JP2023034723A - Resin composition, cured product, laminate, method for manufacturing cured product, method for manufacturing laminate, method for manufacturing semiconductor device, semiconductor device, and compound - Google Patents

Abstract

To provide a resin composition from which a cured product excellent in reliability can be obtained, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for manufacturing the cured product, a method for manufacturing the laminate, a method for manufacturing a semiconductor device including the method for manufacturing the laminate, and a semiconductor device including the cured product or the laminate.SOLUTION: There are provided a resin composition which contains at least one resin selected from the group consisting of a cyclic resin and its precursor, and a compound represented by the following formula (1-1); a cured product obtained by curing the resin composition; a laminate including the cured product; a method for manufacturing the cured product; a method for manufacturing the laminate; a method for manufacturing a semiconductor device including the method for manufacturing the laminate; and a semiconductor device including the cured product or the laminate.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a resin composition, a cured product, a laminate, a method for producing a cured product, a method for producing a laminate, a method for producing a semiconductor device, a semiconductor device, and a compound.

Cyclized resins such as polyimide are used in various applications because of their excellent heat resistance and insulating properties. The use is not particularly limited, but in the case of a semiconductor device for mounting, use as a material for an insulating film or a sealing material, or as a protective film can be mentioned. It is also used as a base film or coverlay for flexible substrates.

For example, in the applications described above, the cyclized resin such as polyimide is used in the form of a resin composition containing a precursor of the cyclized resin such as a polyimide precursor.
Such a resin composition is applied to a substrate, for example, by coating to form a photosensitive film, and then, if necessary, exposure, development, heating, etc. are performed to form a cured product on the substrate. be able to.
A precursor of the cyclized resin such as a polyimide precursor is cyclized, for example, by heating, and becomes a cyclized resin such as polyimide in the cured product.
Since the resin composition can be applied by a known coating method or the like, for example, there is a high degree of freedom in designing the shape, size, application position, etc. of the resin composition to be applied. It can be said that it is excellent in sex. In addition to the high performance possessed by cyclized resins such as polyimide, from the viewpoint of such excellent manufacturing adaptability, industrial application and development of the above-mentioned resin compositions are increasingly expected.

For example, Patent Document 1 discloses a polymer precursor whose reaction to the final product is promoted by a basic substance or by heating in the presence of a basic substance, and a specific structure, and an electromagnetic wave. A photosensitive resin composition is disclosed which is characterized by containing a base generator which generates a base upon irradiation and heating.

JP 2011-121962 A

A resin composition for obtaining a cured product is required to provide a cured film having excellent adhesion between a metal and a cured film after a long period of time (that is, a cured film having excellent reliability).

The present invention provides a resin composition that provides a highly reliable cured product, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for producing the cured product, and the production of the laminate. An object of the present invention is to provide a semiconductor device manufacturing method including a method, a method for manufacturing the laminate, and a semiconductor device including the cured product or the laminate.

式（１－１）中、Ｒ^１はそれぞれ独立に、水素原子又は１価の有機基を表し、Ｒ^２はそれぞれ独立に、芳香族ヘテロ環を表し、Ｒ^３はそれぞれ独立に、水素原子又は１価の有機基を表し、Ｌ^１はそれぞれ独立に、２価の連結基を表し、ｎは１以上の整数を表し、Ｌ^２はｎ価の連結基を表す。
＜２＞ 式（１－１）中のＲ^２がアゾール構造を含む、＜１＞に記載の樹脂組成物。
＜３＞ 式（１－１）中のＲ^２がプリン構造を含む、＜１＞又は＜２＞に記載の樹脂組成物。
＜４＞ 式（１－１）中のｎが１であり、かつ、Ｌ^２が下記式（Ｌ２－１）で表される基である、＜１＞～＜３＞のいずれか１つに記載の樹脂組成物。

式（Ｌ２－１）中、Ａｒは芳香族基を表し、Ｌ^Ｌ２は単結合又は２価の連結基を表し、Ｒ^Ｌ２は水素原子、ヒドロキシ基又は１価の有機基を表し、＊は式（１－１）中のカルボニル基との結合部位を表す。
＜５＞ 式（１－１）中のＲ^３が水素原子である、＜１＞～＜４＞のいずれか１つに記載の樹脂組成物。
＜６＞ 式（１－１）中のＬ^１が下記式（Ｌ１－１）で表される構造である、＜１＞～＜５＞のいずれか１つに記載の樹脂組成物。

