JPWO2020066435A1 - Photosensitive resin compositions, cured films, laminates, methods for producing cured films, semiconductor devices, and thermal base generators. - Google Patents

Abstract

A novel thermobase generator will be provided to enrich materials in the field of photosensitive resin compositions containing specific polymer precursors. Further, if necessary, a method for producing a photosensitive resin composition, a cured film, a laminate, and a cured film capable of achieving both excellent storage stability in the photosensitive resin composition and excellent mechanical properties in the cured film. , And a thermal base generator. The photosensitive resin composition contains at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, a specific thermobase generator, and a photosensitive agent.

Description

The present invention relates to a photosensitive resin composition, a cured film, a laminate, a method for producing a cured film, a semiconductor device, and a thermobase generator.

Cyclized and cured resins such as polyimide resins and polybenzoxazole resins have excellent heat resistance and insulating properties, and are therefore applied to various applications. The application is not particularly limited, and examples of semiconductor devices for mounting include use as a material for an insulating film or a sealing material, or as a protective film (see Non-Patent Documents 1 and 2 and the like). It is also used as a base film and coverlay for flexible substrates.

Such a polyimide resin or the like generally has low solubility in a solvent. Therefore, a method of dissolving in a solvent in the state of a polymer precursor before the cyclization reaction, specifically, a polyimide precursor or a polybenzoxazole precursor, is often used. As a result, excellent handleability can be realized, and when each product as described above is manufactured, it can be applied to a substrate or the like in various forms and processed. It can then be heated to cyclize the polymer precursor to form a cured product. In addition to the high performance of polyimide resins and the like, from the viewpoint of excellent manufacturing adaptability, the industrial application development is expected more and more.

Patent Document 1 discloses an example of a semiconductor device using a polyimide resin or the like as an insulating layer. The polyimide resin or the like constituting this insulating layer is formed by using a composition containing a thermosetting resin such as a polyimide precursor. Therefore, by adopting a specific thermosetting agent to be contained in the present composition, the cyclization reaction of the thermosetting resin can be carried out at a low temperature, and the thermosetting resin composition is excellent in stability. It is stated that it can be used.

International Publication No. WO 2015/199220 Pamphlet

Science & Technology Co., Ltd. "High-performance and applied technology of polyimide" April 2008 Masaaki Kakimoto / Supervision, CMC Technical Library "Basics and Development of Polyimide Materials" published in November 2011

The stability of the thermosetting resin could be improved by the technique of Patent Document 1. On the other hand, further research and development is required to meet the diversified required characteristics of this type of resin in recent years.

Therefore, the present invention provides a novel thermobase generator, and at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor (hereinafter, this is referred to as "specific polymer precursor"). It is an object of the present invention to enrich materials in the field of photosensitive resin compositions containing (may be referred to as). Furthermore, a method for producing a photosensitive resin composition, a cured film, a laminate, a cured film, and a method for producing the photosensitive resin composition, which can achieve both excellent storage stability in the photosensitive resin composition and excellent mechanical properties in the cured film, and An object of the present invention is to provide a thermobase generator.

As a result of studies by the present inventor based on the above problems, it has been found that a thermobase generator having a specific structure having a carboxyl group and an amino group can solve the above problems, and the present invention is completed. It came to. Specifically, the above problems have been solved by the following means.

式中、Ｒ^N1およびＲ^N2はそれぞれ独立に、水素原子または１価の有機基を表し、Ｒ^N3およびＲ^N4はそれぞれ独立に、水素原子または置換基を有していてもよい脂肪族炭化水素基であり、ただし上記置換基はヒドロキシル基以外の酸基であることはなく、Ｒ^N1とＲ^N2は互いに連結して環状構造を形成してもよく、Ｒ^N3とＲ^N4は互いに連結して環状構造を形成してもよく、Ｒ^N1とＲ^N3は互いに連結して環状構造を形成してもよく、Ｒ^N2とＲ^N4は互いに連結して環状構造を形成してもよく、Ｘは単結合またはカルボニル基を表し、Ｘが単結合の場合、Ｙは単結合または２価の有機基を表し、Ｘがカルボニル基の場合、Ｙは２価の有機基を表す。

＜２＞上記式（Ｎ１）または（Ｎ２）で表される熱塩基発生剤において、ＸおよびＹが単結合である、＜１＞に記載の感光性樹脂組成物。

＜３＞上記式(Ｎ１)が下記式（Ｎ１−１）〜（Ｎ１−４）のいずれかである、＜１＞または＜２＞に記載の感光性樹脂組成物。

式中、Ｒ^N31、Ｒ^N32およびＲ^N33は、それぞれ独立に、水素原子または置換基を有していてもよい脂肪族炭化水素基であり、ただし上記置換基はヒドロキシル基以外の酸基であることはなく、Ｒ^N11は１価の有機基を表し、Ｒ^N12は２価の連結基であり、Ａｒ^Nは芳香族炭化水素基であり、

式（Ｎ１−１）において、Ｒ^N31とＲ^N32は連結して環状構造を形成してもよく、Ｒ^N31と式中の窒素原子とカルボニル基の間のメチレン基は連結して環状構造を形成してもよく、Ｒ^N32と式中の窒素原子とカルボニル基の間のメチレン基は連結して環状構造を形成してもよく、

式（Ｎ１−２）において、Ｒ^N33と式中の窒素原子とカルボニル基の間のメチレン基は連結して環状構造を形成してもよく、

式（Ｎ１−３）において、Ｒ^N11とＲ^N11が置換する炭素原子は連結して環状構造を形成してもよく、

式（Ｎ１−４）において、Ｒ^N12とＲ^N12が置換する炭素原子は連結して環状構造を形成してもよく、Ａｒ^NとＲ^N12が置換する炭素原子は連結して環状構造を形成してもよい。

＜４＞上記ポリマー前駆体がポリイミド前駆体を含む、＜１＞〜＜３＞のいずれか１つに記載の感光性樹脂組成物。

＜５＞上記ポリイミド前駆体が下記式（１）で表される、＜４＞に記載の感光性樹脂組成物。

式（１）中、Ａ¹およびＡ²は、それぞれ独立に酸素原子またはＮＨを表し、Ｒ¹¹¹は、２価の有機基を表し、Ｒ¹¹⁵は、４価の有機基を表し、Ｒ¹¹³およびＲ¹¹⁴は、それぞれ独立に、水素原子または１価の有機基を表す。

＜６＞上記感光剤が光重合開始剤と重合性化合物とを含む、＜１＞〜＜５＞のいずれか１つに記載の感光性樹脂組成物。

＜７＞再配線層用層間絶縁膜の形成に用いられる、＜１＞〜＜６＞のいずれか１つに記載の感光性樹脂組成物。

＜８＞＜１＞〜＜７＞のいずれか１つに記載の感光性樹脂組成物を硬化してなる硬化膜。

＜９＞＜８＞に記載の硬化膜を２層以上有し、２層の上記硬化膜の間に金属層を有する、積層体。

＜１０＞＜１＞〜＜７＞のいずれか１つに記載の感光性樹脂組成物を基板に適用して膜を形成する膜形成工程を含む、硬化膜の製造方法。

＜１１＞上記膜を露光する露光工程および露光後の上記膜を現像する現像工程を有する、＜１０＞に記載の硬化膜の製造方法。

＜１２＞＜１０＞に記載の上記膜形成工程後の上記膜を８０〜４５０℃で加熱する工程をさらに含むか、または、＜１１＞に記載の上記現像工程後の上記膜を８０〜４５０℃で加熱する工程を含む、硬化膜の製造方法。

＜１３＞＜８＞に記載の硬化膜または＜９＞に記載の積層体を有する、半導体デバイス。

＜１４＞下記式（Ｎ１）または（Ｎ２）で表される熱塩基発生剤。

式中、Ｒ^N1およびＲ^N2はそれぞれ独立に、水素原子または１価の有機基を表し、Ｒ^N3およびＲ^N4はそれぞれ独立に、水素原子または置換基を有していてもよい脂肪族炭化水素基であり、ただし上記置換基はヒドロキシル基以外の酸基を有することはなく、Ｒ^N1とＲ^N2は互いに連結して環状構造を形成してもよく、Ｒ^N3とＲ^N4は互いに連結して環状構造を形成してもよく、Ｒ^N1とＲ^N3は互いに連結して環状構造を形成してもよく、Ｒ^N2とＲ^N4は互いに連結して環状構造を形成してもよく、Ｘは単結合またはカルボニル基を表し、Ｘが単結合の場合、Ｙは単結合または２価の有機基を表し、Ｘがカルボニル基の場合、Ｙは２価の有機基を表す。

＜１５＞上記式（Ｎ１）または（Ｎ２）で表される熱塩基発生剤において、ＸおよびＹが単結合である、＜１４＞に記載の熱塩基発生剤。

＜１６＞上記式(Ｎ１)が下記式（Ｎ１−１）〜（Ｎ１−４）のいずれかである、＜１４＞または＜１５＞に記載の熱塩基発生剤。

式中、Ｒ^N31、Ｒ^N32およびＲ^N33は、それぞれ独立に、水素原子または置換基を有していてもよい脂肪族炭化水素基であり、ただしこの置換基はヒドロキシル基以外の酸基であることはなく、Ｒ^N11は１価の有機基を表し、Ｒ^N12は２価の連結基であり、Ａｒ^Nは芳香族炭化水素基であり、

式（Ｎ１−１）において、Ｒ^N31とＲ^N32は連結して環状構造を形成してもよく、Ｒ^N31と式中の窒素原子とカルボニル基の間のメチレン基は連結して環状構造を形成してもよく、Ｒ^N32と式中の窒素原子とカルボニル基の間のメチレン基は連結して環状構造を形成してもよく、

式（Ｎ１−２）において、Ｒ^N33と式中の窒素原子とカルボニル基の間のメチレン基は連結して環状構造を形成してもよく、

式（Ｎ１−３）において、Ｒ^N11とＲ^N11が置換する炭素原子は連結して環状構造を形成してもよく、

式（Ｎ１−４）において、Ｒ^N12とＲ^N12が置換する炭素原子は連結して環状構造を形成してもよく、Ａｒ^NとＲ^N12が置換する炭素原子は連結して環状構造を形成してもよい。

<1> At least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, a thermobase generator represented by the following formula (N1) or (N2), and a photosensitive agent. A photosensitive resin composition comprising.

In the formula, ^RN1 and ^RN2 each independently represent a hydrogen atom or a monovalent organic group, and ^RN3 and ^RN4 independently represent an aliphatic hydrocarbon which may have a hydrogen atom or a substituent, respectively. It is a group, however, the substituent is not an acid group other than a hydroxyl group, ^RN1 and ^RN2 may be linked to each other to form a cyclic structure, and ^RN3 and ^RN4 may be linked to each other. An annular structure may be formed, ^RN1 and ^RN3 may be connected to each other to form an annular structure, ^RN2 and ^RN4 may be connected to each other to form an annular structure, and X is simply. When X is a single bond, Y represents a single bond or a divalent organic group, and when X is a carbonyl group, Y represents a divalent organic group.

<2> The photosensitive resin composition according to <1>, wherein X and Y are single bonds in the thermal base generator represented by the above formula (N1) or (N2).

<3> The photosensitive resin composition according to <1> or <2>, wherein the above formula (N1) is any of the following formulas (N1-1) to (N1-4).

In the formula, ^RN31 , ^RN32 and ^RN33 are aliphatic hydrocarbon groups which may independently have a hydrogen atom or a substituent, except that the substituent is an acid group other than a hydroxyl group. R ^N11 represents a monovalent organic group, ^RN12 is a divalent linking group, Ar ^N is an aromatic hydrocarbon group, and

In the formula (N1-1), ^RN31 and ^RN32 may be linked to form a cyclic structure, and ^{the methylene group between RN31} and the nitrogen atom and the carbonyl group in the formula may be linked to form a cyclic structure. ^{Alternatively} , the methylene group between the RN32 and the nitrogen atom and the carbonyl group in the formula may be linked to form a cyclic structure.

In the formula (N1-2), a methylene group between the nitrogen atom and the carbonyl group of R ^N33 and in the formula may form a cyclic structure linked,

In the formula (N1-3), the carbon atom to which R ^N11 and R ^N11 is substituted may form a cyclic structure linked,

In the formula (N1-4), the carbon atom to which R ^N12 and R ^N12 is substituted may form a cyclic structure linked, the carbon atom to which Ar ^N and R ^N12 is substituted to form a cyclic structure linked You may.

<4> The photosensitive resin composition according to any one of <1> to <3>, wherein the polymer precursor contains a polyimide precursor.

<5> The photosensitive resin composition according to <4>, wherein the polyimide precursor is represented by the following formula (1).

In formula (1), A ¹ and A ² independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ independently represents a hydrogen atom or a monovalent organic group.

<6> The photosensitive resin composition according to any one of <1> to <5>, wherein the photosensitive agent contains a photopolymerization initiator and a polymerizable compound.

<7> The photosensitive resin composition according to any one of <1> to <6>, which is used for forming an interlayer insulating film for a rewiring layer.

<8> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <7>.

<9> A laminate having two or more cured films according to <8> and having a metal layer between the two cured films.

<10> A method for producing a cured film, which comprises a film forming step of applying the photosensitive resin composition according to any one of <1> to <7> to a substrate to form a film.

<11> The method for producing a cured film according to <10>, which comprises an exposure step of exposing the film and a developing step of developing the film after exposure.

<12> The step of heating the film after the film forming step according to <10> at 80 to 450 ° C. is further included, or the film after the developing step according to <11> is 80 to 450. A method for producing a cured film, which comprises a step of heating at ° C.

<13> A semiconductor device having the cured film according to <8> or the laminate according to <9>.

<14> A thermobase generator represented by the following formula (N1) or (N2).

In the formula, ^RN1 and ^RN2 each independently represent a hydrogen atom or a monovalent organic group, and ^RN3 and ^RN4 independently represent an aliphatic hydrocarbon which may have a hydrogen atom or a substituent, respectively. It is a group, however, the substituent does not have an acid group other than a hydroxyl group, ^RN1 and ^RN2 may be linked to each other to form a cyclic structure, and ^RN3 and ^RN4 may be linked to each other. An annular structure may be formed, ^RN1 and ^RN3 may be connected to each other to form an annular structure, ^RN2 and ^RN4 may be connected to each other to form an annular structure, and X is simply. When X is a single bond, Y represents a single bond or a divalent organic group, and when X is a carbonyl group, Y represents a divalent organic group.

<15> The thermobase generator according to <14>, wherein X and Y are single bonds in the thermobase generator represented by the above formula (N1) or (N2).

<16> The thermobase generator according to <14> or <15>, wherein the above formula (N1) is any of the following formulas (N1-1) to (N1-4).

In the formula, ^RN31 , ^RN32 and ^RN33 are aliphatic hydrocarbon groups which may independently have a hydrogen atom or a substituent, except that the substituent is an acid group other than a hydroxyl group. R ^N11 represents a monovalent organic group, ^RN12 is a divalent linking group, Ar ^N is an aromatic hydrocarbon group, and

In the formula (N1-1), ^RN31 and ^RN32 may be linked to form a cyclic structure, and ^{the methylene group between RN31} and the nitrogen atom and the carbonyl group in the formula may be linked to form a cyclic structure. ^{Alternatively} , the methylene group between the RN32 and the nitrogen atom and the carbonyl group in the formula may be linked to form a cyclic structure.

