 240 minutes or less. When the heating temperature is 240 to 300 ° C., the heating time is preferably 90 minutes or more. For example, the upper limit is preferably 180 minutes or less. When the heating temperature is 300 to 380, the heating time is preferably 60 minutes or more. For example, the upper limit is preferably 120 minutes or less.
The cooling rate is preferably 1 to 5 ° C./min.
Heating may be performed in stages. For example, the temperature is raised from 20 ° C. to 150 ° C. at 5 ° C./minute, placed at 150 ° C. for 30 minutes, heated from 150 ° C. to 230 ° C. at 5 ° C./minute, and placed at 230 ° C. for 180 minutes A process is mentioned.

The heating step is preferably performed in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon from the viewpoint of preventing decomposition of a polyimide precursor such as polyimide. The oxygen concentration is preferably 50 ppm by volume or less, and more preferably 20 ppm by volume or less.

In this invention, you may perform a pattern formation process between the process of applying the said negative photosensitive resin composition to a board | substrate, and the said process of heating. The pattern forming step can be performed by, for example, a photolithography method. For example, the method of performing through the process of exposing and the process of developing 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 photolithography will be described.

<< Exposure Step >>
In the exposure step, the negative photosensitive resin composition applied to the substrate is irradiated with a predetermined pattern of actinic rays or radiation.
The wavelength of the actinic ray or radiation varies depending on the composition of the negative photosensitive resin composition, but is preferably 200 to 600 nm, and more preferably 300 to 450 nm.
As a light source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, or the like can be used. Actinic rays having a wavelength of 300 nm to 450 nm can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed. The exposure dose is preferably 1 to 1000 mJ / cm ² , more preferably 200 to 800 mJ / cm ² . The value of the present invention is high in that it can be developed with high developability in such a wide range.
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, a lens scanner, and a laser exposure can be used.
When (meth) acrylate and similar olefinically unsaturated compounds are used, their photopolymerization is prevented by oxygen in the air, as is well known, particularly in thin layers. This effect can be mitigated by known conventional methods such as temporary introduction of a coating layer of polyvinyl alcohol, pre-exposure or pre-conditioning in an inert gas.

<< Process for performing development process >>
In the step of developing, the unexposed portion of the negative photosensitive resin composition is developed using a developer. As the developer, an aqueous alkaline developer, an organic solvent, or the like can be used.
Examples of the alkali compound used in the aqueous alkaline developer include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, and metasilicic acid. Examples include potassium, ammonia, and amine. Examples of amines include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, quaternary ammonium hydroxide, tetramethylammonium hydroxide. (TMAH) or tetraethylammonium hydroxide. Of these, alkali compounds containing no metal are preferred. Suitable aqueous alkaline developers are generally up to 0.5 N with respect to alkali, but may be diluted appropriately prior to use. For example, an aqueous alkaline developer having a concentration of about 0.15 to 0.4 N, preferably 0.20 to 0.35 N is also suitable. Only one alkali compound may be used, or two or more alkali compounds may be used. When using 2 or more types of alkali compounds, it is preferable that the sum total is the said range.
As an organic solvent, the thing similar to the solvent which can be used for the negative photosensitive resin composition mentioned above can be used. For example, preferred are n-butyl acetate, γ-butyrolactone, cyclopentanone, and a mixture thereof.
Further, it is preferable to include a step of heating the developed negative photosensitive resin composition at a temperature of 50 to 500 ° C. after the step of performing the development treatment. By passing through such a process, there exists a merit that heat resistance and adhesiveness with a board | substrate improve.

As a field to which the method for producing a cured film of the present invention is applicable, it can be preferably used for an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, and the like. Particularly, since the resolution is good, it can be preferably used for an interlayer insulating film for a rewiring layer in a three-dimensional mounting device.
It can also be used as a photoresist for electronics (galvanic resist, galvanic resist, etching resist, solder top resist).
Also. It can also be used for the production of printing plates such as offset printing plates or screen printing plates, etching of molded parts, the production of protective lacquers and dielectric layers in electronics, in particular microelectronics.