式（Ｌ１－１）中、Ｌ^Ｌ１は２価の連結基を表し、＃は式（１－１）中のＲ^３が結合した窒素原子との結合部位を表し、＊は式（１－１）中のＲ¹が結合した窒素原子との結合部位を表す。
＜７＞ 上記式（１－１）で表される化合物が、光又は熱の作用により塩基を発生する化合物である、＜１＞～＜６＞のいずれか１つに記載の樹脂組成物。
＜８＞ 上記樹脂が、ポリイミド及びポリイミド前駆体から選択される少なくとも１種の樹脂である、＜１＞～＜７＞のいずれか１つに記載の樹脂組成物。
＜９＞ 再配線層用層間絶縁膜の形成に用いられる、＜１＞～＜８＞のいずれか１つに記載の樹脂組成物。
＜１０＞ ＜１＞～＜９＞のいずれか１つに記載の樹脂組成物を硬化してなる硬化物。
＜１１＞ ＜１０＞に記載の硬化物からなる層を２層以上含み、上記硬化物からなる層同士のいずれかの間に金属層を含む積層体。
＜１２＞ ＜１＞～＜９＞のいずれか１つに記載の樹脂組成物を基材上に適用して膜を形成する膜形成工程を含む、硬化物の製造方法。
＜１３＞ 上記膜を選択的に露光する露光工程及び上記膜を現像液を用いて現像してパターンを形成する現像工程を含む、＜１２＞に記載の硬化物の製造方法。
＜１４＞ 上記膜を５０～４５０℃で加熱する加熱工程を含む、＜１２＞又は＜１３＞に記載の硬化物の製造方法。
＜１５＞ ＜１２＞～＜１４＞のいずれか１つに記載の硬化物の製造方法を含む、積層体の製造方法。
＜１６＞ ＜１２＞～＜１４＞のいずれか１つに記載の硬化物の製造方法、又は、＜１５＞に記載の積層体の製造方法を含む、半導体デバイスの製造方法。
＜１７＞ ＜１０＞に記載の硬化物又は＜１１＞に記載の積層体を含む、半導体デバイス。
＜１８＞ 下記式（１－１）で表される
化合物。

式（１－１）中、Ｒ^１はそれぞれ独立に、水素原子又は１価の有機基を表し、Ｒ^２はそれぞれ独立に、芳香族ヘテロ環を表し、Ｒ^３はそれぞれ独立に、水素原子又は１価の有機基を表し、Ｌ^１はそれぞれ独立に、２価の連結基を表し、ｎは１以上の整数を表し、Ｌ^２はｎ価の連結基を表す。 Examples of representative embodiments of the present invention are provided below.
<1> at least one resin selected from the group consisting of cyclized resins and precursors thereof;
A resin composition comprising a compound represented by the following formula (1-1).

In formula (1-1), each R ¹ independently represents a hydrogen atom or a monovalent organic group, each R ² independently represents an aromatic heterocycle, and each R ³ independently represents a hydrogen atom or represents a monovalent organic group, each L ¹ independently represents a divalent linking group, n represents an integer of 1 or more, and L ² represents an n-valent linking group.
<2> The resin composition according to <1>, wherein R ² in formula (1-1) contains an azole structure.
<3> The resin composition according to <1> or <2>, wherein R ² in formula (1-1) contains a purine structure.
<4> Any one of <1> to <3>, wherein n in formula (1-1) is 1, and ^L2 is a group represented by the following formula (L2-1) The described resin composition.

In formula (L2-1), Ar represents an aromatic group, L ^L2 represents a single bond or a divalent linking group, R ^L2 represents a hydrogen atom, a hydroxy group or a monovalent organic group, * represents the formula represents the bonding site with the carbonyl group in (1-1).
<5> The resin composition according to any one of <1> to <4>, wherein R ³ in formula (1-1) is a hydrogen atom.
<6> The resin composition according to any one of <1> to <5>, wherein L ¹ in formula (1-1) has a structure represented by formula (L1-1) below.

In formula (L1-1), L ^L1 represents a divalent linking group, # represents a binding site to the nitrogen atom to which R ³ in formula (1-1) is bonded, * represents formula (1-1 ) represents the bonding site with the nitrogen atom to which R ¹ is bonded.
<7> The resin composition according to any one of <1> to <6>, wherein the compound represented by formula (1-1) above is a compound that generates a base by the action of light or heat.
<8> The resin composition according to any one of <1> to <7>, wherein the resin is at least one resin selected from polyimides and polyimide precursors.
<9> The resin composition according to any one of <1> to <8>, which is used for forming an interlayer insulating film for rewiring layers.
<10> A cured product obtained by curing the resin composition according to any one of <1> to <9>.
<11> A laminate comprising two or more layers of the cured product according to <10> and a metal layer between any of the layers of the cured product.
<12> A method for producing a cured product, comprising a film forming step of applying the resin composition according to any one of <1> to <9> onto a substrate to form a film.
<13> The method for producing a cured product according to <12>, comprising an exposure step of selectively exposing the film and a developing step of developing the film with a developer to form a pattern.
<14> The method for producing a cured product according to <12> or <13>, comprising a heating step of heating the film at 50 to 450°C.
<15> A method for producing a laminate, comprising the method for producing a cured product according to any one of <12> to <14>.
<16> A method for producing a semiconductor device, comprising the method for producing a cured product according to any one of <12> to <14> or the method for producing a laminate according to <15>.
<17> A semiconductor device comprising the cured product according to <10> or the laminate according to <11>.
<18> A compound represented by the following formula (1-1).