In the formula (N1-2), a methylene group between the nitrogen atom and the carbonyl group of R ^N33 and in the formula may form a cyclic structure linked,

In the formula (N1-3), the carbon atom to which R ^N11 and R ^N11 is substituted may form a cyclic structure linked,

In the formula (N1-4), the carbon atom to which R ^N12 and R ^N12 is substituted may form a cyclic structure linked, the carbon atom to which Ar ^N and R ^N12 is substituted to form a cyclic structure linked You may.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a novel thermobase generator and enrich materials in the field of photosensitive resin compositions containing a specific polymer precursor. Further, if necessary, both excellent storage stability of the photosensitive resin composition and excellent mechanical properties of the cured film can be achieved at the same time.

Hereinafter, the contents of the present invention will be described in detail. In addition, in this specification, "~" is used in the meaning that the numerical values described before and after it are included as the lower limit value and the upper limit value.

The description of the components in the present invention described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

In the notation of a group (atomic group) in the present specification, the notation that does not describe substitution and non-substitution includes those having no substituent as well as those having 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). Further, the term alkyl group may be chain or cyclic, and the chain may be linear or branched. These things are also synonymous with the alkenyl group, the alkylene group, and the alkenylene group.

In the present specification, "exposure" includes not only exposure using light but also drawing using particle beams such as an electron beam and an ion beam, unless otherwise specified. Further, as the light used for exposure, generally, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation can be mentioned.

In the present specification, "(meth) acrylate" means both "acrylate" and "methacrylate", or either, and "(meth) acrylic" means both "acrylic" and "methacryl", or. Representing either, "(meth) acryloyl" represents both "acryloyl" and "methacryloyl", or either.

In the present specification, the term "process" is included in this term not only as an independent process but also as long as the desired action of the process is achieved even if it cannot be clearly distinguished from other processes. ..

Unless otherwise specified, the physical property values in the present invention are values at a temperature of 23 ° C. and an atmospheric pressure of 1013.25 hPa.

In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured by gel permeation chromatography (GPC measurement) unless otherwise specified, and are defined as polystyrene-equivalent values. In the present specification, for the weight average molecular weight (Mw) and the number average molecular weight (Mn), for example, HLC-8220 (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be obtained by using Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). In this measurement, THF (tetrahydrofuran) is used as the eluent unless otherwise specified. Unless otherwise specified, a detector having a wavelength of 254 nm for UV rays (ultraviolet rays) is used for detection.

The photosensitive resin composition of the present invention (hereinafter, may be simply referred to as "the composition of the present invention" or "the resin composition of the present invention") is selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor. It is characterized by containing at least one polymer precursor (specific polymer precursor), a thermobase generator represented by the following formula (N1) or (N2), and a photosensitizer.

<Specific thermal base generator>

The thermobase generator of the present invention is represented by the following formula (N1) or (N2). Hereinafter, this thermobase generator may be referred to as a "specific thermobase generator" to distinguish it from other thermobase generators.

式中、Ｒ^N1およびＲ^N2はそれぞれ独立に、水素原子または１価の有機基を表し、Ｒ^N3およびＲ^N4はそれぞれ独立に、水素原子または置換基を有していてもよい脂肪族炭化水素基であり、ただしこの置換基はヒドロキシル基以外の酸基であることはなく、Ｒ^N1とＲ^N2は互いに連結して環状構造を形成してもよく、Ｒ^N3とＲ^N4は互いに連結して環状構造を形成してもよく、Ｒ^N1とＲ^N3は互いに連結して環状構造を形成してもよく、Ｒ^N2とＲ^N4は互いに連結して環状構造を形成してもよく、Ｘは単結合またはカルボニル基を表し、Ｘが単結合の場合、Ｙは単結合または２価の有機基を表し、Ｘがカルボニル基の場合、Ｙは２価の有機基を表す。

In the formula, ^RN1 and ^RN2 each independently represent a hydrogen atom or a monovalent organic group, and ^RN3 and ^RN4 independently represent an aliphatic hydrocarbon which may have a hydrogen atom or a substituent, respectively. It is a group, but this substituent is not an acid group other than a hydroxyl group, ^RN1 and ^RN2 may be linked to each other to form a cyclic structure, and ^RN3 and ^RN4 may be linked to each other. An annular structure may be formed, ^RN1 and ^RN3 may be connected to each other to form an annular structure, ^RN2 and ^RN4 may be connected to each other to form an annular structure, and X is simply. When X is a single bond, Y represents a single bond or a divalent organic group, and when X is a carbonyl group, Y represents a divalent organic group.

In the formula, ^RN1 and ^RN2 each independently represent a hydrogen atom or a monovalent organic group, and ^RN3 and ^RN4 independently represent an aliphatic hydrocarbon which may have a hydrogen atom or a substituent, respectively. It is a group. However, this substituent cannot be an acid group other than a hydroxyl group.

In the present specification, an acid group other than the hydroxyl group may be referred to as "acid group A". Examples of the acid group A include a carboxyl group, a sulfonic acid group, and a phosphoric acid group.

R ^N1 and R ^N2 are independently hydrogen atoms or monovalent organic groups.

As the monovalent organic group, an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms) or an aliphatic hydrocarbon group (preferably 1 to 60 carbon atoms). , 1-36 is more preferable, 1 to 24 is even more preferable), and an aliphatic hydrocarbon group is more preferable. As the aliphatic hydrocarbon group, an alkyl group (preferably having 1 to 36 carbon atoms, more preferably 3 to 24 carbon atoms, still more preferably 4 to 12; for example, a substituent Alk described later, among which a butyl group and a pentyl group, Hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, etc.), alkenyl group (2 to 24 carbon atoms are preferable, 2 to 12 are more preferable, 2 to 6 are even more preferable; For example, a vinyl group, an allyl group, a propenyl group, a butenyl group, a butadienyl group, etc.) are preferable.

When ^RN1 and ^RN2 are aliphatic hydrocarbon groups, the preferred ones are the above alkyl group, the above alkenyl group, and a hydroxyalkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, 1 to 1). 4 is more preferable; the number of hydroxyl groups is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1-3; for example, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, etc.), a sulfanyl alkyl group (for example, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, etc.) The number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, further preferably 1 to 4; the number of sulfanyl groups is preferably 1 to 12, more preferably 1 to 6, further preferably 1-3; for example, sulfanyl. Methyl group, sulfanyl ethyl group, sulfanyl propyl group, etc.), alkyl halide group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3; the number of halogen atoms is preferably 1 to 12). , 1 to 6 are more preferable, and 1 to 3 are even more preferable; for example, an alkyl fluoride group, an alkyl chloride group, an alkyl bromide group, an alkyl iodide group, and an arylalkyl group (7 to 23 carbon atoms are preferable, 7 are preferable. ~ 19 is more preferable, and 7 to 11 is even more preferable; for example, a benzyl group, a phenylethyl group, a naphthylmethyl group, a naphthylethyl group, a biphenylmethyl group, etc.), a hydroxyarylalkyl group (preferably 7 to 23 carbon atoms, 7). ~ 19 are more preferable, 7 to 11 are more preferable), alkoxyalkyl groups (2 to 12 carbon atoms are preferable, 2 to 6 are more preferable, and 2 to 3 are more preferable), aryloxyalkyl groups (7 to 7 carbon atoms are more preferable). 23 is preferable, 7 to 19 is more preferable, 7 to 11 is further preferable), an alkylthioalkyl group (2 to 12 carbon atoms is preferable, 2 to 6 is more preferable, and 2 to 3 is more preferable), an arylthioalkyl group. (Preferably 7 to 23 carbon atoms, more preferably 7 to 19; even more preferably 7 to 11), alkenyloxyalkyl groups (preferably 3 to 24 carbon atoms, more preferably 3 to 12 carbon atoms, even more preferably 3 to 6 carbon atoms). ), An alkenylthioalkyl group (preferably having 3 to 24 carbon atoms, more preferably 3 to 12 carbon atoms, still more preferably 3 to 6 carbon atoms) and the like.

^RN1 and ^RN2 may further have a substituent, and may further have a substituent T, which will be described later.

It is preferable that ^RN1 and ^RN2 are both hydrogen atoms, or one is a hydrogen atom and one is a monovalent organic group.

R ^N1 and R ^N2 may be connected to each other to form an annular structure. As used herein, the term "linkage" means that two or more groups are bonded to form a continuous state, and that some atoms are lost and condensed. When forming the cyclic structure, an oxygen atom, a sulfur atom, a nitrogen atom (amino group) or the like may be interposed. Examples of the ring formed include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a pyrrolidine ring, a piperidine ring, an oxylan ring, an oxetane ring, a tetrahydrofuran ring, a tetrahydropyran ring, a tetrahydronaphthalene ring, and a decahydro. A naphthalene ring and the like can be mentioned.

^RN3 and ^RN4 are aliphatic hydrocarbon groups which may independently have a hydrogen atom or a substituent. However, this substituent does not have an acid group A (an acid group other than the hydroxyl group, for example, a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc.). That is, when the substituent has an acid group, the acid group is a hydroxyl group. The aliphatic hydrocarbon group may have an aromatic hydrocarbon group (for example, a substituent Aly described later) as a substituent.

As the substituent of the aliphatic hydrocarbon group (in the present specification, the substituent defined here is referred to as "substituent T"), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms). 6 to 10 are more preferred), hydroxyl groups, alkoxyl groups (preferably 1 to 12 carbons, more preferably 1 to 6 and even more preferably 1-3), aryloxy groups (preferably 6 to 22 carbons, 6). ~ 18 is more preferable, 6 to 10 are more preferable), alkenyloxy groups (2 to 12 carbon atoms are preferable, 2 to 6 are more preferable, 2 to 3 are more preferable), arylalkyloxy groups (7 to 7 carbon atoms are more preferable). 23 is preferable, 7 to 19 is more preferable, 7 to 11 is more preferable), an acyl group (2 to 12 carbon atoms is preferable, 2 to 6 is more preferable, 2 to 3 is more preferable), and an aryloyl group (carbon number is preferable). 7 to 23 are preferable, 7 to 19 are more preferable, 7 to 11 are further preferable), an alkoxycarbonyl group (2 to 12 carbon atoms are preferable, 2 to 6 are more preferable, and 2 to 3 are more preferable), aryloxy. A carbonyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 11), an alkylsulfonyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms). (Preferably), arylsulfonyl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10), halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), sulfanyl group, alkylthio Group (preferably 1-12 carbon atoms, more preferably 1-6, further preferably 1-3), alkenylthio group (preferably 2-12 carbon atoms, more preferably 2-6, still more preferably 2-3 ), Arylthio groups (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10), arylalkylthio groups (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, 7 to 11 carbon atoms). Is more preferable), cyano group, nitro group and the like.

Of the substituents exemplified above, those that can be substituted may have each of the substituents exemplified above as long as the effects of the present invention are exhibited. For example, it may be an aryl halide group in which a halogen atom is substituted on the aryl group.

When ^RN3 and ^RN4 are aliphatic hydrocarbon groups which may have a substituent, the total number of carbon atoms including the substituent is preferably 1 to 60, more preferably 1 to 36, and 1 to 24. Is even more preferable, 1 to 18 is even more preferable, and 1 to 12 is even more preferable. Specifically, as the aliphatic hydrocarbon group, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4; for example, a substituent Alk described later, among which a methyl group is used. , Ethyl group, propyl group, butyl group, pentyl group, hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (2 to 24 carbon atoms are preferable, 2 to 12 are more preferable, 2 ~ 6 is more preferred; for example, a vinyl group, an allyl group, a propenyl group, a butenyl group, a butazienyl group, etc.) are preferable.

When ^RN3 and ^RN4 are organic groups other than hydrogen, they are excellent in solvent solubility because they are aliphatic hydrocarbon groups instead of aromatic hydrocarbon groups. Further, when it is an aliphatic hydrocarbon group, it does not contain an acid group A, so that it is similarly excellent in solvent solubility.

R ^N3 and R ^N4 is preferably at least one of R ^N3 and R ^N4 is an aliphatic hydrocarbon group when R ^N1 and R ^N2 are both hydrogen atoms, either R ^N1 and R ^N2 are monovalent When it is an organic group of, it is preferable that both ^RN3 and ^{RN4 are hydrogen atoms.}

R ^N3 and R ^N4 may be connected to each other to form an annular structure. In forming the cyclic structure, an oxygen atom, a sulfur atom, a nitrogen atom (amino group) or the like may be interposed. The cyclic structure to be formed is preferably a 5-membered ring or a 6-membered ring, and for example, a pyrrol ring, a pyrroline ring, an imidazole ring, an imidazoline ring, a pyrazole ring, a pyrazoline ring, a pyrrolidine ring, an imidazolidine ring, a pyrazolidine ring, and a piper. Examples include a lysine ring, a piperazine ring, and a morpholine ring.

R ^N1 and R ^N3 and R ^N2 and R ^N4 may be connected to each other to form an annular structure. The cyclic structure to no R ^N1 and R ^N3 R ^N2 and R ^N4 are formed by connecting, for example, pyrrole ring, pyrroline ring, an imidazole ring, imidazoline ring, pyrazole ring, pyrazoline ring, pyrrolidine ring, imidazolidine ring, Examples thereof include a pyrazolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring. However, it is preferable that ^RN1 and ^RN3 , and ^RN3 and ^RN4 do not form a cyclic structure from the viewpoint of decomposing by heating and releasing a base.

X represents a single bond or a carbonyl group. When X is a single bond, Y represents a single bond or a divalent organic group. When X is a carbonyl group, Y represents a divalent organic group. When X is a carbonyl group, it is preferable because decarboxylation proceeds more effectively when a specific thermobase generator is decomposed by heat. In the present invention, it is preferable that X and Y are single bonds.

When Y is a divalent organic group, its structure is not particularly limited, but an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10; for example, described later). The substituent (Ary) or the aliphatic hydrocarbon group (preferably 1 to 60 carbon atoms, more preferably 1 to 36, still more preferably 1 to 24) is preferable, and the aliphatic hydrocarbon group is more preferable. As the aliphatic hydrocarbon group, an alkylene group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3; for example, a methylene group, an ethylene group, a propanediyl group, a butanjiyl group, a pentandiyl group). , Hexandiyl group, heptandyl group, octanediyl group, nonandyl group, decandyl group, undecandyl group, dodecandyl group, etc.), alkenylene group (2 to 12 carbon atoms are preferable, 2 to 6 are more preferable, and 2 to 3 are further. Preferred; for example, a vinylene group, an allylene group, a metallicene group, a propenylene group, etc.), an arylene group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10; for example, a phenylene group, a naphthylene group. Etc.), arylene alkylene group (7 to 23 carbon atoms are preferable, 7 to 19 is more preferable, 7 to 11 is more preferable; for example, phenylene methylene group, phenylene ethylene group, naphthylene methylene group, naphthylene ethylene group, phenylene. Bismethylene group, etc.), an alkylene group interposing an oxygen atom or a sulfur atom (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3; the number of oxygen atom or sulfur atom is 1 to 12 Of the above, 1 to 6 are more preferable, and 1 to 3 are even more preferable; for example, an oxylangidiyl group, an oxetandyl group, a tetrahydrofurandiyl group, a tetrahydropyrandiyl group, formula (O):-[(CH ₂ ) _no −Z. −] _mo − (CH ₂ ) _no −, no = 1-6, mo = 1-6, Z: O, C (= O), OC (= O), C (= O) O, S), these A linking group in which a plurality of the groups of the above are linked is preferable.

When Y is an organic group, Y may have a substituent T, which will be described later.