<Semiconductor devices>
Next, an embodiment of a semiconductor device using the negative photosensitive resin composition as an interlayer insulating film for a rewiring layer will be described.
A semiconductor device 100 shown in FIG. 1 is a so-called three-dimensional mounting device, and a stacked body 101 in which a plurality of semiconductor elements (semiconductor chips) 101 a to 101 d are stacked is arranged on a wiring board 120.
In this embodiment, the case where the number of stacked semiconductor elements (semiconductor chips) is four will be mainly described. However, the number of stacked semiconductor elements (semiconductor chips) is not particularly limited. It may be a layer, 8 layers, 16 layers, 32 layers, or the like. Moreover, one layer may be sufficient.

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

The stacked body 101 has a structure in which a semiconductor element 101a having no through electrode and semiconductor elements 101b to 101d having through electrodes 102b to 102d are flip-chip connected.
That is, the electrode pad of the semiconductor element 101a having no through electrode and the connection pad on the semiconductor element 101a side of the semiconductor element 101b having the adjacent through electrode 102b are connected by the metal bump 103a such as a solder bump, The connection pad on the other side of the semiconductor element 101b having the electrode 102b is connected to the connection pad on the semiconductor element 101b side of the semiconductor element 101c having the penetrating electrode 102c adjacent thereto by a metal bump 103b such as a solder bump. Similarly, the connection pad on the other side of the semiconductor element 101c having the through electrode 102c is connected to the connection pad on the semiconductor element 101c side of the semiconductor element 101d having the adjacent through electrode 102d by the metal bump 103c such as a solder bump. ing.

An underfill layer 110 is formed in the gaps between the semiconductor elements 101a to 101d, and the semiconductor elements 101a to 101d are stacked via the underfill layer 110.

The stacked body 101 is stacked on the wiring board 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 board 120 to which the resin board is applied include a multilayer copper-clad laminate (multilayer printed wiring board).

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

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Unless otherwise specified, “%” and “parts” are based on mass. NMR is an abbreviation for nuclear magnetic resonance.

(Synthesis Example 1)
[Synthesis of polyimide precursor (A-1: polyimide precursor having no radically polymerizable group) from pyromellitic dianhydride, 4,4′-oxydianiline and benzyl alcohol]
14.06 g (64.5 mmol) pyromellitic dianhydride (dried at 140 ° C. for 12 hours) and 14.22 g (131.58 mmol) benzyl alcohol were suspended in 50 ml N-methylpyrrolidone. And dried with molecular sieves. The suspension was heated at 100 ° C. for 3 hours. A clear solution was obtained several minutes after the start of heating. The reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) pyridine and 90 ml N-methylpyrrolidone were added. The reaction mixture was then cooled to −10 ° C. and 16.12 g (135.5 mmol) of SOCl ₂ was added over 10 minutes while maintaining the temperature at −10 ± 4 ° C. During the addition of SOCl ₂ the viscosity increased. After dilution with 50 ml N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, a solution of 11.08 g (58.7 mmol) of 4,4′-oxydianiline dissolved in 100 ml of N-methylpyrrolidone was added dropwise to the reaction mixture at 20-23 ° C. over 20 minutes. The reaction mixture was then stirred overnight at room temperature. The polyimide precursor was then precipitated in 5 liters of water and the water-polyimide precursor mixture was stirred for 15 minutes at a speed of 5000 rpm. The polyimide precursor was collected by filtration, poured into 4 liters of water again, stirred for another 30 minutes, and filtered again. Next, the obtained polyimide precursor was dried at 45 ° C. under reduced pressure for 3 days to obtain a polyimide precursor (A-1) having a structure represented by the following formula.

(Synthesis Example 2)
[Synthesis of polyimide precursor (A-2: polyimide precursor having a radical polymerizable group) from pyromellitic dianhydride, 4,4′-oxydianiline and 2-hydroxyethyl methacrylate]
14.06 g (64.5 mmol) pyromellitic dianhydride (dried at 140 ° C. for 12 hours), 18.6 g (129 mmol) 2-hydroxyethyl methacrylate, 0.05 g hydroquinone, 7 g of pyridine and 140 g of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at a temperature of 60 ° C. for 18 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Next, the obtained diester was chlorinated with SOCl ₂ and then converted into a polyimide precursor with 4,4′-oxydianiline in the same manner as in Synthesis Example 1, and in the same manner as in Synthesis Example 1, the following formula A polyimide precursor (A-2) having a structure represented by the formula:

(Synthesis Example 3)
[Synthesis of polyimide precursor (A-3: polyimide precursor having radical polymerizable group) from 4,4′-oxydiphthalic anhydride, 4,4′-oxydianiline and 2-hydroxyethyl methacrylate]
20.0 g (64.5 mmol) 4,4′-oxydiphthalic anhydride (dried at 140 ° C. for 12 hours), 18.6 g (129 mmol) 2-hydroxyethyl methacrylate, 0.05 g hydroquinone 10.7 g of pyridine and 140 g of diglyme were mixed and stirred at a temperature of 60 ° C. for 18 hours to produce a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Next, the obtained diester was chlorinated with SOCl ₂ and then converted into a polyimide precursor with 4,4′-oxydianiline in the same manner as in Synthesis Example 1, and in the same manner as in Synthesis Example 1, the following formula A polyimide precursor (A-3) having a structure represented by the formula:

Synthesis Example 4 [Synthesis of polyimide precursor (A-4: polyimide precursor having a carboxyl group) from 4,4′-oxydiphthalic anhydride and 4,4′-oxydianiline]
20.0 g (64.5 mmol) of 4,4′-oxydiphthalic anhydride (dried at 140 ° C. for 12 hours) was dissolved in 180 ml of NMP (N-methyl-2-pyrrolidone), and an additional 21.43 g (270.9 mmol) of pyridine was added and the reaction was cooled to −10 ° C. and 11.08 g (58.7 mmol) of 4,4′-oxydithiol while maintaining the temperature at −10 ± 4 ° C. A solution obtained by dissolving aniline in 100 ml of NMP was added dropwise over 30 minutes, and then the reaction mixture was stirred at room temperature overnight. Then, it was poured into 5 liters of water to precipitate the polyimide precursor, and the water-polyimide precursor mixture was stirred at a speed of 5000 rpm for 15 minutes. The polyimide precursor was collected by filtration, poured into 4 liters of water again, stirred for another 30 minutes, and collected again by filtration. Next, the obtained polyimide precursor was dried at 45 ° C. under reduced pressure for 3 days to obtain a polyimide precursor (A-4) having a structure represented by the following formula.

(Synthesis Example 5) [Synthesis of Polymer for Comparative Example (RA-1)]
27.0 g (153.2 mmol) benzyl methacrylate, 20 g (157.3 mmol) N-isopropylmethacrylamide, 39 g (309.2 mmol) allyl methacrylate, 13 g (151.0 mmol) methacrylic acid, A polymerization initiator (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) (3.55 g, 15.4 mmol) and 3-methoxy-2-propanol (300 g) were mixed. The mixed solution was dropped into 300 g of 3-methoxy-2-propanol heated to 75 ° C. in a nitrogen atmosphere 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 precipitated by pouring into 5 liters of water and stirred for 15 minutes at a speed of 5000 rpm. The acrylic resin was collected by filtration, poured into 4 liters of water again, stirred for another 30 minutes, and collected again by filtration. Next, the obtained acrylic resin was dried at 45 ° C. under reduced pressure for 3 days to obtain a comparative polymer (RA-1) represented by the following formula.

<Examples and Comparative Examples>
The following components were mixed to prepare a photosensitive resin composition coating solution as a uniform solution.
<< Composition of photosensitive resin composition >>
Polyimide precursor: parts by mass listed in Table 6 Radical polymerization initiator: parts by mass listed in Table 6 First polymerization inhibitor: parts by weight listed in Table 6 Second polymerization inhibitor: parts by weight listed in Table 6 Radical polymerization Compound: parts by mass listed in Table 6 Thermal base generator: parts by mass listed in Table 6 (other components)
γ-butyrolactone: 60.00 parts by mass

Abbreviations described in Table 6 are as follows.
(A) Polyimide precursor or comparative resins A-1 to A-4 and RA-1: Resins synthesized in Synthesis Examples 1 to 5

(B) Photoradical polymerization initiator B-1: Irgacure OXE-01 (manufactured by BASF)
B-2: Irgacure 369 (BASF)
B-3: Irgacure 784 (BASF)