In formula (1-1), each R ¹ independently represents a hydrogen atom or a monovalent organic group, each R ² independently represents an aromatic heterocycle, and each R ³ independently represents a hydrogen atom or represents a monovalent organic group, each L ¹ independently represents a divalent linking group, n represents an integer of 1 or more, and L ² represents an n-valent linking group.

According to the present invention, a resin composition that provides a highly reliable cured product, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for producing the cured product, and the laminate and a method for manufacturing a semiconductor device including the method for manufacturing the laminate, and a semiconductor device including the cured product or the laminate.

Principal embodiments of the present invention are described below. However, the invention is not limited to the illustrated embodiments.
In this specification, a numerical range represented by the symbol "to" means a range including the numerical values before and after "to" as lower and upper limits, respectively.
As used herein, the term "process" is meant to include not only independent processes, but also processes that are indistinguishable from other processes as long as the desired effects of the process can be achieved.
In the description of a group (atomic group) in the present specification, a description that does not describe substitution or unsubstituted includes a group (atomic group) having no substituent as well as a group (atomic group) having a substituent. For example, the term “alkyl group” includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).
As used herein, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Light used for exposure includes actinic rays or radiation such as emission line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
As used herein, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", and "(meth)acrylic" means both "acrylic" and "methacrylic", or , and “(meth)acryloyl” means either or both of “acryloyl” and “methacryloyl”.
In this specification, Me in the structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
As used herein, the term "total solid content" refers to the total mass of all components of the composition excluding the solvent. Moreover, in this specification, the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values measured using a gel permeation chromatography (GPC) method, unless otherwise specified, and are defined as polystyrene conversion values. In the present specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) are, for example, HLC-8220GPC (manufactured by Tosoh Corporation), guard column HZ-L, TSKgel Super HZM-M, TSKgel It can be obtained by connecting Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation) in series. Unless otherwise stated, their molecular weights were determined using THF (tetrahydrofuran) as an eluent. However, NMP (N-methyl-2-pyrrolidone) can also be used when THF is not suitable as an eluent, such as when the solubility is low. In addition, detection in GPC measurement uses a UV ray (ultraviolet) wavelength detector of 254 nm unless otherwise specified.
In this specification, when the positional relationship of each layer constituting the laminate is described as "above" or "below", it means that another layer is above or below the reference layer among the layers of interest. It would be nice if there was That is, a third layer or element may be interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other. In addition, unless otherwise specified, the direction in which the layers are stacked with respect to the base material is referred to as "upper", or when there is a resin composition layer, the direction from the base material to the resin composition layer is referred to as "upper". and the opposite direction is called "down". It should be noted that such setting of the vertical direction is for the sake of convenience in this specification, and in an actual aspect, the "upward" direction in this specification may differ from the vertically upward direction.
In this specification, unless otherwise specified, the composition may contain two or more compounds corresponding to each component contained in the composition. In addition, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component.
In this specification, the temperature is 23° C., the pressure is 101,325 Pa (1 atm), and the relative humidity is 50% RH, unless otherwise stated.
Combinations of preferred aspects are more preferred aspects herein.

式（１－１）中、Ｒ^１はそれぞれ独立に、水素原子又は１価の有機基を表し、Ｒ^２はそれぞれ独立に、芳香族ヘテロ環を表し、Ｒ^３はそれぞれ独立に、水素原子又は１価の有機基を表し、Ｌ^１はそれぞれ独立に、２価の連結基を表し、ｎは１以上の整数を表し、Ｌ^２はｎ価の連結基を表す。 (resin composition)
The resin composition of the present invention comprises at least one resin selected from the group consisting of cyclized resins and precursors thereof, and a compound represented by the following formula (1-1) (hereinafter also referred to as "specific compound" .) and including.

In formula (1-1), each R ¹ independently represents a hydrogen atom or a monovalent organic group, each R ² independently represents an aromatic heterocycle, and each R ³ independently represents a hydrogen atom or represents a monovalent organic group, each L ¹ independently represents a divalent linking group, n represents an integer of 1 or more, and L ² represents an n-valent linking group.

The resin composition of the present invention is preferably used for forming a photosensitive film subjected to exposure and development, and is preferably used for forming a film subjected to exposure and development using a developer containing an organic solvent. preferable.
INDUSTRIAL APPLICABILITY The resin composition of the present invention can be used, for example, to form an insulating film for semiconductor devices, an interlayer insulating film for rewiring layers, a stress buffer film, and the like, and can be used to form an interlayer insulating film for rewiring layers. preferable.
Further, the resin composition of the present invention may be used for forming a photosensitive film for positive development, or may be used for forming a photosensitive film for negative development.
In the present invention, negative development refers to development in which non-exposed areas are removed by development in exposure and development, and positive development refers to development in which exposed areas are removed by development.
The exposure method, the developer, and the development method include, for example, the exposure method described in the exposure step, the developer and the development method described in the development step in the description of the method for producing a cured product described later. is used.