The specific thermal base generator is preferably used by being contained in the photosensitive resin composition, and is preferably decomposed by heating in the photosensitive resin composition to generate a base. The decomposition temperature is not particularly limited, but is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, and even more preferably 100 ° C. or higher. The upper limit is preferably 450 ° C. or lower, more preferably 350 ° C. or lower, and even more preferably 250 ° C. or lower.

As described above, the specific thermal base generator is preferably decomposed by heating in the photosensitive resin composition, and the decomposed base acts as a curing agent for cyclizing and curing the specific polymer precursor. Is particularly preferable. In such an embodiment, according to the specific thermobase generator, the photosensitivity after curing is not impaired by reacting with the photosensitizer contained in the photosensitive resin composition or the like. Is particularly preferable because it can be effectively maintained and the subsequent good exposure and development characteristics can be exhibited.

When a specific thermobase generator is decomposed by heating, it is preferable that the carboxyl group site in the formula is dissociated from other sites and decomposed by decarboxylation. The boiling point (pressure 1013.25 hPa) of a compound containing a nitrogen atom that becomes a base after decomposition, in other words, a compound containing an amino group (hereinafter, this compound may be referred to as a "decomposition-generated base") is 30 ° C. The temperature is preferably 50 ° C. or higher, more preferably 65 ° C. or higher, and even more preferably 65 ° C. or higher. When the boiling point of the decomposition-generated base is not too low, it is possible to effectively cyclize a specific polymer precursor and cure the photosensitive resin composition without volatilizing from the photosensitive resin composition.

From this point of ^{view, R N1, R N2, R} N3, R N4 , alone, or in combinations thereof, preferably has a carbon number of accordingly. The total number of carbon atoms of ^{R N1, R N2, R N3} , R N4 is preferably 3 or more, and more preferably 4 or more. The upper limit is preferably 20 or less.

The upper limit of the boiling point of the decomposition-produced base is not particularly limited, but it is preferably 600 ° C. or lower, more preferably 400 ° C. or lower, and further preferably 300 ° C. or lower.

式中、Ｒ^N31、Ｒ^N32およびＲ^N33は、それぞれ独立に、水素原子または置換基を有していてもよい脂肪族炭化水素基である。ただしこの置換基は酸基Ａを有することはない。脂肪族炭化水素基は、置換基として、芳香族炭化水素基（例えば、後述する置換基Ａｒｙ）を有していてもよい。脂肪族炭化水素基が有してもよい置換基としては、上記置換基Ｔが挙げられる。

The above formula (N1) is preferably any of the following formulas (N1-1) to (N1-4).

In the formula, ^RN31 , ^RN32 and ^RN33 are aliphatic hydrocarbon groups which may independently have a hydrogen atom or a substituent. However, this substituent does not have an acid group A. The aliphatic hydrocarbon group may have an aromatic hydrocarbon group (for example, a substituent Aly described later) as a substituent. Examples of the substituent that the aliphatic hydrocarbon group may have include the above-mentioned Substituent T.

When ^RN31 , ^RN32 and ^RN33 are aliphatic hydrocarbon groups which may have substituents, the total number of carbon atoms including the substituents is preferably 1 to 60, more preferably 1 to 36. Preferably, 1 to 24 are even more preferable, 1 to 18 are even more preferable, and 1 to 12 are even more preferable. Specifically, as the aliphatic hydrocarbon group, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4; for example, a substituent Alk described later, among which a methyl group is used. , Ethyl group, propyl group, butyl group, pentyl group, hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (2 to 24 carbon atoms are preferable, 2 to 12 are more preferable, 2 ~ 6 is more preferred; for example, a vinyl group, an allyl group, a propenyl group, a butenyl group, a butazienyl group, etc.) are preferable.

R ^N31 and R ^N32 may be connected to each other to form an annular structure. In forming the cyclic structure, an oxygen atom, a sulfur atom, a nitrogen atom (amino group) or the like may be interposed. The cyclic structure to be formed is preferably a 5-membered ring or a 6-membered ring, and for example, a pyrrol ring, a pyrroline ring, an imidazole ring, an imidazoline ring, a pyrazole ring, a pyrazoline ring, a pyrrolidine ring, an imidazolidine ring, a pyrazolidine ring, and a piper. Examples include a lysine ring, a piperazine ring, and a morpholine ring.

^RN31 , ^RN32 and ^RN33 may each independently connect with the methylene group between the nitrogen atom and the carbonyl group in the formula to form a cyclic structure. Examples of the cyclic structure formed include a pyrrol ring, a pyrroline ring, an imidazole ring, an imidazoline ring, a pyrazole ring, a pyrazoline ring, a pyrrolidine ring, an imidazolidine ring, a pyrazolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring. Can be mentioned. However, it is preferable that the annular structure here is not formed.

^RN11 represents a monovalent organic group.

As the monovalent organic group, an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms) or an aliphatic hydrocarbon group (preferably 1 to 60 carbon atoms). , 1-36 is more preferable, 1 to 24 is even more preferable), and an aliphatic hydrocarbon group is more preferable. As the aliphatic hydrocarbon group, an alkyl group (preferably having 1 to 36 carbon atoms, more preferably 3 to 24 carbon atoms, still more preferably 4 to 12; for example, a substituent Alk described later, among which a butyl group and a pentyl group, Hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, etc.), alkenyl group (2 to 24 carbon atoms are preferable, 2 to 12 are more preferable, 2 to 6 are even more preferable; For example, a vinyl group, an allyl group, a propenyl group, a butenyl group, a butadienyl group, etc.) are preferable.

When ^RN11 is an aliphatic hydrocarbon group, the preferred ones are the above alkyl group, the above alkenyl group, and a hydroxyalkyl group (1 to 12 carbon atoms are preferable, 1 to 6 are more preferable, and 1 to 4 are further preferable. Preferred; the number of hydroxyl groups is preferably 1-12, more preferably 1-6, even more preferably 1-3; for example, hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, etc.), sulfanylalkyl group (1 carbon number). ~ 12 is preferred, 1-6 is more preferred; 1-4 is more preferred; the number of sulfanyl groups is preferably 1-12, 1-6 is more preferred, 1-3 is more preferred; for example, sulfanylmethyl groups, Sulfanyl ethyl group, sulfanyl propyl group, etc.), alkyl halide groups (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3; the number of halogen atoms is preferably 1 to 12 and 1 to 1 6 is more preferable, 1 to 3 is more preferable; for example, an alkyl fluoride group, an alkyl chloride group, an alkyl bromide group, an alkyl iodide group, an aryl alkyl group (7 to 23 carbon atoms are preferable, and 7 to 19 are preferable. More preferably, 7 to 11 are even more preferable; for example, a benzyl group, a phenylethyl group, a naphthylmethyl group, a naphthylethyl group, a biphenylmethyl group, etc.), a hydroxyarylalkyl group (preferably having 7 to 23 carbon atoms, preferably 7 to 19). More preferably, 7 to 11 are more preferable), an alkoxyalkyl group (2 to 12 carbon atoms are preferable, 2 to 6 are more preferable, and 2 to 3 are more preferable), and an aryloxyalkyl group (7 to 23 carbon atoms is preferable). , 7-19 is more preferred, 7-11 is more preferred), alkylthioalkyl groups (2-12 carbon atoms are preferred, 2-6 are more preferred, 2-3 are more preferred), arylthioalkyl groups (carbon atoms are preferred). 7 to 23 are preferable, 7 to 19 are more preferable, 7 to 11 are further preferable), alkenyloxyalkyl groups (3 to 24 carbon atoms are preferable, 3 to 12 are more preferable, 3 to 6 are more preferable), alkenyl. Examples thereof include a thioalkyl group (preferably having 3 to 24 carbon atoms, more preferably 3 to 12 carbon atoms, and even more preferably 3 to 6 carbon atoms).

^RN11 may further have a substituent, and may further have the above-mentioned substituent T.

^RN11 may be linked to the carbon atom it substitutes to form a cyclic structure. In forming the cyclic structure, an oxygen atom, a sulfur atom, a nitrogen atom (amino group) or the like may be interposed. Examples of the ring formed include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a pyrrolidine ring, a piperidine ring, an oxylan ring, an oxetane ring, a tetrahydrofuran ring, a tetrahydropyran ring, a tetrahydronaphthalene ring, and a decahydro. A naphthalene ring and the like can be mentioned.

^RN12 is a divalent linking group, and examples of Y in the above formula (N1) can be mentioned. Among them, an alkylene group (preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, 1 or 2 is preferable. More preferred; for example, methylene group, ethylene group, etc.), alkenylene group (2 to 12 carbon atoms are preferable, 2 to 6 are more preferable, and 2 to 3 are even more preferable; for example, vinylene group, arylene group, metalylene group, propenylene. Group etc.) is preferable. ^RN12 may have a substituent T.

Ar ^N is an aromatic hydrocarbon group (for example, the substituent Ary described later is mentioned), and among them, an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms). For example, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, etc.) are preferable. Ar ^N may have a substituent T.

^RN12 or Ar ^N may ^{be linked with the carbon atom substituted by RN12} or the nitrogen atom in the formula to form a cyclic structure.

The ^{cyclic structure formed by connecting RN12} and the carbon atom substituted by the RN12 may be mediated by an oxygen atom, a sulfur atom, a nitrogen atom (amino group) or the like. Examples of the ring formed include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a pyrrolidine ring, a piperidine ring, an oxylan ring, an oxetane ring, a tetrahydrofuran ring, a tetrahydropyran ring, a tetrahydronaphthalene ring, and a decahydro. A naphthalene ring and the like can be mentioned.

Examples of the cyclic structure formed by linking Ar ^N and ^{the carbon atom substituted by RN12} include a benzocyclobutane ring, a benzocyclopentane ring, a tetrahydronaphthalene ring, a fluorene ring, an indane ring, and an acenaphthene ring.

Examples of the ^{cyclic structure formed by connecting Ar N} and the nitrogen atom in the formula include an indole ring, an isoindoline ring, an indole ring, an isoindole ring, and a tetrahydroquinoline ring.

Examples of the compound represented by the formula (N1) or (N2) include the following exemplified compounds, but the present invention is not construed as being limited thereto. The following exemplified compound shows the embodiment of the formula (N1). These can be converted into the embodiment of the formula (N2) by a coexisting solvent or the like.

The compound represented by the formula (N1) or (N2) can be produced by a conventional method. Moreover, a commercially available reagent can be utilized. For example, among the compounds listed in the catalog of amino acid / peptide-related reagents manufactured by Tokyo Chemical Industry Co., Ltd., those satisfying the formula (N1) or (N2) can be preferably used.

The molecular weight of the specific thermobase generator is preferably 30 to 1000, more preferably 80 to 500.

The content of the specific thermal base generator is preferably 0.01 to 50% by mass with respect to the total solid content of the photosensitive resin composition. The lower limit is more preferably 0.05% by mass or more, further preferably 0.1% by mass or more. The upper limit is more preferably 10% by mass or less, further preferably 5% by mass or less.

The content of the specific thermobase generator with respect to 100 parts by mass of the polymer precursor is preferably 0.015 parts by mass or more, more preferably 0.075 parts by mass or more, and 0.15 parts by mass or more. Is more preferable. The upper limit is, for example, preferably 15.0 parts by mass or less, more preferably 7.5 parts by mass or less, and further preferably 1.5 parts by mass or less.

By setting the content of the specific thermobase generator to the above lower limit value or more, it is preferable in that good storage stability can be ensured in the photosensitive resin composition and the mechanical properties of the cured film can be suitably realized. By setting the value to the above upper limit or less, it is preferable in that corrosion resistance of a metal (for example, copper used for wiring or the like) can be ensured.

As the specific thermobase generator, one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.

The photosensitive resin composition of the present invention may or may not contain a thermobase generator other than the specific thermobase generator. When other thermobase generators are included, those described in WO2015 / 199219A and WO2015 / 199220A are exemplified, and their contents are incorporated in the present specification. Further, in the present invention, it is possible to make the configuration substantially free of other thermobase generators other than the specific thermobase generator. The term "substantially free" means that the content of the specific thermobase generator contained in the photosensitive resin composition of the present invention is 5% by mass or less, preferably 3% by mass or less, and more preferably 1. It means that it is mass%.

Further, the photobase generator may or may not be contained together with the specific thermobase generator.

<Polymer precursor>

The photosensitive resin composition of the present invention contains a polymer precursor (specific polyimide precursor) selected from a polyimide precursor and a polybenzoxazole precursor. As the specific polymer precursor, a polyimide precursor is more preferable.

Ａ¹およびＡ²は、それぞれ独立に酸素原子またはＮＨを表し、Ｒ¹¹¹は、２価の有機基を表し、Ｒ¹¹⁵は、４価の有機基を表し、Ｒ¹¹³およびＲ¹¹⁴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 polyimide precursor preferably contains a structural unit represented by the following formula (1). With such a configuration, a composition having more excellent film strength can be obtained.

A ¹ and A ² independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ are independent, respectively. Represents a hydrogen atom or a monovalent organic group.

A ¹ and A ² are independently oxygen atoms or NH, and oxygen atoms are preferable.

<<< R ¹¹¹ >>>

R ¹¹¹ represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, a heteroaromatic group, or a group consisting of a combination thereof, which have 2 to 20 carbon atoms. A linear aliphatic group, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group consisting of a combination thereof. Preferably, an aromatic group having 6 to 20 carbon atoms is more preferable.

R ¹¹¹ is preferably derived from diamine. Examples of the diamine used for producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one kind of diamine may be used, or two or more kinds of diamines may be used.

Specifically, the diamine is derived from a linear aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof. It is preferably a diamine containing an aromatic group having 6 to 20 carbon atoms, and more preferably a diamine containing an aromatic group. Examples of aromatic groups include:

In the formula, A is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be replaced with a single bond or a fluorine atom, −O−, −C (= O) −, −S−, −S. (= O) _2- , -NHCO-, and a group selected from a combination thereof are preferable, and a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O- , -C (= O) -, - more preferably a group selected from, -CH ₂ - - S- and _{-SO 2, - O -, -} S -, - SO 2 -, - C ( It is more preferably a divalent group selected from the group consisting of CF ₃ ) ₂ − and −C (CH ₃ ) _{2 −.}

Specific examples of the diamine include 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; meta and paraphenylenediamine, diaminotoluene, 4,4'-and 3 , 3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'-and 3,3'-diaminodiphenylmethane, 4,4'-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 (4,4'-diamino-2,2'-dimethylbiphenyl), 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4-amino) Phenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) ) Hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxy) Phenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 4,4'-diaminoparatelphenyl, 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'-diaminodiphenyl sulfone, 1,3-bis (4-aminophenoxy) Nzen, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenyl) 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- (3', 5'-diaminobenzoyloxy) ethyl methacrylate, 2,4- And 2,5-diaminocumen, 2,5-dimethyl-paraphenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-paraphenylenediamine, 2,4,6-trimethyl-metaphenylenediamine, bis ( 3-Aminopropyl) tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-aminophenyl) ethane, diaminobenzanilide, ester of diaminobenzoic acid, 1,5 -Diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis (4-aminophenyl) hexafluoropropane, 1,4-bis (4-aminophenyl) octafluorobutane, 1,5-bis (4-aminophenyl) Decafluoropentane, 1,7-bis (4-aminophenyl) tetradecafluoroheptane, 2,2-bis [4- (3-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-Aminophenoxy) -3,5-bis (trifluoromethyl) phenyl] hexafluoropropane, parabis (4-amino-2-trifluoromethi) Ruphenoxy) Benzene, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4,4'- Bis (4-amino-2-trifluoromethylphenoxy) diphenyl sulfone, 4,4'-bis (3-amino-5-trifluoromethylphenoxy) diphenyl sulfone, 2,2-bis [4- (4-amino-) 3-Trifluoromethylphenoxy) phenyl] hexafluoropropane, 3,3', 5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoro) Included are at least one diamine selected from methyl) biphenyl, 2,2', 5,5', 6,6'-hexafluorotridin and 4,4'-diaminoquaterphenyl.