(C) First polymerization inhibitor C-1: 4-methoxyphenol (manufactured by Tokyo Chemical Industry)
C-2: 2,6-di-tert-butyl-4-methylphenol (manufactured by Tokyo Chemical Industry)
C-3: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (manufactured by BASF, Irganox 1010)
C-4: Thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (manufactured by BASF, Irganox 1035)
C-5: Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (manufactured by BASF, Irganox 1076)
C-6: N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide] (manufactured by BASF, Irganox 1098)
C-7: 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesitylene-2,4,6-triyl) tri-p-cresol (BASF, Irganox 1330)
C-8: Ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] (Irganox 245, manufactured by BASF)
C-9: Hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (manufactured by BASF, Irganox 259)
C-10: 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (BASF, Irganox 3114)
C-11: Catechol (manufactured by Tokyo Chemical Industry)
C-12: tert-butyl-catechol (manufactured by Tokyo Chemical Industry)

(D) Second polymerization inhibitor D-1: 2,4,6-Tris-t-butyl-nitrosobenzene (manufactured by Tokyo Chemical Industry)
D-2: Phenyl-t-butylnitrone (manufactured by Tokyo 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-Toluquinone (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-oxyl (manufactured by Tokyo Chemical Industry) D-8: 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (Tokyo Chemical Industry) Made)
D-9: 4-Methacryloyloxy-2,2,6,6-tetramethylpiperidine 1-oxyl (manufactured by Tokyo Chemical Industry)
D-10: N-nitrosodiphenylamine (manufactured by Tokyo Chemical Industry)
D-11: Phenothiazine (manufactured by Tokyo Chemical Industry)

Ｅ－２：ＮＫエステル　４Ｇ　（新中村化学工業（株）製　２官能メタリレート　下記構造）

Ｅ－３：　ＮＫエステル　Ａ－９３００　（新中村化学工業（株）製　３官能アクリレート　下記構造）

(E) Radical polymerizable compound E-1: NK ester M-40G (manufactured by Shin-Nakamura Chemical Co., Ltd., monofunctional methacrylate, following structure)

E-2: NK ester 4G (Shin Nakamura Chemical Co., Ltd., bifunctional metallate, following structure)

E-3: NK Ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd., trifunctional acrylate following structure)

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

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

<Evaluation>
[Exposure latitude]
The photosensitive resin composition layer on the silicon wafer was exposed using a stepper (Nikon NSR2005 i9C). The exposure is performed with i-line, and at a wavelength of 365 nm, using a line and space photomask in increments of 1 μm from 5 μm to 25 μm with each exposure energy of 200, 300, 400, 500, 600, 700, 800 mJ / cm ^2. , Exposure was performed.

The exposed photosensitive resin composition layer was developed with cyclopentanone for 60 seconds. The line width that was able to have good edge sharpness was evaluated according to the following criteria. The smaller the line width of the photosensitive resin composition layer, the greater the difference in solubility in the developer between the light-irradiated part and the light non-irradiated part, which is a preferable result. Further, if the change in the line width is small with respect to the change in exposure energy, it indicates that the exposure latitude is wide, which is a preferable result. The measurement limit is 5 μm. The results are shown in Table 7.
A: 5 μm to 8 μm B: Over 8 μm to 10 μm or less C: Over 10 μm to 15 μm or less D: Over 15 μm to 20 μm or less E: Over 20 μm.

[Heat-resistant]
The exposed photosensitive resin composition layer is heated at 300 ° C. for 3 hours in a nitrogen atmosphere, and then the exposed photosensitive resin composition layer is scraped off, and a thermal mass is obtained in nitrogen at a temperature rising rate of 10 ° C./min. Analytical measurement was performed, the thermal decomposition temperature was measured, and evaluated according to the following criteria. The results are shown in Table 7.
A: 5% mass reduction temperature is 300 ° C. or more B: 5% mass reduction temperature is less than 300 ° C.