According to the resin composition of the present invention, a highly reliable cured film can be obtained.
Conventionally, a nitrogen-containing compound (a compound having a triazole structure or a tetrazole structure, etc.) is used in a resin composition containing a cyclized resin or a precursor thereof to improve adhesion to metals. However, there is still room for improvement from the viewpoint of the adhesion between the metal and the cured film after a long period of time.
Therefore, as a result of intensive studies by the present inventors, by using a resin composition containing a specific compound, a cured film having excellent adhesion between the metal and the cured film after a long period of time (that is, a cured film having excellent reliability ) can be obtained.
Although the mechanism by which the above effects are obtained is unknown, it is presumed as follows.
It is believed that the compound represented by formula (1-1) is decomposed by heating or the like to generate a compound having an amino group and an aromatic heterocycle.
The aromatic heterocyclic structure in this compound is highly adsorbable to metals, and the amino group in the generated compound forms a strong bond such as an imide bond with the cyclized resin or its precursor resin. , the above aromatic heterocycle is considered to be introduced into the resin. As a result, it is believed that the adhesion between the resin and the metal is improved, and a highly reliable cured film is obtained.
Furthermore, as described above, due to the heating during the formation of the cured film, the decomposition of the specific compound produces a compound that has high adsorption to metal and forms a strong bond such as an imide bond with the resin. It is presumed that the cured film and the metal layer of No. 2 are unlikely to form voids at their boundaries even after a long period of time.
In addition, since the specific compound before decomposition has low basicity, it is considered that the storage stability of the composition is also excellent.
Furthermore, a compound having an amino group is generated from the specific compound after decomposition as described above. The amino group promotes cyclization of the unclosed portion of the precursor of the cyclized resin and the cyclized resin, so that the obtained cured product is considered to be excellent in elongation at break.

Here, Patent Document 1 does not describe a resin composition containing a specific compound.

The components contained in the resin composition of the present invention are described in detail below.

<Specific resin>
The resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of cyclized resins and precursors thereof.
The cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in its main chain structure.
In the present invention, the main chain represents the relatively longest connecting chain in the resin molecule.
Examples of cyclized resins include polyimide, polybenzoxazole, and polyamideimide.
A precursor of a cyclized resin is a resin that undergoes a change in chemical structure by an external stimulus to become a cyclized resin, preferably a resin that undergoes a change in chemical structure by heat to become a cyclized resin. A resin that becomes a cyclized resin by forming a ring structure is more preferable.
Precursors of the cyclized resin include polyimide precursors, polybenzoxazole precursors, polyamideimide precursors, and the like.
That is, the resin composition of the present invention contains, as a specific resin, at least one selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, polyamideimides, and polyamideimide precursors. It preferably contains a resin (specific resin).
The resin composition of the present invention preferably contains, as the specific resin, at least one resin selected from the group consisting of polyimides and polyimide precursors.
Moreover, the specific resin preferably has a polymerizable group, and more preferably contains a radically polymerizable group.
When the specific resin has a radically polymerizable group, the resin composition of the present invention preferably contains a radical polymerization initiator described later, and contains a radical polymerization initiator described later and a radical cross-linking agent described later. is more preferred. Further, if necessary, a sensitizer described later can be included. For example, a negative photosensitive film is formed from the resin composition of the present invention.
Moreover, the specific resin may have a polarity conversion group such as an acid-decomposable group.
When the specific resin has an acid-decomposable group, the resin composition of the present invention preferably contains a photoacid generator, which will be described later. From such a resin composition of the present invention, for example, a chemically amplified positive photosensitive film or negative photosensitive film is formed.

式（２）中、Ａ^１及びＡ^２は、それぞれ独立に、酸素原子又は－ＮＨ－を表し、Ｒ^１１１は、２価の有機基を表し、Ｒ^１１５は、４価の有機基を表し、Ｒ^１１３及びＲ^１１４は、それぞれ独立に、水素原子又は１価の有機基を表す。 [Polyimide precursor]
Although the type of the polyimide precursor used in the present invention is not particularly limited, it preferably contains a repeating unit represented by the following formula (2).

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

A ¹ and A ² in formula (2) each independently represent an oxygen atom or —NH—, preferably an oxygen atom.
R ¹¹¹ in formula (2) represents a divalent organic group. Examples of divalent organic groups include groups containing linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, linear or branched aliphatic groups having 2 to 20 carbon atoms, A cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable. In the straight-chain or branched aliphatic group, the hydrocarbon group in the chain may be substituted with a group containing a heteroatom, and in the cyclic aliphatic group and the aromatic group, the ring-membered hydrocarbon group is a heteroatom. may be substituted with a group containing Groups represented by -Ar- and -Ar-L-Ar- are exemplified as preferred embodiments of the present invention, and groups represented by -Ar-L-Ar- are particularly preferred. However, Ar is each independently an aromatic group, L is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms optionally substituted with a fluorine atom, -O-, -CO-, —S—, —SO ₂ — or —NHCO—, or a group consisting of a combination of two or more of the above. Preferred ranges for these are as described above.