Further, the diamines (DA-1) to (DA-18) shown below are also preferable.

Further, a diamine having at least two or more alkylene glycol units in the main chain is also mentioned as a preferable example. A diamine containing two or more of one or both of an ethylene glycol chain and a propylene glycol chain in one molecule is preferable, and a diamine containing no aromatic ring is preferable. Specific examples include Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, Jeffamine (registered trademark) ED-900, Jeffamine (registered trademark) ED-2003, and Jeffamine (registered trademark). ) EDR-148, Jeffamine® EDR-176, D-200, D-400, D-2000, D-4000 (trade name, manufactured by HUNTSMAN), 1- (2- (2- (2)) -Aminopropoxy) ethoxy) propoxy) propoxy) propan-2-amine, 1- (1- (1- (2-aminopropoxy) propoxy-2-yl) oxy) propan-2-amine, etc., but are limited to these. Not done.

Jeffamine® KH-511, Jeffamine® ED-600, Jeffamine® ED-900, Jeffamine® ED-2003, Jeffamine® EDR-148, The structure of Jeffamine® EDR-176 is shown below.

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

R ¹¹¹ is preferably represented by ^{−Ar 0} −L ⁰ −Ar ⁰ − from the viewpoint of the flexibility of the obtained cured film. However, Ar ⁰ is independently an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), and a phenylene group is preferable. L ⁰ is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, −O−, −C (= O) −, −S−, −S (= O). ₂ -, - NHCO- and represents a group selected from these combinations. The preferred range is synonymous with A above.

Ｒ⁵⁰〜Ｒ⁵⁷は、それぞれ独立に水素原子、フッ素原子または１価の有機基であり、Ｒ⁵⁰〜Ｒ⁵⁷の少なくとも１つはフッ素原子、メチル基、フルオロメチル基、ジフルオロメチル基、または、トリフルオロメチル基である。

Ｒ⁵⁰〜Ｒ⁵⁷の１価の有機基として、炭素数１〜１０（好ましくは炭素数１〜６）の無置換のアルキル基、炭素数１〜１０（好ましくは炭素数１〜６）のフッ化アルキル基等が挙げられる。

Ｒ⁵⁸およびＲ⁵⁹は、それぞれ独立にフッ素原子、フルオロメチル基、ジフルオロメチル基、または、トリフルオロメチル基である。

式（５１）または（６１）の構造を与えるジアミン化合物としては、ジメチル−４,４’−ジアミノビフェニル、２，２’−ビス（トリフルオロメチル）−４，４’−ジアミノビフェニル、２，２’−ビス（フルオロ）−４，４’−ジアミノビフェニル、４，４’−ジアミノオクタフルオロビフェニル等が挙げられる。これらの１種を用いるか、２種以上を組み合わせて用いてもよい。

From the viewpoint of i-ray transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, a divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-ray transmittance and availability.

R ^{50 to} R ⁵⁷ are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and ^{at least one of R 50 to} R ⁵⁷ is a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group, or It is a trifluoromethyl group.

As a ^{monovalent organic group of R 50 to} R ⁵⁷ , an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a hook having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkylated group.

R ⁵⁸ and R ⁵⁹ are independently fluorine atoms, fluoromethyl groups, difluoromethyl groups, or trifluoromethyl groups, respectively.

Examples of the diamine compound giving the structure of the formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2. Examples thereof include'-bis (fluoro) -4,4'-diaminobiphenyl and 4,4'-diaminooctafluorobiphenyl. One of these may be used, or two or more thereof may be used in combination.

Ｒ¹¹²は、Ａと同義であり、好ましい範囲も同じである。

<<< R ¹¹⁵ >>>

^{R 115} in the formula (1) represents a tetravalent organic group. The tetravalent organic group is preferably a group containing an aromatic ring, and more preferably a group represented by the following formula (5) or formula (6).

R ¹¹² is synonymous with A and has the same preferred range.

Ｒ¹¹⁵は、４価の有機基を表す。Ｒ¹¹⁵は式（１）のＲ¹¹⁵と同義である。

^{Specific examples of the tetravalent organic group represented by R 115} in the formula (1) include a tetracarboxylic acid residue remaining after removing the acid dianhydride group from the tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).

R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ has the same meaning as R ¹¹⁵ in formula (1).

Specific examples of tetracarboxylic acid dianhydrides include pyromellitic acid, pyromellitic acid dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 3,3', 4. , 4'-diphenylsulfide tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylmethanetetracarboxylic acid dianhydride, 2,2', 3,3'-diphenylmethanetetracarboxylic acid dianhydride, 2,3,3', 4'-biphenyltetracarboxylic acid Dianoxide, 2,3,3', 4'-benzophenone tetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1 , 4,5,7-naphthalenetetracarboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propanedi Anhydrous, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenyl hexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydride, 1, 4,5,6-naphthalenetetracarboxylic acid dianhydride, 2,2', 3,3'-diphenyltetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 1, 2,4,5-Naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride, 1,1- Bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, In addition, at least one selected from these alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms is exemplified.

Further, the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below are also mentioned as preferable examples.

<<< R ¹¹³ and R ¹¹⁴ >>>

^{R 113} and R ¹¹⁴ in the formula (1) independently represent a hydrogen atom or a monovalent organic group. At ^{least one of R 113} and R ¹¹⁴ preferably contains a radically polymerizable group, and more preferably both contain a radically polymerizable group. Examples of the radically polymerizable group include a group capable of a cross-linking reaction by the action of a radical, and a preferable example thereof is a group having an ethylenically unsaturated bond.

Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth) acryloyl group, and a group represented by the following formula (III).

In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, with a methyl group being more preferred.

In formula (III), R ²⁰¹ is an alkylene group having 2 to 12 carbon atoms, −CH ₂ CH (OH) CH ₂ − or a (poly) oxyalkylene group having 4 to 30 carbon atoms (the alkylene group has 1 carbon atom). ~ 12 is preferable, 1 to 6 is more preferable, and 1 to 3 are particularly preferable; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3). The (poly) oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.

Examples of suitable R ²⁰¹ are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butandyl group, 1,3-butandyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group. , -CH ₂ CH (OH) CH _{2-, and} more preferably an ethylene group, a propylene group, a trimethylene group, and -CH ₂ CH (OH) CH _2-.

Particularly preferably, R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethylene group.

As a preferred embodiment of the polyimide precursor in the present invention, an aliphatic group, an aromatic group and an aryl having one, two or three, preferably one acid group as the monovalent organic group of ^{R 113} or R ^114. Alkyl groups and the like can be mentioned. Specific examples thereof include an aromatic group having an acid group having 6 to 20 carbon atoms and an arylalkyl group having an acid group having 7 to 25 carbon atoms. More specifically, a phenyl group having an acid group and a benzyl group having an acid group can be mentioned. The acid group is preferably a hydroxyl group. That is, R ¹¹³ or R ¹¹⁴ is preferably a group having a hydroxyl group.

As the ^{monovalent organic group represented by R 113} or R ^114, a substituent that improves the solubility of the developing solution is preferably used.

It is more preferable that R ¹¹³ or R ¹¹⁴ is 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 ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and an alkyl group substituted with an aromatic group is more preferable.

The alkyl group preferably has 1 to 30 carbon atoms (3 or more in the case of a cyclic group). 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. , Isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, and 2-ethylhexyl group. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl 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 cyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a phenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group and a pinenyl group. Can be mentioned. Further, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described below is preferable. In the present specification, the alkyl group defined here is referred to as "Alk".

Specific examples of the aromatic group include a substituted or unsubstituted aromatic hydrocarbon group (the cyclic structure constituting the group includes a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an inden ring, and azulene. Rings, heptalene rings, indacen rings, perylene rings, pentacene rings, acenaphthene rings, phenanthrene rings, anthracene rings, naphthacene rings, chrysen rings, triphenylene rings, etc.) The group is referred to as "Ary") or a substituted or unsubstituted aromatic heterocyclic group (the cyclic structure constituting the group includes a fluorene ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, etc. Ppyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indridin ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthylidine ring, quinoxalin ring, quinoxazoline ring, isoquinoline ring. , Carbazole ring, phenanthridin ring, aclysine ring, phenanthroline ring, thiantolene ring, chromene ring, xanthene ring, phenoxatiin ring, phenothiazine ring or phenazine ring) It is called "Aro").

It is also preferable that the polyimide precursor has a fluorine atom in the constituent unit. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, more preferably 20% by mass or less. There is no particular upper limit, but 50% by mass or less is practical.

Further, for the purpose of improving the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with the structural unit represented by the formula (1). Specific examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (paraaminophenyl) octamethylpentasiloxane.

Ａ¹¹およびＡ¹²は、酸素原子またはＮＨを表し、Ｒ¹¹¹およびＲ¹¹²は、それぞれ独立に、２価の有機基を表し、Ｒ¹¹³およびＲ¹¹⁴は、それぞれ独立に、水素原子または１価の有機基を表し、Ｒ¹¹³およびＲ¹¹⁴の少なくとも一方は、ラジカル重合性基を含む基であり、ラジカル重合性基であることが好ましい。

The structural unit represented by the formula (1) is preferably the structural unit represented by the formula (1-A).

A ¹¹ and A ¹² represent an oxygen atom or NH, R ¹¹¹ and R ¹¹² each independently represent a divalent organic radical, and R ¹¹³ and R ¹¹⁴ independently represent a hydrogen atom or a monovalent. Representing an organic group, ^{at least one of R 113} and R ¹¹⁴ is a group containing a radically polymerizable group, and is preferably a radically polymerizable group.

A ¹¹ , A ¹² , R ¹¹¹ , R ¹¹³ and R ^{114 are independently synonymous with A 1} , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in equation (1), respectively, and so are the preferred ranges. be.

R ¹¹² has the same meaning as R ¹¹² in formula (5), and preferred ranges are also the same.

In the polyimide precursor, the structural unit represented by the formula (1) may be one kind, or two or more kinds. Further, the structural isomer of the structural unit represented by the formula (1) may be contained. Further, the polyimide precursor may contain other types of structural units in addition to the structural units of the above formula (1).

As one embodiment of the polyimide precursor in the present invention, a polyimide precursor in which 50 mol% or more, more 70 mol% or more, particularly 90 mol% or more of all the structural units is the structural unit represented by the formula (1). Is exemplified. The upper limit is practically 100 mol% or less.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 2000 to 500000, more preferably 5000 to 100,000, and even more preferably 1000 to 50000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2000 to 50000, and even more preferably 4000 to 25000.

The degree of dispersion of the molecular weight of the polyimide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.

The polyimide precursor can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, the dicarboxylic acid or the dicarboxylic acid derivative is obtained by halogenating it with a halogenating agent and then reacting it with a diamine.

In the method for producing a polyimide precursor, it is preferable to use an organic solvent in the reaction. The organic solvent may be one kind or two or more kinds.

The organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.

In the production of the polyimide precursor, it is preferable to include a step of precipitating a solid. Specifically, the polyimide precursor in the reaction solution can be precipitated in water, and the polyimide precursor such as tetrahydrofuran can be dissolved in a soluble solvent to precipitate a solid.

Ｒ¹²¹は、２価の有機基を表し、Ｒ¹²²は、４価の有機基を表し、Ｒ¹²³およびＲ¹²⁴は、それぞれ独立に、水素原子または１価の有機基を表す。

<< Polybenzoxazole precursor >>

The polybenzoxazole precursor preferably contains a structural unit represented by the following formula (2).

R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ independently represent a hydrogen atom or a monovalent organic group.

R ¹²¹ represents a divalent organic group. The divalent organic group includes an aliphatic group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms) and an aromatic group (preferably 6 to 22 carbon atoms, 6 to 14 carbon atoms). Is more preferable, and a group containing at least one of (6 to 12 is particularly preferable) is preferable. Examples of the aromatic group constituting R ^{121 include R 111} of the above formula (1). As the aliphatic group, a linear aliphatic group is preferable. R ¹²¹ is preferably derived from 4,4'-oxydibenzoyl chloride.

In formula (2), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same ^{meaning as R 115} in the above formula (1), and the preferable range is also the same. R ¹²² is preferably derived from 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.

R ¹²³ and R ¹²⁴ independently represent a hydrogen atom or a monovalent organic group, ^{which are synonymous with R 113} and R ¹¹⁴ in the above formula (1), and the preferable range is also the same.

The polybenzoxazole precursor may contain other types of structural units in addition to the structural units of the above formula (2).

The precursor preferably contains a diamine residue represented by the following formula (SL) as another type of structural unit in that the occurrence of warpage of the cured film due to ring closure can be suppressed.

Ｚは、ａ構造とｂ構造を有し、Ｒ^1sは水素原子または炭素数１〜１０の炭化水素基（好ましくは炭素数１〜６、より好ましくは炭素数１〜３）であり、Ｒ^2sは炭素数１〜１０の炭化水素基（好ましくは炭素数１〜６、より好ましくは炭素数１〜３）であり、Ｒ^3s、Ｒ^4s、Ｒ^5s、Ｒ^6sのうち少なくとも１つは芳香族基（好ましくは炭素数６〜２２、より好ましくは炭素数６〜１８、特に好ましくは炭素数６〜１０）で、残りは水素原子または炭素数１〜３０（好ましくは炭素数１〜１８、より好ましくは炭素数１〜１２、特に好ましくは炭素数１〜６）の有機基で、それぞれ同一でも異なっていてもよい。ａ構造およびｂ構造の重合は、ブロック重合でもランダム重合でもよい。Ｚ部分において、好ましくは、ａ構造は５〜９５モル％、ｂ構造は９５〜５モル％であり、ａ＋ｂは１００モル％である。

Z has an a structure and a b structure, R ^1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and R ^2s. Is a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and at least one of ^{R 3s} , R ^4s , R ^5s , and R ^{6s is aromatic.} A group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), and the rest are hydrocarbon atoms or 1 to 30 carbon atoms (preferably 1 to 18 carbon atoms, etc.). It is preferably an organic group having 1 to 12 carbon atoms, particularly preferably 1 to 6) carbon atoms, and may be the same or different from each other. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. In the Z moiety, preferably, the a structure is 5 to 95 mol%, the b structure is 95 to 5 mol%, and a + b is 100 mol%.

In the formula (SL), preferred Z includes those in which R ^5s and R ^6s in the b structure are phenyl groups. The molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. The molecular weight can be determined by commonly used gel permeation chromatography. By setting the molecular weight in the above range, the elastic modulus of the polybenzoxazole precursor after dehydration ring closure can be lowered, and the effect of suppressing warpage and the effect of improving solubility can be achieved at the same time.

When the precursor contains a diamine residue represented by the formula (SL) as another type of structural unit, the removal of the acid dianhydride group from the tetracarboxylic acid dianhydride is further carried out in terms of improving alkali solubility. It is preferable to include the tetracarboxylic acid residue remaining later as a constituent unit. Examples of such a tetracarboxylic acid residue include the example of R ¹¹⁵ in the formula (1).

The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2000 to 500000, more preferably 5000 to 100,000, and even more preferably 1000 to 50000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2000 to 50000, and even more preferably 4000 to 25000.

The degree of dispersion of the molecular weight of the polybenzoxazole precursor is preferably 1.5 to 3.5, more preferably 2 to 3.