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

<Example 100>
The negative photosensitive resin composition of Example 1 was subjected to pressure filtration through a filter having a pore width of 0.8 μm and then applied to a resin substrate on which a thin copper layer was formed by spinning (3500 rpm, 30 seconds). did. The negative photosensitive resin composition applied to the resin substrate was dried at 100 ° C. for 5 minutes and then exposed using an aligner (Karl-Suss MA150). Exposure was performed with a high-pressure mercury lamp, and exposure energy at a wavelength of 365 nm was measured. After exposure, the image was developed with cyclopentanone for 75 seconds.
Subsequently, it heated at 180 degreeC for 20 minutes. In this way, an interlayer insulating film for a rewiring layer was formed.
This interlayer insulation film for rewiring layers was excellent in insulation.
Moreover, when a semiconductor device was manufactured using this interlayer insulating film for rewiring layer, it was confirmed that it operated without any problem.

100: Semiconductor devices 101a to 101d: Semiconductor elements 101: Stacked bodies 102b to 102d: Through electrodes 103a to 103e: Metal bumps 105: Rewiring layers 110, 110a, 110b: Underfill layers 115: Insulating layers 120: Wiring substrates 120a: Surface electrode

Claims (19)

Polyimide precursor; radical polymerization initiator; at least one first polymerization inhibitor selected from compounds having an aromatic hydroxyl group; and nitroso compounds, N-oxide compounds, quinone compounds, N-oxyl compounds, and phenothiazines A negative photosensitive resin composition comprising at least one second polymerization inhibitor selected from compounds. The negative photosensitive resin composition according to claim 1, wherein the polyimide precursor includes a repeating unit represented by the following general formula (1);
General formula (1)

In general formula (1), A ¹ and A ² each independently represent an oxygen atom or —NH—, R ¹¹ represents a divalent organic group, and R ¹² represents a tetravalent organic group. , R ¹³ and R ¹⁴ each independently represents a hydrogen atom or a monovalent organic group. In the general formula (1), at least one of R ¹³ and R ¹⁴ comprises a radical polymerizable group, the negative photosensitive resin composition of claim 2. The negative photosensitive resin composition according to any one of claims 1 to 3, further comprising a radical polymerizable compound. The negative photosensitive resin composition of Claim 4 in which the said radically polymerizable compound has two or more radically polymerizable groups. The negative photosensitive resin composition according to any one of claims 1 to 5, wherein the second polymerization inhibitor is selected from a quinone compound and an N-oxyl compound. The negative photosensitive resin composition according to any one of claims 1 to 6, wherein a mass ratio of the first polymerization inhibitor and the second polymerization inhibitor is 10:90 to 90:10. object. The negative photosensitive resin composition according to any one of claims 1 to 7, wherein a mass ratio of the first polymerization inhibitor to the radical polymerization initiator is 1:99 to 10:90. The negative photosensitive resin composition according to any one of claims 1 to 8, wherein, in the general formula (1), R ¹² is a tetravalent group containing an aromatic ring. The negative photosensitive resin composition according to any one of claims 1 to 9, further comprising a thermal base generator. The negative photosensitive resin composition according to claim 10, wherein the thermal base generator has an ammonium cation represented by the following general formula (Y);

In general formula (Y), Ar ¹⁰ represents an aromatic group, R ¹¹ to R ¹⁵ each independently represents a hydrogen atom or a hydrocarbon group, and R ¹⁴ and R ¹⁵ are bonded to each other to form a ring. And n represents an integer of 1 or more. The negative photosensitive resin composition according to any one of claims 1 to 11, which is used for an interlayer insulating film for a rewiring layer. A cured film obtained by curing the negative photosensitive resin composition according to any one of claims 1 to 12. The cured film of Claim 13 which is an interlayer insulation film for rewiring layers. A method for producing a cured film, comprising using the negative photosensitive resin composition according to any one of claims 1 to 12. Applying the negative photosensitive resin composition to a substrate;
A step of exposing the negative photosensitive resin composition applied to the substrate by irradiation with actinic rays or radiation, and
The manufacturing method of the cured film of Claim 15 which has a process of developing with respect to the said exposed negative photosensitive resin composition. The method for producing a cured film according to claim 16, comprising a step of heating the developed negative photosensitive resin composition at a temperature of 50 to 500 ° C after the step of performing the development treatment. The method for producing a cured film according to any one of claims 15 to 17, wherein the film thickness of the cured film is 3 to 30 µm. A semiconductor device comprising the cured film according to claim 13 or 14, or the cured film produced by the method according to any one of claims 15 to 18.

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