R ¹¹¹ is preferably derived from a diamine. Diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, or two or more types may be used.
Specifically, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferably a diamine containing, more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. In the straight-chain or branched aliphatic group, the hydrocarbon group in the chain may be substituted with a group containing a heteroatom. may be substituted with a group containing Examples of groups containing aromatic groups include:

式中、Ａは単結合又は２価の連結基を表し、単結合、又は、フッ素原子で置換されていてもよい炭素数１～１０の脂肪族炭化水素基、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ－、－ＳＯ_２－、－ＮＨＣＯ－、又は、これらの組み合わせから選択される基であることが好ましく、単結合、フッ素原子で置換されていてもよい炭素数１～３のアルキレン基、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ－、又は、－ＳＯ_２－から選択される基であることがより好ましく、－ＣＨ_２－、－Ｏ－、－Ｓ－、－ＳＯ_２－、－Ｃ（ＣＦ_３）_２－、又は、－Ｃ（ＣＨ_３）_２－であることが更に好ましい。
式中、＊は他の構造との結合部位を表す。

In the formula, A represents a single bond or a divalent linking group, a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms optionally substituted with a fluorine atom, -O-, -C (= O)-, -S-, -SO ₂ -, -NHCO-, or preferably a group selected from a combination thereof, having 1 to 3 carbon atoms optionally substituted by a single bond or a fluorine atom , an alkylene group of -O-, -C(=O)-, -S-, or -SO ₂ -, more preferably a group selected from -CH ₂ -, -O-, -S- , —SO ₂ —, —C(CF ₃ ) ₂ —, or —C(CH ₃ ) ₂ — are more preferred.
In the formula, * represents a binding site with other structures.

Specific examples of diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; ,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4- aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4′-diamino-3,3′-dimethylcyclohexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4′- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- and 3,3'-diaminodiphenylmethane, 4,4'- and 3,3'-diamino diphenyl sulfone, 4,4'- and 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2 '-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl ) hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino -4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl) ) sulfone, 4,4′-diaminoparaterphenyl, 4,4′-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy ) phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3′- dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-a 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, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2, 4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1 , 2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters 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, p-bis(4-amino- 2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone, 4,4'-bis( 3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3′,5,5′- tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolysine and At least one diamine selected from 4,4'-diaminoquaterphenyl may be used.

Also preferred are the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of WO 2017/038598.

Also preferably used are diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of WO 2017/038598.

R ¹¹¹ is preferably represented by -Ar-L-Ar- from the viewpoint of the flexibility of the resulting organic film. However, Ar is each independently an aromatic group, L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- , —SO ₂ — or —NHCO—, or a group consisting of a combination of two or more of the above. Ar is preferably a phenylene group, L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- or -SO ₂ - . The aliphatic hydrocarbon group here is preferably an alkylene group.

式（５１）中、Ｒ^５０～Ｒ^５７は、それぞれ独立に、水素原子、フッ素原子又は１価の有機基であり、Ｒ^５０～Ｒ^５７の少なくとも１つは、フッ素原子、メチル基又はトリフルオロメチル基であり、＊はそれぞれ独立に、式（２）中の窒素原子との結合部位を表す。
Ｒ^５０～Ｒ^５７の１価の有機基としては、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。

式（６１）中、Ｒ^５８及びＲ^５９は、それぞれ独立に、フッ素原子、メチル基、又はトリフルオロメチル基であり、＊はそれぞれ独立に、式（２）中の窒素原子との結合部位を表す。
式（５１）又は（６１）の構造を与えるジアミンとしては、２，２’－ジメチルベンジジン、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。これらは１種で又は２種以上を組み合わせて用いてもよい。 From the viewpoint of i-line transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or (61). In particular, from the viewpoint of i-line transmittance and availability, a divalent organic group represented by Formula (61) is more preferable.
Equation (51)

In formula (51), R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group or a trifluoro It is a methyl group, and each * independently represents a binding site to the nitrogen atom in formula (2).
The monovalent organic groups represented by R ⁵⁰ to R ⁵⁷ include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), A fluorinated alkyl group and the like can be mentioned.

In formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, a methyl group, or a trifluoromethyl group, and * is each independently a bonding site to the nitrogen atom in formula (2) show.
Diamines that give the structure of formula (51) or (61) include 2,2′-dimethylbenzidine, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 2,2′-bis (Fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like. These may be used alone or in combination of two or more.

式（５）中、Ｒ^１１２は単結合又は２価の連結基であり、単結合、又は、フッ素原子で置換されていてもよい炭素数１～１０の脂肪族炭化水素基、－Ｏ－、－ＣＯ－、－Ｓ－、－ＳＯ_２－、及び－ＮＨＣＯ－、ならびに、これらの組み合わせから選択される基であることが好ましく、単結合、フッ素原子で置換されていてもよい炭素数１～３のアルキレン基、－Ｏ－、－ＣＯ－、－Ｓ－及び－ＳＯ_２－から選択される基であることがより好ましく、－ＣＨ_２－、－Ｃ（ＣＦ_３）_２－、－Ｃ（ＣＨ_３）_２－、－Ｏ－、－ＣＯ－、－Ｓ－及び－ＳＯ_２－からなる群から選択される２価の基であることが更に好ましい。 R ¹¹⁵ in formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or (6) is more preferable.
In formula (5) or (6), each * independently represents a binding site to another structure.