The content of the polymer precursor in the photosensitive resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and 40% by mass, based on the total solid content of the composition. The above is more preferable, 50% by mass or more is further preferable, 60% by mass or more is further preferable, and 70% by mass or more is further preferable. Further, the content of the polymer precursor in the photosensitive resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, based on the total solid content of the composition. It is more preferably 98% by mass or less, further preferably 95% by mass or less, and even more preferably 95% by mass or less.

The photosensitive resin composition of the present invention may contain only one type of polymer precursor, or may contain two or more types of polymer precursors. When two or more kinds are included, the total amount is preferably in the above range.

<Photosensitizer>

The photosensitive resin composition of the present invention preferably contains a photosensitive agent. Examples of the photosensitizer include a photoradical polymerization initiator, and may also include, for example, a photocuring accelerator and a thermal radical polymerization initiator.

<< Photopolymerization Initiator >>

The photopolymerization initiator that can be used as the photosensitizer is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited and may be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. Further, it may be an activator that produces an active radical by causing some action with the photoexcited sensitizer.

The photoradical polymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 in the range of about 300 to 800 nm (preferably 330 to 500 nm). The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

When the photosensitive resin composition according to the preferred embodiment of the present invention contains a specific thermal base generator and a photoradical polymerization initiator, the following actions are expected.

The photosensitive resin composition is applied to a substrate such as a semiconductor wafer to form a photosensitive resin composition layer, and then heated to cyclize a precursor of a heterocyclic-containing polymer and cure the composition (primary curing). can do. In this heat curing, the specific thermobase generator according to the present invention is useful. Next, the cured photosensitive resin composition layer is irradiated with light. As a result, curing caused by radicals generated by the action of the photoradical polymerization initiator occurs (secondary curing). At this time, for example, if the precursor of the heterocyclic-containing polymer has a radical-polymerizable group, it is not necessary to separately add a radical-polymerizable compound, but if necessary, a radical-polymerizable compound is contained and this is polymerized. It may be in a form of photocuring by doing so. As a result, the solubility in the light-irradiated portion can be reduced. There is an advantage that regions having different solubilitys can be easily prepared by utilizing this action. Specifically, the photosensitive resin composition layer is exposed through a photomask having a pattern that masks only the electrode portion. This makes it possible to prepare regions having different solubilitys according to the pattern of the electrodes.

As the photoradical polymerization initiator, a known compound can be arbitrarily used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives and the like. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. Can be mentioned. For details thereof, the description in paragraphs 0165 to 0182 of JP2016-0273557 and paragraphs 0138 to 0151 of International Publication WO2015 / 199219 can be referred to, and the contents thereof are incorporated in the present specification.

Examples of the ketone compound include the compounds described in paragraph 0087 of JP2015-087611, the contents of which are incorporated in the present specification. As a commercially available product, KayaCure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

As the photoradical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in JP-A-10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used.

As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and 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.

As the aminoacetophenone-based initiator, the compound described in JP-A-2009-191179, in which the absorption maximum wavelength is matched with a wavelength light source such as 365 nm or 405 nm, can also be used.

Examples of the acylphosphine-based initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names, both manufactured by BASF) can be used.

Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF).

市販品ではＩＲＧＡＣＵＲＥ ＯＸＥ ０１、ＩＲＧＡＣＵＲＥ ＯＸＥ ０２、ＩＲＧＡＣＵＲＥ ＯＸＥ ０３、ＩＲＧＡＣＵＲＥ ＯＸＥ ０４（以上、ＢＡＳＦ社製）、アデカオプトマーＮ−１９１９（ＡＤＥＫＡ社製、特開２０１２−１４０５２号公報に記載の光ラジカル重合開始剤２）も好適に用いられる。また、ＴＲ−ＰＢＧ−３０４（常州強力電子新材料有限公司製）、アデカアークルズＮＣＩ−８３１およびアデカアークルズＮＣＩ−９３０（ＡＤＥＫＡ社製）も用いることができる。また、ＤＦＩ−０９１（ダイトーケミックス株式会社製）を用いることができる。

さらに、また、フッ素原子を有するオキシム化合物を用いることも可能である。そのようなオキシム化合物の具体例としては、特開２０１０−２６２０２８号公報に記載されている化合物、特表２０１４−５００８５２号公報の段落０３４５に記載されている化合物２４、３６〜４０、特開２０１３−１６４４７１号公報の段落０１０１に記載されている化合物（Ｃ−３）などが挙げられる。

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。

The photoradical polymerization initiator is more preferably an oxime compound. By using the oxime compound, the exposure latitude can be improved more effectively. The oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a photocuring accelerator.

As specific examples of the oxime compound, the compound described in JP-A-2001-233842, the compound described in JP-A-2000-80068, and the compound described in JP-A-2006-342166 can be used.

Preferred oxime compounds include, for example, compounds having the following structures, 3-benzooxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, and 2-acetoxy. Iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one , And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like. In the photosensitive resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as the photoradical polymerization initiator. Oxime-based photopolymerization initiators have a> C = N—O—C (= O) − linking group in the molecule.

Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), and ADEKA PUTMER N-1919 (manufactured by ADEKA, JP2012-14052). The initiator 2) is also preferably used. Further, TR-PBG-304 (manufactured by Changshu Powerful Electronics New Materials Co., Ltd.), ADEKA ARCLUS NCI-831 and ADEKA ARCLUDS NCI-930 (manufactured by ADEKA) can also be used. Further, DFI-091 (manufactured by Daito Chemix Co., Ltd.) can be used.

Furthermore, it is also possible to use an oxime compound having a fluorine atom. Specific examples of such an oxime compound include compounds described in JP-A-2010-262028, compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013. Examples thereof include the compound (C-3) described in paragraph 0101 of JP-A-164471.

The most preferable oxime compound includes an oxime compound having a specific substituent shown in JP-A-2007-269779 and an oxime compound having a thioaryl group shown in JP-A-2009-191061.

式（Ｉ）中、Ｒ^I00は、炭素数１〜２０のアルキル基、１個以上の酸素原子によって中断された炭素数２〜２０のアルキル基、炭素数１〜１２のアルコキシル基、フェニル基、炭素数１〜２０のアルキル基、炭素数１〜１２のアルコキシル基、ハロゲン原子、シクロペンチル基、シクロヘキシル基、炭素数２〜１２のアルケニル基、１個以上の酸素原子によって中断された炭素数２〜１８のアルキル基および炭素数１〜４のアルキル基の少なくとも１つで置換されたフェニル基、またはビフェニルであり、Ｒ^I01は、式（ＩＩ）で表される基であるか、Ｒ^I00と同じ基であり、Ｒ^I02〜Ｒ^I04は各々独立に炭素数１〜１２のアルキル、炭素数１〜１２のアルコキシまたはハロゲンである。

式中、Ｒ^I05〜Ｒ^I07は、上記式（Ｉ）のＲ^I02〜Ｒ^I04と同じである。

From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, or a triaryl. Selected from the group consisting of imidazole dimer, onium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halomethyloxaziazole compound, 3-aryl substituted coumarin compound. Compounds are preferred.

More preferable photoradical polymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds and acetophenone compounds. At least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferable, and metallocene compounds or oxime compounds are even more preferable, and oxime compounds are even more preferable. Is even more preferable.

The photoradical polymerization initiator is N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone). Aromatic ketones such as -2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, alkylanthraquinone, etc. It is also possible to use quinones fused to the aromatic ring of the above, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkyl benzoin, and benzyl derivatives such as benzyl dimethyl ketal. Further, a compound represented by the following formula (I) can also be used.

In formula (I), ^RI00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxyl group having 1 to 12 carbon atoms, a phenyl group, and the like. Alkyl group with 1 to 20 carbon atoms, alkoxyl group with 1 to 12 carbon atoms, halogen atom, cyclopentyl group, cyclohexyl group, alkenyl group with 2 to 12 carbon atoms, carbon number 2 to interrupted by one or more oxygen atoms 18 alkyl group and at least one substituted phenyl group of the alkyl group having 1 to 4 carbon atoms or a biphenyl,, R ^I01 is a group represented by formula (II), the same as R ^I00 The groups, R ^{I02 to} R I ^04, are independently alkyl having 1 to 12 carbon atoms and alkoxy or halogen having 1 to 12 carbon atoms, respectively.

In the formula, R ^{I05 to} R I ⁰⁷ are the same as ^{R I 02 to} R I ^{04 in} the above formula (I).

Further, as the photoradical polymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication WO2015 / 125469 can also be used.

When the photopolymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the photosensitive resin composition of the present invention. It is more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more kinds of photopolymerization initiators are contained, the total is preferably in the above range.

<< Thermal Radical Polymerization Initiator >>

A thermal radical polymerization initiator may be used as the photosensitizer. A thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, it is possible to proceed with the polymerization reaction of the polymer precursor as well as the cyclization of the polymer precursor, so that a higher degree of heat resistance can be achieved.

Specific examples of the thermal radical polymerization initiator include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-63554.

When the thermal radical polymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the photosensitive resin composition of the present invention. %, More preferably 5 to 15% by mass. Only one type of thermal radical polymerization initiator may be contained, or two or more types may be contained. When two or more types of thermal radical polymerization initiators are contained, the total is preferably in the above range.

<Polymerizable compound>

<< Radical Polymerizable Compound >>

The photosensitive resin composition of the present invention preferably contains a polymerizable compound. As the polymerizable compound, a radically polymerizable compound can be used. The radically polymerizable compound is a compound having a radically polymerizable group. Examples of the radically polymerizable group include groups having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth) acryloyl group. The radically polymerizable group is preferably a (meth) acryloyl group.

The number of radically polymerizable groups contained in the radically polymerizable compound may be one or two or more, but the radically polymerizable compound preferably has two or more radically polymerizable groups, and preferably has three or more radically polymerizable groups. More preferred. The upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.

The molecular weight of the radically polymerizable compound is preferably 2000 or less, more preferably 1500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radically polymerizable compound is preferably 100 or more.

From the viewpoint of developability, the photosensitive resin composition of the present invention preferably contains at least one bifunctional or higher functional radical polymerizable compound containing two or more polymerizable groups, and contains a trifunctional or higher functional radical polymerizable compound. It is more preferable to contain at least one kind. Further, it may be a mixture of a bifunctional radical polymerizable compound and a trifunctional or higher functional radical polymerizable compound. The number of functional groups of the radically polymerizable compound means the number of radically polymerizable groups in one molecule.

Specific examples of the radically polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides, and preferred examples thereof. Esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a sulfanyl group with a monofunctional or polyfunctional isocyanate or an epoxy, or a monofunctional or polyfunctional group. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a parentionic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, an amine or a thiol, and a halogen group. Substitution reaction products of unsaturated carboxylic acid esters or amides having a releasable substituent such as tosyloxy group and monofunctional or polyfunctional alcohols, amines and thiols are also suitable. Further, as another example, it is also possible to use a compound group in which the above-mentioned unsaturated carboxylic acid is replaced with a vinylbenzene derivative such as unsaturated phosphonic acid or styrene, vinyl ether, allyl ether or the like. As a specific example, the description in paragraphs 0113 to 0122 of Japanese Patent Application Laid-Open No. 2016-0273557 can be referred to, and these contents are incorporated in the present specification.

Further, as the radically polymerizable compound, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable. Examples include polyethylene glycol di (meth) acrylate, trimethyl ethanetri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol. Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylpropantri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin, trimethylolethane, etc. A compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, is described in JP-A-48-41708, JP-A-50-6034, and JP-A-51-37193. Urethane (meth) acrylates, such as those described in JP-A-48-64183, JP-A-49-43191, and JP-A-52-30490, polyester acrylates, epoxy resins and (meth) acrylics. Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acids, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Further, a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether group such as glycidyl (meth) acrylate and a compound having an ethylenically unsaturated bond can also be mentioned.

Further, as a preferable radically polymerizable compound other than the above, it has a fluorene ring and has an ethylenically unsaturated bond, which is described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216 and the like. It is also possible to use a compound having two or more groups having the above, or a cardo resin.

Further, as other examples, the specific unsaturated compounds described in Japanese Patent Publication No. 46-43946, Japanese Patent Publication No. 1-4537, and Japanese Patent Application Laid-Open No. 1-4536, and Japanese Patent Application Laid-Open No. 2-25493. Vinyl phosphonic acid compounds and the like can also be mentioned. Further, a compound containing a perfluoroalkyl group described in JP-A-61-22048 can also be used. Furthermore, the journal of the Japan Adhesive Association vol. 20, No. Those introduced as photopolymerizable monomers and oligomers on pages 7, 300-308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964 and the compounds described in paragraphs 0087 to 0131 of International Publication WO2015 / 199219 can also be preferably used, and the contents thereof are described in the present specification. Incorporated in.

Further, the compound described in Japanese Patent Application Laid-Open No. 10-62986 together with specific examples as formulas (1) and (2) after addition of ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated is also used. It can be used as a radically polymerizable compound.

Further, the compounds described in paragraphs 0104 to 0131 of JP2015-187211A can also be used as other radically polymerizable compounds, and their contents are incorporated in the present specification.

Examples of radically polymerizable compounds include dipentaerythritol triacrylate (commercially available KAYARAD D-330 manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available KAYARAD D-320 Nippon Kayaku Co., Ltd.). , A-TMMT Shin-Nakamura Chemical Co., Ltd.), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310 Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available) KAYARAD DPHA Nippon Kayaku Co., Ltd., A-DPH Shin-Nakamura Chemical Industry Co., Ltd.), and the structure in which these (meth) acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues. preferable. These oligomer types can also be used.

Commercially available products of the radically polymerizable compound include, for example, SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer, and SR-209, which is a bifunctional methacrylate having four ethyleneoxy chains. , 231, 239, DPCA-60, a hexafunctional acrylate having 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd., TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS- 10, UAB-140 (manufactured by Nippon Paper Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPHA-40H ( Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (manufactured by Nichiyu Co., Ltd.), etc. Can be mentioned.

Examples of the radically polymerizable compound include urethane acrylates as described in JP-A-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. , Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 are also suitable. Further, as the radically polymerizable compound, 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 used. It can also be used.

The radically polymerizable compound may be a radically polymerizable compound having an acid group such as a carboxyl group or a phosphoric acid group. The radical polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid is obtained by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. A radically polymerizable compound having a group is more preferable. Particularly preferably, in a radical polymerizable compound in which an unreacted hydroxyl group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to have an acid group, the aliphatic polyhydroxy compound is pentaerythritol or dipenta. It is a compound that is erythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

The acid value of the radically polymerizable compound having an acid group is preferably 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When the acid value of the radically polymerizable compound is within the above range, it is excellent in manufacture and handling, and further excellent in developability. Moreover, the polymerizable property is good.

In the photosensitive resin composition of the present invention, a monofunctional radically polymerizable compound can be preferably used as the radically polymerizable compound from the viewpoint of suppressing warpage associated with controlling the elastic modulus of the cured film. Examples of the monofunctional radical polymerizable compound include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl (meth). (Meta) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and the like (meth) ) Acrylate derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allylglycidyl ether, diallyl phthalate, and triallyl trimellitate are preferably used. As the monofunctional radical polymerizable compound, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.

<< Polymerizable compounds other than the radically polymerizable compounds mentioned above >>

The photosensitive resin composition of the present invention may further contain a polymerizable compound other than the radically polymerizable compound described above. Examples of the polymerizable compound other than the above-mentioned radically polymerizable compound include a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group; an epoxy compound; an oxetane compound; and a benzoxazine compound.