In formula (5), R ¹¹² is a single bond or a divalent linking group, a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, -CO-, -S-, -SO ₂ -, and -NHCO-, and preferably a group selected from a combination thereof, having 1 to 1 carbon atoms optionally substituted by a single bond or a fluorine atom 3 alkylene group, -O-, -CO-, -S- and -SO ₂ -, and -CH ₂ -, -C(CF ₃ ) ₂ -, -C( It is more preferably a divalent group selected from the group consisting of CH ₃ ) ₂ -, -O-, -CO-, -S- and -SO ₂ -.

式（Ｏ）中、Ｒ^１１５は、４価の有機基を表す。Ｒ^１１５の好ましい範囲は式（２）におけるＲ^１１５と同義であり、好ましい範囲も同様である。 Specifically, R ¹¹⁵ includes a tetracarboxylic acid residue remaining after removal of an anhydride group from a tetracarboxylic dianhydride. The polyimide precursor may contain only one type of tetracarboxylic dianhydride residue as a structure corresponding to ^R115 , or may contain two or more types thereof.
The tetracarboxylic dianhydride is preferably represented by the following formula (O).

In formula (O), R ¹¹⁵ represents a tetravalent organic group. The preferred range of R ¹¹⁵ is synonymous with R ¹¹⁵ in formula (2), and the preferred range is also the same.

Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′- Diphenyl sulfide tetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′ ,4,4′-diphenylmethanetetracarboxylic dianhydride, 2,2′,3,3′-diphenylmethanetetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-benzophenonetetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5 ,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2 , 2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5, 6-naphthalenetetracarboxylic dianhydride, 2,2′,3,3′-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4, 5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2, 3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and these C1-6 alkyl and C1-6 alkoxy derivatives are included.

Further, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017/038598 are also preferred examples.

In formula (2), it is also possible that at least one of R ¹¹¹ and R ¹¹⁵ has an OH group. More specifically, R ¹¹¹ includes residues of bisaminophenol derivatives.

R ¹¹³ and R ¹¹⁴ in formula (2) each independently represent a hydrogen atom or a monovalent organic group. The monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. At least one of R ¹¹³ and R ¹¹⁴ preferably contains a polymerizable group, more preferably both contain a polymerizable group. It is also preferred that at least one of R ¹¹³ and R ¹¹⁴ contains two or more polymerizable groups. The polymerizable group is a group capable of undergoing a cross-linking reaction by the action of heat, radicals, or the like, and is preferably a radically polymerizable group. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. be done. As the radically polymerizable group possessed by the polyimide precursor, a group having an ethylenically unsaturated bond is preferred.
Groups having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., a vinylphenyl group), and a (meth)acrylamide group. , a (meth)acryloyloxy group, a group represented by the following formula (III), and the like, and a group represented by the following formula (III) is preferable.

In formula (III), R ²⁰⁰ represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, preferably a hydrogen atom or a methyl group.
In formula (III), * represents a binding site with another structure.
In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, —CH ₂ CH(OH)CH ₂ —, a cycloalkylene group or a polyalkyleneoxy group.
Suitable examples of R ²⁰¹ include ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, alkylene groups such as dodecamethylene, 1,2-butanediyl, 1, 3-butanediyl group, —CH ₂ CH(OH)CH ₂ —, polyalkyleneoxy group, ethylene group, alkylene group such as propylene group, —CH ₂ CH(OH)CH ₂ —, cyclohexyl group, polyalkylene An oxy group is more preferred, and an alkylene group such as an ethylene group, a propylene group, or a polyalkyleneoxy group is even more preferred.
In the present invention, a polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
When the polyalkyleneoxy group contains multiple types of alkyleneoxy groups with different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement or a block arrangement. Alternatively, it may be arranged in a pattern such as an alternating pattern.
The number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, and 2 to 6. is more preferred, 2 to 5 is more preferred, 2 to 4 is even more preferred, 2 or 3 is particularly preferred, and 2 is most preferred.
Moreover, the said alkylene group may have a substituent. Preferred substituents include alkyl groups, aryl groups, and halogen atoms.
The number of alkyleneoxy groups contained in the polyalkyleneoxy group (repeating number of polyalkyleneoxy groups) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.
As the polyalkyleneoxy group, from the viewpoint of solvent solubility and solvent resistance, a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a plurality of ethyleneoxy groups and a plurality of propylene A group to which an oxy group is bonded is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is still more preferable. In the group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, or may be arranged to form blocks. , may be arranged in a pattern such as alternately. Preferred embodiments of the number of repetitions of ethyleneoxy groups and the like in these groups are as described above.

In formula (2), when R ¹¹³ is a hydrogen atom, or when R ¹¹⁴ is a hydrogen atom, the polyimide precursor may form a tertiary amine compound having an ethylenically unsaturated bond and a counter salt. good. Examples of such tertiary amine compounds having ethylenically unsaturated bonds include N,N-dimethylaminopropyl methacrylate.