<<< Compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group >>>

As the compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, a compound represented by the following formula (AM1), (AM4) or (AM5) is preferable.

（式中、ｔは、１〜２０の整数を示し、Ｒ¹⁰⁴は炭素数１〜２００のｔ価の有機基を示し、Ｒ¹⁰⁵は、−ＯＲ¹⁰⁶または、−ＯＣＯ−Ｒ¹⁰⁷で示される基を示し、Ｒ¹⁰⁶は、水素原子または炭素数１〜１０の有機基を示し、Ｒ¹⁰⁷は、炭素数１〜１０の有機基を示す。）

(In the formula, t represents an integer of 1 to 20, R ¹⁰⁴ represents an organic group having a t-valence of 1 to 200 carbon atoms, and R ¹⁰⁵ is a group represented by -OR ¹⁰⁶ or -OCO-R ^107. R ¹⁰⁶ indicates a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R ¹⁰⁷ indicates an organic group having 1 to 10 carbon atoms.)

（式中、Ｒ⁴⁰⁴は炭素数１〜２００の２価の有機基を示し、Ｒ⁴⁰⁵は、−ＯＲ⁴⁰⁶または、−ＯＣＯ−Ｒ⁴⁰⁷で示される基を示し、Ｒ⁴⁰⁶は、水素原子または炭素数１〜１０の有機基を示し、Ｒ⁴⁰⁷は、炭素数１〜１０の有機基を示す。）

(In the formula, R ⁴⁰⁴ represents a divalent organic group having 1 to 200 carbon atoms, R ⁴⁰⁵ represents a group represented by -OR ⁴⁰⁶ or -OCO-R ⁴⁰⁷ , and R ⁴⁰⁶ is a hydrogen atom or carbon. It represents an organic group having a number of 1 to 10, and R ⁴⁰⁷ indicates an organic group having 1 to 10 carbon atoms.)

（式中ｕは３〜８の整数を示し、Ｒ⁵⁰⁴は炭素数１〜２００のｕ価の有機基を示し、Ｒ⁵⁰⁵は、−ＯＲ⁵⁰⁶または、−ＯＣＯ−Ｒ⁵⁰⁷で示される基を示し、Ｒ⁵⁰⁶は、水素原子または炭素数１〜１０の有機基を示し、Ｒ⁵⁰⁷は、炭素数１〜１０の有機基を示す。）

(In the formula, u represents an integer of 3 to 8, R ⁵⁰⁴ represents a u-valent organic group having 1 to 200 carbon atoms, and R ⁵⁰⁵ represents a group represented by -OR ⁵⁰⁶ or -OCO-R ^507. , R ⁵⁰⁶ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R ⁵⁰⁷ represents an organic group having 1 to 10 carbon atoms.)

Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML. -PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.), NIKARAC MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacethoxymethyl-p-cresol, etc. Be done.

Specific examples of the compound represented by the formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, and the like. HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), NIKALAC MX-280, Examples thereof include NIKALAC MX-270 and NIKALAC MW-100LM (above, trade name, manufactured by Sanwa Chemical Co., Ltd.).

<<< Epoxy compound (compound having an epoxy group) >>>

The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a cross-linking reaction at 200 ° C. or lower, and the dehydration reaction derived from the cross-linking does not occur, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in suppressing low temperature curing and warpage of the composition.

The epoxy compound preferably contains a polyethylene oxide group. As a result, the elastic modulus can be further reduced and warpage can be suppressed. The polyethylene oxide group means that the number of constituent units of ethylene oxide is 2 or more, and the number of constituent units is preferably 2 to 15.

Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resin such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether; polymethyl (glycidi). Examples include, but are not limited to, epoxy group-containing silicones such as loxypropyl) siloxane. Specifically, Epicron® 850-S, Epicron® HP-4032, Epicron® HP-7200, Epicron® HP-820, Epicron® HP-4700, Epicron® EXA-4710, Epicron® HP-4770, Epicron® EXA-859CRP, Epicron® EXA-1514, Epicron® EXA-4880, Epicron® EXA-4850-150, Epicron EXA-4850-1000, Epicron (registered trademark) EXA-4816, Epicron (registered trademark) EXA-4822 (trademark above, manufactured by DIC), Rica Resin (registered trademark) BEO-60E (trademark) Names include Shin Nihon Rika Co., Ltd., EP-4003S, EP-4000S (trade names above, manufactured by ADEKA) and the like. Among these, an epoxy resin containing a polyethylene oxide group is preferable because it suppresses warpage and is excellent in heat resistance. For example, Epicron® EXA-4880, Epicron® EXA-4822, and Ricaresin® BEO-60E are preferred because they contain polyethylene oxide groups.

<<< Oxetane compound (compound having an oxetanyl group) >>>

Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, and the like. Examples thereof include 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester and the like. As a specific example, the Aron Oxetane series manufactured by Toagosei Co., Ltd. (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, and these can be used alone or individually. Two or more kinds may be mixed.

<<< Benzoxazine compound (compound having a benzoxazolyl group) >>>

Since the benzoxazine compound is a cross-linking reaction derived from the ring-opening addition reaction, degassing does not occur during curing, and heat shrinkage is further reduced to suppress the occurrence of warpage, which is preferable.

Preferred examples of the benzoxazine compound are BA-type benzoxazine, B-m-type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, and phenol novolac-type dihydrobenzo. Oxazine compounds can be mentioned. These may be used alone or in combination of two or more.

When the polymerizable compound is contained, the content thereof is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the photosensitive resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.

One type of the polymerizable compound may be used alone, or two or more types may be mixed and used. When two or more types are used in combination, the total amount is preferably in the above range.

<Solvent>

The photosensitive resin composition of the present invention preferably contains a solvent. As the solvent, a known solvent can be arbitrarily used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.

Examples of esters include ethyl acetate, -n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone. , Δ-Valerolactone, alkylalkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.) )), 3-alkyloxypropionic acid alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-). Methyl ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate) Etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyloxy-2-methylpropion Methyl acetate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, pyruvin Suitable examples include propyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutate and the like.

Examples of ethers include 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, and propylene glycol. Suitable examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.

As the ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like are preferable.

As the aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene and the like are preferable.

As the sulfoxides, for example, dimethyl sulfoxide is preferable.

As the amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like are preferable.

As the solvent, a form in which two or more kinds are mixed is also preferable from the viewpoint of improving the coating surface properties.

In the present invention, 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- Consists of one solvent selected from butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, or two or more. The mixed solvent to be mixed is preferable. The combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

From the viewpoint of coatability, the content of the solvent is preferably such that the total solid content concentration of the photosensitive resin composition of the present invention is 5 to 80% by mass, and is preferably 5 to 75% by mass. It is more preferable that the amount is 10 to 70% by mass, and more preferably 40 to 70% by mass. The solvent content may be adjusted according to the desired thickness and coating method.

Only one type of solvent may be contained, or two or more types may be contained. When two or more kinds of solvents are contained, the total is preferably in the above range.

<Migration inhibitor>

The photosensitive resin composition of the present invention preferably further contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress the movement of metal ions derived from the metal layer (metal wiring) into the photosensitive resin composition layer.

The migration inhibitor is not particularly limited, but a heterocycle (pyran ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isooxazole ring, isothiazole ring, tetrazole ring, pyridine ring, etc. Pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring, piperazine ring, morpholin ring, 2H-pyran ring and 6H-pyran ring, triazine ring), thiourea and sulfanyl group compounds, hindered phenol compounds , Salicylic acid derivative compound, hydrazide derivative compound and the like. In particular, triazole-based compounds such as 1,2,4-triazole and benzotriazole, and tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

It is also possible to use an ion trap agent that traps anions such as halogen ions.

Examples of other migration inhibitors include rust preventives described in paragraph 0094 of JP2013-15701, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-59656A. The compound described in paragraph 0052, the compound described in paragraphs 0114, 0116 and 0118 of JP2012-194520A, the compound described in paragraph 0166 of International Publication WO2015 / 199219, and the like can be used.

Specific examples of the migration inhibitor include the following compounds.

When the photosensitive resin composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the photosensitive resin composition, and is 0. .05 to 2.0% by mass is more preferable, and 0.1 to 1.0% by mass is further preferable.

The migration inhibitor may be only one type or two or more types. When there are two or more types of migration inhibitors, the total is preferably in the above range.

本発明の感光性樹脂組成物が重合禁止剤を有する場合、重合禁止剤の含有量は、本発明の感光性樹脂組成物の全固形分に対して、０．０１〜５質量％であることが好ましく、０．０２〜３質量％であることがより好ましく、０．０５〜２．５質量％であることがさらに好ましい。

重合禁止剤は１種のみでもよいし、２種以上であってもよい。重合禁止剤が２種以上の場合は、その合計が上記範囲であることが好ましい。

<Polymerization inhibitor>

The photosensitive resin composition of the present invention preferably contains a polymerization inhibitor.

Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'. -Thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine , N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1 -Nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, Bis (4-hydroxy-3,5-tert-butyl) phenylmethane and the like are preferably used. Further, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compound described in paragraphs 0031 to 0046 of International Publication WO2015 / 125469 can also be used.

In addition, the following compounds can be used (Me is a methyl group).

When the photosensitive resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor shall be 0.01 to 5% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. Is more preferable, 0.02 to 3% by mass is more preferable, and 0.05 to 2.5% by mass is further preferable.

The polymerization inhibitor may be only one kind or two or more kinds. When there are two or more types of polymerization inhibitors, the total is preferably in the above range.

<Metal adhesion improver>

The photosensitive resin composition of the present invention preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like. Examples of the metal adhesiveness improving agent include a silane coupling agent.

Examples of the silane coupling agent include the compounds described in paragraph 0167 of International Publication WO2015 / 199219, the compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, and paragraphs 0063 to WO2011 / 080992A1 of International Publication WO2011 / 080992A1. The compounds described in 0071, the compounds described in paragraphs 0060 to 0061 of JP-A-2014-191252, the compounds described in paragraphs 0045-0052 of JP-A-2014-41264, paragraph 0055 of International Publication WO2014 / 097594. The described compounds are mentioned. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A. Further, it is also preferable to use the following compounds as the silane coupling agent. In the following formula, Et represents an ethyl group.

Further, as the metal adhesion improver, the compounds described in paragraphs 0046 to 0049 of JP2014-186186A and the sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935 can also be used.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further preferably 0, based on 100 parts by mass of the polymer precursor. It is in the range of 5 to 5 parts by mass. When it is at least the above lower limit value, the adhesiveness between the cured film and the metal layer after the curing step is good, and when it is at least the above upper limit value, the heat resistance and mechanical properties of the cured film after the curing step are good. The metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more types are used, the total is preferably in the above range.

<Other additives>

The photosensitive resin composition of the present invention contains various additives such as a sensitizing dye, a chain transfer agent, a surfactant, a higher fatty acid derivative, and inorganic particles, if necessary, as long as the effects of the present invention are not impaired. , Curing agent, curing catalyst, filler, antioxidant, ultraviolet absorber, anti-aggregation agent and the like can be blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the composition.

<< Sensitive Dye >>

The photosensitive resin composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs a specific active radiation and becomes an electron-excited state. The sensitizing dye in the electron-excited state comes into contact with a thermal curing accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and acts such as electron transfer, energy transfer, and heat generation occur. As a result, the thermosetting accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo a chemical change and decompose to generate radicals, acids, or bases. For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP2016-027357A can be referred to, and this content is incorporated in the present specification.

When the photosensitive resin composition of the present invention contains a sensitizing dye, the content of the sensitizing dye may be 0.01 to 20% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. It is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass. The sensitizing dye may be used alone or in combination of two or more.

<< Chain Transfer Agent >>

The photosensitive resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, 2005), pp. 683-684. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals. In particular, a thiol compound can be preferably used. Further, as the chain transfer agent, the compounds described in paragraphs 0152 to 0153 of International Publication WO2015 / 199219 can also be used.

When the photosensitive resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition of the present invention. Preferably, 1 to 10 parts by mass is more preferable, and 1 to 5 parts by mass is further preferable. The chain transfer agent may be only one kind or two or more kinds. When there are two or more types of chain transfer agents, the total is preferably in the above range.

また、界面活性剤は、国際公開ＷＯ２０１５／１９９２１９号の段落０１５９〜０１６５に記載の化合物を用いることもできる。

<< Surfactant >>

Each type of surfactant may be added to the photosensitive resin composition of the present invention from the viewpoint of further improving the coatability. As the surfactant, various types of surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. The following surfactants are also preferable.

Further, as the surfactant, the compound described in paragraphs 0159 to 0165 of International Publication WO2015 / 199219 can also be used.

When the photosensitive resin composition of the present invention has a surfactant, the content of the surfactant is 0.001 to 2.0% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. It is preferably 0.005 to 1.0% by mass, more preferably 0.005 to 1.0% by mass. The surfactant may be only one kind or two or more kinds. When there are two or more types of surfactant, the total is preferably in the above range.

<< Higher fatty acid derivatives >>

In the photosensitive resin composition of the present invention, in order to prevent polymerization inhibition due to oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide is added, and the surface of the composition is dried in the process of drying after application. It may be unevenly distributed in.

Further, as the higher fatty acid derivative, the compound described in paragraph 0155 of International Publication WO2015 / 199219 can also be used.

When the photosensitive resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative shall be 0.1 to 10% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. Is preferable. The higher fatty acid derivative may be only one kind or two or more kinds. When there are two or more higher fatty acid derivatives, the total is preferably in the above range.

<Restrictions on other contained substances>

The water content of the photosensitive resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass from the viewpoint of coating surface properties.

From the viewpoint of insulating properties, the metal content of the photosensitive resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are contained, the total of these metals is preferably in the above range.

Further, as a method for reducing metal impurities unintentionally contained in the photosensitive resin composition of the present invention, a raw material having a low metal content is selected as a raw material constituting the photosensitive resin composition of the present invention. Methods such as filtering the raw materials constituting the photosensitive resin composition of the present invention with a filter, lining the inside of the apparatus with polytetrafluoroethylene or the like, and performing distillation under conditions in which contamination is suppressed as much as possible can be mentioned. be able to.

Considering the use as a semiconductor material, the photosensitive resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and more preferably 200 mass ppm from the viewpoint of wiring corrosiveness. Less than ppm is more preferred. Among them, those existing in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of chlorine atom and bromine atom, or chlorine ion and bromine ion is in the above range, respectively.

A conventionally known storage container can be used as the storage container for the photosensitive resin composition of the present invention. In addition, as the storage container, for the purpose of suppressing impurities from being mixed into the raw materials and compositions, the inner wall of the container is made of a multi-layer bottle composed of 6 types and 6 layers of resin, and 6 types of resin are formed into a 7-layer structure. It is also preferable to use a bottle of plastic. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.

<Preparation of composition>

The photosensitive resin composition of the present invention can be prepared by mixing each of the above components. The mixing method is not particularly limited, and a conventionally known method can be used.

Further, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the composition. The filter pore diameter 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 polytetrafluoroethylene, polyethylene or nylon. The filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When using a plurality of types of filters, filters having different pore diameters or materials may be used in combination. Moreover, you may filter various materials a plurality of times. When filtering a plurality of times, circulation filtration may be used. Moreover, you may pressurize and perform filtration. When pressurizing and filtering, the pressurizing pressure is preferably 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. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

<Cured film, laminate, semiconductor device, and their manufacturing method>

Next, a cured film, a laminate, a semiconductor device, and a method for manufacturing them will be described.

The cured film of the present invention is obtained by curing the photosensitive resin composition of the present invention. The film thickness of the cured film of the present invention can be, for example, 0.5 μm or more, and can be 1 μm or more. Further, the upper limit value can be 100 μm or less, and can be 30 μm or less.

The cured film of the present invention may be laminated in two or more layers, and further in three to seven layers to form a laminated body. The laminate having two or more cured films of the present invention preferably has a metal layer between the cured films. Such a metal layer is preferably used as a metal wiring such as a rewiring layer.

Examples of applicable fields of the cured film of the present invention include an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like. Other examples include forming a pattern by etching on a sealing film, a substrate material (base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above. For these applications, for example, Science & Technology Co., Ltd. "High-performance and applied technology of polyimide" April 2008, Masaaki Kakimoto / supervision, CMC technical library "Basics and development of polyimide materials" published in November 2011 , Japan Polyimide / Aromatic Polymer Study Group / ed., "Latest Polyimide Basics and Applications" NTS, August 2010, etc. can be referred to.

The cured film in the present invention can also be used for manufacturing plate surfaces such as offset plate surfaces or screen plate surfaces, for etching molded parts, and for manufacturing protective lacquers and dielectric layers in electronics, especially microelectronics.

The method for producing a cured film of the present invention includes using the photosensitive resin composition of the present invention. Specifically, a film forming step of applying the photosensitive resin composition of the present invention to a substrate to form a film (layer forming step of forming a layer) and a layered photosensitive resin composition at 80 to 450 ° C. It is preferable to include a heating step of heating. Preferably, the method for producing the cured film is, after the film forming step (layer forming step), an exposure step of exposing the film and the exposed photosensitive resin composition layer (film, that is, a resin layer). On the other hand, a manufacturing method including a developing process for performing a developing process can be mentioned. After this development, the exposed resin layer can be further cured by heating (preferably heating at 80 to 450 ° C.). As described above, when the photosensitive resin composition is used, the composition is cured by exposure in advance, and then if necessary, desired processing (for example, the following lamination) is performed, and the composition is further cured by heating. be able to.

The method for producing a laminate of the present invention includes the method for producing a cured film of the present invention. In the method for producing a laminate of the present invention, after forming a cured film according to the above-mentioned method for producing a cured film, the photosensitive resin composition is further subjected to a film forming step (layer forming step) and a heating step, or a photosensitive step. When properties are added, it is preferable to carry out the film forming step (layer forming step), the exposure step, and the developing treatment step (if necessary, further heating step) in the above order. In particular, it is preferable to carry out each of the above steps a plurality of times, for example, 2 to 5 times (that is, 3 to 6 times in total) in order. By laminating the cured film in this way, a laminated body can be obtained. In the present invention, it is particularly preferable to provide a metal layer on the portion provided with the cured film, between the cured films, or both.

These details will be described below.

<< Membrane formation process (layer formation process) >>

The production method according to a preferred embodiment of the present invention includes a film forming step (layer forming step) in which the photosensitive resin composition is applied to a substrate to form a film (layered).

The type of substrate can be appropriately determined depending on the application, but semiconductor fabrication substrates such as silicon, silicon nitride, polysilicon, polysilicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, thin film, and magnetic film. , Reflective film, metal substrate such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, plasma display panel (PDP) electrode plate, and the like are not particularly limited.

In the present invention, a semiconductor-made substrate is particularly preferable, and a silicon substrate is more preferable.

Further, when the photosensitive resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer serves as a substrate.

Coating is preferable as a means for applying the photosensitive resin composition to the substrate.

Specifically, the means to be applied include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, and a slit coating method. And the inkjet method and the like are exemplified. From the viewpoint of the uniformity of the thickness of the photosensitive resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an inkjet method are more preferable. A resin layer having a desired thickness can be obtained by adjusting an appropriate solid content concentration and coating conditions according to the method. The coating method can be appropriately selected depending on the shape of the substrate. For circular substrates such as wafers, the spin coating method, spray coating method, inkjet method, etc. are preferable, and for rectangular substrates, the slit coating method, spray coating method, inkjet, etc. The method or the like is preferable. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 2000 rpm for about 10 seconds to 1 minute.

<< Drying process >>

The production method of the present invention may include a step of forming the photosensitive resin composition layer, followed by a film forming step (layer forming step), and then drying to remove the solvent. The preferred drying temperature is 50 to 150 ° C, more preferably 70 ° C to 130 ° C, still more preferably 90 ° C to 110 ° C. The drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.

<< Exposure process >>

The production method of the present invention may include an exposure step of exposing the photosensitive resin composition layer. Exposure is not particularly limited so long as it can be cured photosensitive resin composition, for example, it is preferable to irradiate 100~10000mJ / cm ² at an exposure energy conversion at a wavelength 365nm, 200~8000mJ / cm ² irradiated Is more preferable.

The exposure wavelength can be appropriately determined in the range of 190 to 1000 nm, preferably 240 to 550 nm.

The exposure wavelengths are as follows: (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength 436 nm), h. Line (wavelength 405 nm), i-line (wavelength 365 nm), broad (3 wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer Examples thereof include a laser (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), and (6) electron beam. Regarding the photosensitive resin composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferable, and exposure with an i-line is particularly preferable. As a result, particularly high exposure sensitivity can be obtained.

<< Development process >>

The production method of the present invention may include a development treatment step of performing a development treatment on the exposed photosensitive resin composition layer. By developing, the unexposed portion (non-exposed portion) is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and for example, a developing method such as paddle, spray, immersion, or ultrasonic wave can be adopted.

Development is performed using a developing solution. The developer can be used without particular limitation as long as the unexposed portion (non-exposed portion) is removed. The developer preferably contains an organic solvent, and more preferably the developer contains 90% or more of the organic solvent. In the present invention, the developer preferably contains an organic solvent having a ClogP value of −1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting a structural formula in ChemBioDraw.

Examples of the organic solvent include ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and γ-butyrolactone. , Ε-caprolactone, δ-valerolactone, alkylalkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, (Ethyl ethoxyacetate, etc.)), alkyl esters of 3-alkyloxypropionic acid (eg, methyl 3-alkyloxypropionic acid, ethyl 3-alkyloxypropionic acid, etc.), etc. (eg, methyl 3-methoxypropionate, 3-methoxypropionic acid, etc.) Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl) Propyl oxypropionate and the like (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvin Ethyl acetate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., and as ethers, for example, 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, etc. As ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene. As the sulfoxides, dimethyl sulfoxide is preferably mentioned.

In the present invention, cyclopentanone and γ-butyrolactone are particularly preferable, and cyclopentanone is more preferable.

The developing solution preferably contains 50% by mass or more of an organic solvent, more preferably 70% by mass or more of an organic solvent, and further preferably 90% by mass or more of an organic solvent.

Further, the developing solution may be 100% by mass of an organic solvent.

The development time is preferably 10 seconds to 5 minutes. The temperature of the developing solution at the time of development is not particularly specified, but is usually 20 to 40 ° C.

After the treatment with the developing solution, further rinsing may be performed. The rinsing is preferably performed with a solvent different from that of the developing solution. For example, it can be rinsed with a solvent contained in the photosensitive resin composition. The rinsing time is preferably 5 seconds to 1 minute.

<< Heating process >>

The production method of the present invention preferably includes a step of heating after a film forming step (layer forming step), a drying step, or a developing step. In the heating step, the cyclization reaction of the polymer precursor proceeds. Further, although the composition of the present invention may contain a radically polymerizable compound other than the polymer precursor, curing of the radically polymerizable compound other than the unreacted polymer precursor can also proceed in this step. The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, further preferably 140 ° C. or higher, and 150 ° C. or higher. Is even more preferable, 160 ° C. or higher is even more preferable, and 170 ° C. or higher is even more preferable. The upper limit is preferably 500 ° C. or lower, more preferably 450 ° C. or lower, further preferably 350 ° C. or lower, further preferably 250 ° C. or lower, and preferably 220 ° C. or lower. Even more preferable.

The heating is preferably performed at a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min. By setting the temperature rise rate to 1 ° C./min or more, it is possible to prevent excessive volatilization of amine while ensuring productivity, and by setting the temperature rise rate to 12 ° C./min or less, the cured film can be prevented. Residual stress can be relaxed.

The temperature at the start of heating is preferably 20 ° C. to 150 ° C., more preferably 20 ° C. to 130 ° C., and even more preferably 25 ° C. to 120 ° C. The temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature is started. For example, when the photosensitive resin composition is applied onto a substrate and then dried, the temperature of the film (layer) after drying is, for example, 30 higher than the boiling point of the solvent contained in the photosensitive resin composition. It is preferable to gradually raise the temperature from a temperature as low as about 200 ° C.

The heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and even more preferably 30 to 240 minutes.

In particular, when forming a multi-layered laminate, the heating temperature is preferably 180 ° C. to 320 ° C., more preferably 180 ° C. to 260 ° C., from the viewpoint of adhesion between layers of the cured film. The reason is not clear, but it is considered that the ethynyl groups of the polymer precursors between the layers are undergoing a cross-linking reaction at this temperature.

Heating may be performed in stages. As an example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min and held at 180 ° C. for 60 minutes, the temperature is raised from 180 ° C. to 200 ° C. at 2 ° C./min, and held at 200 ° C. for 120 minutes. , Etc. may be performed. The heating temperature as the pretreatment step is preferably 100 to 200 ° C., more preferably 110 to 190 ° C., and even more preferably 120 to 185 ° C. In this pretreatment step, it is also preferable to perform the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547. It is possible to improve the characteristics of the film by such a pretreatment step. The pretreatment step is preferably performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps. For example, the pretreatment step 1 may be performed in the range of 100 to 150 ° C., and then the pretreatment step 2 may be performed in the range of 150 to 200 ° C.

Further, it may be cooled after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.

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 the polymer precursor. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

<< Metal layer forming process >>

The production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the photosensitive resin composition layer after the development treatment.

As the metal layer, existing metal species can be used without particular limitation, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified, copper and aluminum are more preferable, and copper is preferable. More preferred.

The method for forming the metal layer is not particularly limited, and an existing method can be applied. For example, the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a combination method thereof can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electroplating can be mentioned.

The thickness of the metal layer is preferably 0.1 to 50 μm, more preferably 1 to 10 μm at the thickest portion.

<< Laminating process >>

The production method of the present invention preferably further includes a laminating step.

The laminating step is the film forming step (layer forming step) and the heating step again on the surface of the cured film (resin layer) or the metal layer, or the film forming step (layer forming) on the photosensitive resin composition. Step), the exposure step, and the development processing step are a series of steps including performing the steps in the above order. Needless to say, the laminating step may further include the above-mentioned drying step, heating step, and the like.

When the laminating step is further performed after the laminating step, the surface activation treatment step may be further performed after the heating step, the exposure step, or the metal layer forming step. An example of the surface activation treatment is plasma treatment.

The laminating step is preferably performed 2 to 5 times, more preferably 3 to 5 times.

In the present invention, it is preferable that the laminate has two or more cured films and has a metal layer between the cured films. More preferably, the resin layer has a structure of 3 layers or more and 7 layers or less, such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, and 3 layers or more and 5 layers or less are further preferable.

That is, in the present invention, in particular, after the metal layer is provided, a film forming step (layer forming step) and a heating step of the photosensitive resin composition or a photosensitive resin composition so as to cover the metal layer is further performed. It is preferable that the film forming step (layer forming step), the exposure step, and the developing treatment step (if necessary, further heating step) are performed in the above order. By alternately performing the laminating step of laminating the photosensitive resin composition layer (resin) and the metal layer forming step, the photosensitive resin composition layer (resin layer) and the metal layer can be laminated alternately.

The present invention also discloses a semiconductor device having the cured film or laminate of the present invention. As specific examples of the semiconductor device in which the photosensitive resin composition of the present invention is used to form the interlayer insulating film for the rewiring layer, the description in paragraphs 0213 to 0218 and the description in FIG. 1 of JP-A-2016-0273557 are taken into consideration. Yes, these contents are incorporated herein.

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.

<Synthesis example 1>

[Synthesis of polyimide precursor (A-1: polyimide precursor having no radical polymerizable group) from pyromellitic acid dianhydride, 4,4'-diaminodiphenyl ether and benzyl alcohol]

14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C. for 12 hours) and 14.22 g (131.58 mmol) of benzyl alcohol were suspended in 50 mL of N-methylpyrrolidone. , Dryed with a molecular sieve. The suspension was heated at 100 ° C. for 3 hours. A clear solution was obtained a few minutes after heating. The reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) of pyridine and 90 mL of N-methylpyrrolidone were added. 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 keeping the temperature at −10 ± 4 ° C. Viscosity increased while adding SOCL _2. After diluting with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, a solution prepared by dissolving 11.08 g (58.7 mmol) of 4,4′-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at −5 to 0 ° C. over 20 minutes. Then, the reaction mixture was reacted at 0 ° C. for 1 hour, 70 g of ethanol was added, and the mixture was stirred at room temperature overnight. The polyimide precursor was then precipitated in 5 liters of water and the water-polyimide precursor mixture was stirred at a rate of 5000 rpm for 15 minutes. The polyimide precursor was filtered off, stirred again in 4 liters of water for 30 minutes and filtered again. The obtained polyimide precursor was then dried under reduced pressure at 45 ° C. for 3 days. The weight average molecular weight of this polyimide precursor was 18,000.

A-1

<Synthesis example 2>

[Synthesis of polyimide precursor (A-2: polyimide precursor having radical polymerizable group) from pyromellitic acid dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate]

14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, and 20 .4 g of pyridine (258 mmol) and 100 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 is _{chlorinated with SOCL 2} , converted to a polyimide precursor with 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example 1, and the polyimide precursor is converted into a polyimide precursor in the same manner as in Synthesis Example 1. Obtained. The weight average molecular weight of this polyimide precursor was 19,000.

A-2

<Synthesis example 3>

[Synthesis of polyimide precursor (A-3: polyimide precursor having radical polymerizable group) from 4,4'-oxydiphthalic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate]

20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140 ° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, and 0.05 g of hydroquinone. , 20.4 g of pyridine (258 mmol) and 100 g of diglime were mixed and stirred at a temperature of 60 ° C. for 18 hours to prepare a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. .. Next, the obtained diester is _{chlorinated with SOCL 2} , converted to a polyimide precursor with 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example 1, and the polyimide precursor is converted into a polyimide precursor in the same manner as in Synthesis Example 1. Obtained. The weight average molecular weight of this polyimide precursor was 18,000.

A-3

<Synthesis example 4>

Polyimide precursor (A-4: radically polymerizable group) from 4,4'-oxydiphthalic anhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (orthotrizine) and 2-hydroxyethyl methacrylate Synthesis of polyimide precursor)]

20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140 ° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, and 0.05 g of hydroquinone. , 20.4 g of pyridine (258 mmol) and 100 g of diglime were mixed and stirred at a temperature of 60 ° C. for 18 hours to prepare 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'-diamino-2,2'-dimethylbiphenyl in the same manner as in Synthesis Example 1, and the same as in Synthesis Example 1. A polyimide precursor was obtained by the above method. The weight average molecular weight of this polyimide precursor was 19,000.

A-4

<Synthesis example 5>

[Synthesis of polybenzoxazole precursor (A-5) from 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 4,4'-oxydibenzoyl chloride]

To 100 mL of N-methyl-2-pyrrolidone, 13.92 g of 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added and dissolved by stirring. Subsequently, 11.21 g of 4,4'-oxydibenzoyl chloride was added dropwise over 10 minutes while maintaining the temperature at 0 to 5 ° C., and then stirring was continued for 60 minutes. The polybenzoxazole precursor was then precipitated in 6 liters of water and the water-polybenzoxazole precursor mixture was stirred at a rate of 5000 rpm for 15 minutes. The polybenzoxazole precursor was filtered off and stirred again in 6 liters of water for 30 minutes and filtered again. The resulting polybenzoxazole precursor was then dried under reduced pressure at 45 ° C. for 3 days. The weight average molecular weight of this polybenzoxazole precursor was 15,000.