In formula (2), at least one of R ¹¹³ and R ¹¹⁴ may be a polarity conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxyl group. , a tertiary alkyl ester group and the like are preferable, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferable.
Specific examples of acid-decomposable groups include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, and tert-butoxycarbonylmethyl. groups, trimethylsilyl ether groups, and the like. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.

Also, the polyimide precursor preferably has a fluorine atom in its structure. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

For the purpose of improving adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, there is an embodiment using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, or the like as the diamine.

式（２－Ａ）中、Ａ^１及びＡ^２は、酸素原子を表し、Ｒ^１１１及びＲ^１１２は、それぞれ独立に、２価の有機基を表し、Ｒ^１１３及びＲ^１１４は、それぞれ独立に、水素原子又は１価の有機基を表し、Ｒ^１１３及びＲ^１１４の少なくとも一方は、重合性基を含む基であり、両方が重合性基を含む基であることが好ましい。 The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one polyimide precursor used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By including the repeating unit represented by the formula (2-A) in the polyimide precursor, it becomes possible to further widen the width of the exposure latitude.
Formula (2-A)

In formula (2-A), A ¹ and A ² represent an oxygen atom, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, R ¹¹³ and R ¹¹⁴ each independently represents a hydrogen atom or a monovalent organic group, at least one of R ¹¹³ and R ¹¹⁴ is a group containing a polymerizable group, and both are preferably groups containing a polymerizable group.

A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ are each independently synonymous with A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (2), and preferred ranges are also the same. .
R ¹¹² has the same definition as R ¹¹² in formula (5), and the preferred range is also the same.

The polyimide precursor may contain one type of repeating unit represented by formula (2), but may contain two or more types thereof. It may also contain structural isomers of the repeating unit represented by formula (2). It goes without saying that the polyimide precursor may also contain other types of repeating units in addition to the repeating units of formula (2) above.

One embodiment of the polyimide precursor of the present invention includes a mode in which the content of the repeating unit represented by formula (2) is 50 mol % or more of the total repeating units. The total content is more preferably 70 mol % or more, still more preferably 90 mol % or more, and particularly preferably more than 90 mol %. The upper limit of the total content is not particularly limited, and all repeating units in the polyimide precursor excluding terminals may be repeating units represented by formula (2).

The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, still more preferably 15,000 to 40,000. Also, the number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, still more preferably 4,000 to 20,000.
The polyimide precursor preferably has a molecular weight distribution of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. Although the upper limit of the polyimide precursor's molecular weight dispersity is not particularly defined, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
In the present specification, the molecular weight dispersity is a value calculated by weight average molecular weight/number average molecular weight.
Moreover, when the resin composition contains a plurality of polyimide precursors as the specific resin, the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one polyimide precursor are preferably within the above ranges. It is also preferable that the weight-average molecular weight, the number-average molecular weight, and the degree of dispersion calculated from the plurality of types of polyimide precursors as one resin are within the ranges described above.

[Polyimide]
The polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide soluble in a developer containing an organic solvent as a main component.
In the present specification, the alkali-soluble polyimide refers to a polyimide that dissolves in 100 g of a 2.38% by mass tetramethylammonium aqueous solution at 23° C. by 0.1 g or more, and from the viewpoint of pattern formation, 0.5 g or more. It is preferably a polyimide that dissolves, and more preferably a polyimide that dissolves 1.0 g or more. Although the upper limit of the dissolved amount is not particularly limited, it is preferably 100 g or less.
Moreover, the polyimide is preferably a polyimide having a plurality of imide structures in its main chain from the viewpoint of the film strength and insulating properties of the resulting organic film.
As used herein, the term "main chain" refers to the relatively longest linking chain in the molecule of the polymer compound that constitutes the resin, and the term "side chain" refers to the other linking chain.

- Fluorine atom -
From the viewpoint of the film strength of the organic film to be obtained, the polyimide preferably has a fluorine atom.
A fluorine atom is preferably included in, for example, R132 in a repeating unit represented by formula (4) described later or ^R131 in a repeating unit represented by formula (4) described later. ) or R131 in the repeating unit represented by the formula (4) described below as a fluorinated alkyl group.
The amount of fluorine atoms relative to the total mass of polyimide is preferably 5% by mass or more and preferably 20% by mass or less.

-Silicon atom-
From the viewpoint of the film strength of the organic film to be obtained, the polyimide preferably has a silicon atom.
A silicon atom, for example, is preferably contained in R131 in a repeating unit represented by formula (4) described later, and organically modified (poly)siloxane described later in R131 in a repeating unit represented by formula (4) described later More preferably included as a structure.
The silicon atom or the organically modified (poly)siloxane structure may be contained in the side chain of the polyimide, but is preferably contained in the main chain of the polyimide.
The amount of silicon atoms relative to the total mass of polyimide is preferably 1% by mass or more, and more preferably 20% by mass or less.