A-5

<Examples and Comparative Examples>

The components listed in the table below were mixed to obtain each photosensitive resin composition. The obtained photosensitive resin composition was pressure-filtered through a filter having a pore width of 0.8 μm. Each performance test described later was carried out for each photosensitive resin composition. The test results are also shown in Tables 1 to 3 below.

光重合開始剤：下記の市販試薬

ＩＲＧＡＣＵＲＥ製 ＯＸＥ０１（商品名）

ＩＲＧＡＣＵＲＥ製 ７８４（商品名）

ＩＲＧＡＣＵＲＥ製 ＯＸＥ０１／７８４の５０／５０（質量比）の混合物重合性化合物：下記の市販試薬

ＳＲ−２０９（２官能）（サートマー社製）

Ａ−ＴＭＭＴ（４官能）（新中村化学工業社製）

Ａ−ＤＰＨ（６官能）（新中村化学工業社製）

重合禁止剤

上記＜重合禁止剤＞の項に記載の化合物Ｆ−１〜Ｆ−３マイグレーション抑制剤

上記＜マイグレーション抑制剤＞の項に記載の化合物Ｍ−１〜Ｍ−４金属接着性改良剤

上記＜金属接着性改良剤＞の項に記載の化合物ＳＣ−１〜ＳＣ−５

溶剤：下記の化合物

ＮＭＰ／乳酸エチル：Ｎ−メチル−２−ピロリドン（Ａｓｈｌａｎｄ社製）と乳酸エチルの混合液（４０：６０質量基準）

ＧＢＬ／ＤＭＳＯ：ジメチルスルホキシド（和光純薬工業社製）とγ−ブチロラクトン（三和油化社製）の混合液（２０：８０質量基準）

The numerical value is the compounding amount (mass%).

Polymer precursor: The compound shown in the table synthesized above.

Thermal base generator, etc .:

B-1 to B-6: Exemplified compounds exemplified above in the section <Thermal base generator>

Compounds for comparison

X-6: The following compounds

Photopolymerization Initiator: The following commercially available reagents

OXE01 made by IRGACURE (trade name)

Made by IRGACURE 784 (trade name)

50/50 (mass ratio) mixture of OXE01 / 784 manufactured by IRGACURE Polymerizable compound: The following commercially available reagents

SR-209 (bifunctional) (manufactured by Sartmer)

A-TMMT (4 functional) (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

A-DPH (6-functional) (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

Polymerization inhibitor

Compound F-1 to F-3 migration inhibitor according to the above <polymerization inhibitor>

Compound M-1 to M-4 metal adhesion improver according to the above <Migration inhibitor>

Compounds SC-1 to SC-5 according to the above <Metal Adhesive Improvement Agent>

Solvent: The following compounds

NMP / Ethyl lactate: A mixture of N-methyl-2-pyrrolidone (manufactured by Ashland) and ethyl lactate (based on 40:60 mass)

GBL / DMSO: A mixture of dimethyl sulfoxide (manufactured by Wako Pure Chemical Industries, Ltd.) and γ-butyrolactone (manufactured by Sanwa Yuka Co., Ltd.) (based on 20:80 mass)

<Storage stability>

The viscosity (0 days) of the photosensitive resin composition after filtration was measured using an E-type viscometer. After allowing the photosensitive resin composition to stand in a closed container at 25 ° C. for 14 days, the viscosity (14 days) was measured again using an E-type viscometer. The viscosity volatility was calculated from the following formula. The lower the viscosity volatility, the higher the storage stability.

Viscosity variability rate = | 100 x {1- (viscosity (14 days) / viscosity (0 days))} |

The viscosity was measured at 25 ° C., and the others were in accordance with JIS Z 8803: 2011.

A: Viscosity volatility is 5% or less

B: Viscosity volatility exceeds 5% and 10% or less

C: Viscosity volatility exceeds 10% and 15% or less

D: Viscosity volatility exceeds 15% and 20% or less

E: Viscosity volatility exceeds 20%

<Mechanical properties (tensile strength)>

Each photosensitive resin composition was applied onto a silicon wafer by a spin coating method to form a photosensitive resin composition layer. The silicon wafer to which the obtained photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 4 minutes to obtain a uniform photosensitive resin composition layer having a thickness of 20 μm on the silicon wafer. ^{The photosensitive resin composition layer on the silicon wafer was exposed with an exposure energy of 400 mJ / cm 2} using a broadband exposure machine (UX-1000SN-EH01 manufactured by Ushio, Inc.), and the exposed photosensitive resin composition layer was exposed. The (resin layer) was heated at a heating rate of 5 ° C./min under a nitrogen atmosphere, reached 230 ° C., and then heated for 3 hours. The cured resin layer was immersed in a 3% hydrofluoric acid solution, and the resin layer was peeled off from the silicon wafer to obtain a resin film.

A tensile strength test was performed on the resin film peeled from the silicon wafer. The test was performed using a tensile tester (Tencilon) with a crosshead speed of 300 mm / min, a width of 10 mm, and a sample length of 50 mm in an environment of 25 ° C. and 65% RH (relative humidity) in the longitudinal and width directions of the film. Measured in accordance with JIS-K6251 (Japanese Industrial Standards). For the evaluation, the elongation at break at the time of cutting was measured 10 times each, and the average value was used. The results were evaluated by classifying them as follows.

A: 60% or more

B: 50% or more and less than 60%

C: less than 50%

<Developer solubility in unexposed areas>

Each photosensitive resin composition was applied on a silicon wafer by spin coating. A silicon wafer to which the photosensitive resin composition was applied was heated on a hot plate at 100 ° C. for 4 minutes to obtain a photosensitive resin composition layer having a thickness of 20 μm. The dissolution rate was calculated by immersing the photosensitive resin composition layer in cyclopentanone at 23 ° C. and measuring the time required for complete dissolution. A resist development analyzer (RDA-790EB manufactured by LTJ) was used for the test. The results were evaluated by classifying them as follows.

A: 0.55 μm / sec or more

B: 0.4 μm / sec or more and less than 0.55 μm / sec

C: Less than 0.4 μm / sec

<Evaluation of lithography>

Each of the photosensitive resin compositions after filtration was spin-coated on a silicon wafer. A silicon wafer to which the photosensitive resin composition was applied was dried on a hot plate at 100 ° C. for 5 minutes to form a uniform photosensitive resin composition layer having a film thickness of 20 μm on the silicon wafer. The photosensitive resin composition layer on the silicon wafer was exposed using a stepper (Nikon NSR 2005 i9C). Exposure is i-line, with 200, 300, 400, 500, 600, 700, 800 mJ / cm ² exposure energies at a wavelength of 365 nm, using line-and-space photomasks from 5 μm to 25 μm in 1 μm increments. , Exposure was performed to obtain a resin layer.

The resin layer was developed with cyclopentanone for 60 seconds. The smaller the line width of the obtained resin layer (line pattern), the finer the pattern can be formed, which is a preferable result. Further, the more the minimum line width that can be formed is less likely to change with respect to the fluctuation of the exposure amount, the more arbitrary the exposure amount in forming the fine pattern increases, which is a preferable result. The measurement limit is 5 μm.

A: It was 5 μm or more and 8 μm or less.

B: It was more than 8 μm and less than 10 μm.

C: It exceeded 10 μm

As can be seen from the above results, in the present invention, a combination of a specific polymer precursor, a specific thermobase generator and a photosensitizer (photopolymerization initiator) achieves both high storage stability and mechanical properties. It was found that this can be realized (Examples 1 to 12). In addition, if necessary, the obtained photosensitive cured film shows solubility in the developing solution of the unexposed portion, is suitable for negative type development, and further achieves good lithographic properties, and is a photosensitive material. It was found that high performance can be exhibited according to the needs in (Examples 4, 5, 7 to 12).

On the other hand, in Comparative Examples 1 and 2 in which the thermal base generator was not used, both storage stability and mechanical properties could not be achieved at the same time. Even when the thermal base generator (X-6) of Comparative Example was used, both storage stability and mechanical properties could not be achieved at the same time, and the developer solubility of the unexposed portion was also inferior (Comparative Example 3). In addition, all of Comparative Examples 1 to 3 were inferior in lithographic properties, and it was difficult to exhibit performance according to the photosensitive material.

From this result, it was found that the photosensitive resin composition of the present invention is suitable for manufacturing a cured film, a laminate using the cured film, and a semiconductor device, and can exhibit excellent performance in the product.

Further, from the above results, the thermobase generator of the present invention (compound represented by the formula (N1) or (N2)) has usefulness and is photosensitive using a polyimide precursor and a polybenzoxazole precursor. It was found that it contributes to the abundance of materials in the use of resin compositions.

<Example 100>

The photosensitive resin composition of Example 1 is pressure-filtered through a filter having a pore width of 1.0 μm, and then spun (3500 rpm, 30 seconds) on the surface of a resin substrate on which a thin copper layer is formed. bottom. The photosensitive resin composition applied to the resin substrate was dried at 100 ° C. for 2 minutes and then exposed using a stepper (NSR1505i6 manufactured by Nikon Corporation). The exposure was carried out through a mask at a wavelength of 365 nm and an exposure amount of ^{200 mJ / cm 2.} After exposure, baking was performed, developed with cyclopentanone for 30 seconds, and rinsed with propylene glycol monomethyl ether acetate (PGMEA) for 20 seconds to obtain a pattern.

Then, it was heated at 230 ° C. for 3 hours to form an interlayer insulating film for the rewiring layer. The interlayer insulating film for the rewiring layer was excellent in insulating properties.

Claims (16)

It contains at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, a thermobase generator represented by the following formula (N1) or (N2), and a photosensitive agent. Photosensitive resin composition.

In the formula, ^RN1 and ^RN2 each independently represent a hydrogen atom or a monovalent organic group, and ^RN3 and ^RN4 independently represent an aliphatic hydrocarbon which may have a hydrogen atom or a substituent, respectively. It is a group, however, the substituent is not an acid group other than a hydroxyl group, ^RN1 and ^RN2 may be linked to each other to form a cyclic structure, and ^RN3 and ^RN4 may be linked to each other. An annular structure may be formed, ^RN1 and ^RN3 may be connected to each other to form an annular structure, ^RN2 and ^RN4 may be connected to each other to form an annular structure, and X is simply. When X is a single bond, Y represents a single bond or a divalent organic group, and when X is a carbonyl group, Y represents a divalent organic group.

The photosensitive resin composition according to claim 1, wherein X and Y are single bonds in the thermal base generator represented by the formula (N1) or (N2).

The photosensitive resin composition according to claim 1 or 2, wherein the formula (N1) is any of the following formulas (N1-1) to (N1-4).

In the formula, ^RN31 , ^RN32 and ^RN33 are aliphatic hydrocarbon groups which may independently have a hydrogen atom or a substituent, except that the substituent is an acid group other than a hydroxyl group. R ^N11 represents a monovalent organic group, ^RN12 is a divalent linking group, Ar ^N is an aromatic hydrocarbon group, and

In the formula (N1-1), ^RN31 and ^RN32 may be linked to form a cyclic structure, and ^{the methylene group between RN31} and the nitrogen atom and the carbonyl group in the formula may be linked to form a cyclic structure. ^{Alternatively} , the methylene group between the RN32 and the nitrogen atom and the carbonyl group in the formula may be linked to form a cyclic structure.

In the formula (N1-2), a methylene group between the nitrogen atom and the carbonyl group of R ^N33 and in the formula may form a cyclic structure linked,

In the formula (N1-3), the carbon atom to which R ^N11 and R ^N11 is substituted may form a cyclic structure linked,

In the formula (N1-4), the carbon atom to which R ^N12 and R ^N12 is substituted may form a cyclic structure linked, the carbon atom to which Ar ^N and R ^N12 is substituted to form a cyclic structure linked You may.

The photosensitive resin composition according to any one of claims 1 to 3, wherein the polymer precursor contains a polyimide precursor.

The photosensitive resin composition according to claim 4, wherein the polyimide precursor is represented by the following formula (1).

In formula (1), A ¹ and A ² independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ independently represents a hydrogen atom or a monovalent organic group.

The photosensitive resin composition according to any one of claims 1 to 5, wherein the photosensitive agent contains a photopolymerization initiator and a polymerizable compound.

The photosensitive resin composition according to any one of claims 1 to 6, which is used for forming an interlayer insulating film for a rewiring layer.

A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 7.

A laminated body having two or more cured films according to claim 8 and having a metal layer between the two cured films.

A method for producing a cured film, which comprises a film forming step of applying the photosensitive resin composition according to any one of claims 1 to 7 to a substrate to form a film.

The method for producing a cured film according to claim 10, further comprising an exposure step of exposing the film and a developing step of developing the film after exposure.

A step of heating the film after the film forming step according to claim 10 at 80 to 450 ° C. is further included, or the film after the developing step according to claim 11 is heated at 80 to 450 ° C. A method for producing a cured film, which further comprises a step of making a cured film.

A semiconductor device having the cured film according to claim 8 or the laminate according to claim 9.

A thermobase generator represented by the following formula (N1) or (N2).

In the formula, ^RN1 and ^RN2 each independently represent a hydrogen atom or a monovalent organic group, and ^RN3 and ^RN4 independently represent an aliphatic hydrocarbon which may have a hydrogen atom or a substituent, respectively. It is a group, however, the substituent does not have an acid group other than a hydroxyl group, ^RN1 and ^RN2 may be linked to each other to form a cyclic structure, and ^RN3 and ^RN4 may be linked to each other. An annular structure may be formed, ^RN1 and ^RN3 may be connected to each other to form an annular structure, ^RN2 and ^RN4 may be connected to each other to form an annular structure, and X is simply. When X is a single bond, Y represents a single bond or a divalent organic group, and when X is a carbonyl group, Y represents a divalent organic group.

The thermobase generator according to claim 14, wherein X and Y are single bonds in the thermobase generator represented by the formula (N1) or (N2).

The thermobase generator according to claim 14 or 15, wherein the formula (N1) is any of the following formulas (N1-1) to (N1-4).

In the formula, ^RN31 , ^RN32 and ^RN33 are aliphatic hydrocarbon groups which may independently have a hydrogen atom or a substituent, except that the substituent is an acid group other than a hydroxyl group. R ^N11 represents a monovalent organic group, ^RN12 is a divalent linking group, Ar ^N is an aromatic hydrocarbon group, and

In the formula (N1-1), ^RN31 and ^RN32 may be linked to form a cyclic structure, and ^{the methylene group between RN31} and the nitrogen atom and the carbonyl group in the formula may be linked to form a cyclic structure. ^{Alternatively} , the methylene group between the RN32 and the nitrogen atom and the carbonyl group in the formula may be linked to form a cyclic structure.

In the formula (N1-2), a methylene group between the nitrogen atom and the carbonyl group of R ^N33 and in the formula may form a cyclic structure linked,

In the formula (N1-3), the carbon atom to which R ^N11 and R ^N11 is substituted may form a cyclic structure linked,

In the formula (N1-4), the carbon atom to which R ^N12 and R ^N12 is substituted may form a cyclic structure linked, the carbon atom to which Ar ^N and R ^N12 is substituted to form a cyclic structure linked You may.