- Ethylenically unsaturated bond -
From the viewpoint of the film strength of the resulting organic film, the polyimide preferably has an ethylenically unsaturated bond.
The polyimide may have an ethylenically unsaturated bond at the end of its main chain or in a side chain, preferably in a side chain.
The ethylenically unsaturated bond preferably has radical polymerizability.
The ethylenically unsaturated bond is preferably contained in R ¹³² in a repeating unit represented by the formula (4) described later, or R ¹³¹ in a repeating unit represented by the formula (4) described later. It is more preferably included as a group having an ethylenically unsaturated bond in R ¹³² in the repeating unit represented by (4) or R ¹³¹ in the repeating unit represented by formula (4) described below.
Among these, the ethylenically unsaturated bond is preferably contained in R ¹³¹ in the repeating unit represented by formula (4) described later, and ethylene is contained in R ¹³¹ in the repeating unit represented by formula (4) described later It is more preferably included as a group having a polyunsaturated bond.
The group having an ethylenically unsaturated bond includes a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acrylamide group, a (meth) Examples include an acryloyloxy group and a group represented by the following formula (IV).

In formula (IV), R ²⁰ represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, preferably a hydrogen atom or a methyl group.

In formula (IV), R ²¹ is an alkylene group having 2 to 12 carbon atoms, —O—CH ₂ CH(OH)CH ₂ —, —C(═O)O—, —O(C═O)NH— , a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12, 1 to 6 are more preferred, and 1 to 3 are particularly preferred), or a group in which two or more of these are combined.
In addition, the alkylene group having 2 to 12 carbon atoms may be a linear, branched, cyclic, or a combination of these alkylene groups.
As the alkylene group having 2 to 12 carbon atoms, an alkylene group having 2 to 8 carbon atoms is preferable, and an alkylene group having 2 to 4 carbon atoms is more preferable.

式（Ｒ１）～（Ｒ３）中、Ｌは単結合、又は、炭素数２～１２のアルキレン基、炭素数２～３０の（ポリ）アルキレンオキシ基若しくはこれらを２以上結合した基を表し、Ｘは酸素原子又は硫黄原子を表し、＊は他の構造との結合部位を表し、●は式（ＩＶ）中のＲ^２１が結合する酸素原子との結合部位を表す。
式（Ｒ１）～（Ｒ３）中、Ｌにおける炭素数２～１２のアルキレン基、又は、炭素数２～３０の（ポリ）アルキレンオキシ基の好ましい態様は、上述のＲ^２１における、炭素数２～１２のアルキレン基、又は、炭素数２～３０の（ポリ）アルキレンオキシ基の好ましい態様と同様である。
式（Ｒ１）中、Ｘは酸素原子であることが好ましい。
式（Ｒ１）～（Ｒ３）中、＊は式（ＩＶ）中の＊と同義であり、好ましい態様も同様である。
式（Ｒ１）で表される構造は、例えば、フェノール性ヒドロキシ基等のヒドロキシ基を有するポリイミドと、イソシアナト基及びエチレン性不飽和結合を有する化合物（例えば、２－イソシアナトエチルメタクリレート等）とを反応することにより得られる。
式（Ｒ２）で表される構造は、例えば、カルボキシ基を有するポリイミドと、ヒドロキシ基及びエチレン性不飽和結合を有する化合物（例えば、２－ヒドロキシエチルメタクリレート等）とを反応することにより得られる。
式（Ｒ３）で表される構造は、例えば、フェノール性ヒドロキシ基等のヒドロキシ基を有するポリイミドと、グリシジル基及びエチレン性不飽和結合を有する化合物（例えば、グリシジルメタクリレート等）とを反応することにより得られる。 Among these, R ²¹ is preferably a group represented by any one of the following formulas (R1) to (R3), more preferably a group represented by formula (R1).

In formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group in which two or more of these are combined, and X represents an oxygen atom or a sulfur atom, * represents a bonding site with another structure, and ● represents a bonding site with the oxygen atom to which R ²¹ in formula (IV) bonds.
In formulas (R1) to (R3), a preferred embodiment of an alkylene group having 2 to 12 carbon atoms or a (poly)alkyleneoxy group having 2 to 30 carbon atoms in L is the above-mentioned R ²¹ having 2 to 12 carbon atoms. It is the same as the preferred embodiment of the 12 alkylene group or the (poly)alkyleneoxy group having 2 to 30 carbon atoms.
In formula (R1), X is preferably an oxygen atom.
In formulas (R1) to (R3), * has the same meaning as * in formula (IV), and preferred embodiments are also the same.
The structure represented by formula (R1) is, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group, and a compound having an isocyanato group and an ethylenically unsaturated bond (e.g., 2-isocyanatoethyl methacrylate, etc.). Obtained by reaction.
The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (eg, 2-hydroxyethyl methacrylate, etc.).
The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (e.g., glycidyl methacrylate, etc.) can get.

In formula (IV), * represents a bonding site with another structure, preferably a bonding site with the main chain of polyimide.

The amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001-0.1 mol/g, more preferably 0.0005-0.05 mol/g.

-Polymerizable Groups Other than Groups Having Ethylenically Unsaturated Bonds-
Polyimide may have a polymerizable group other than the group having an ethylenically unsaturated bond.
Polymerizable groups other than groups having an ethylenically unsaturated bond include cyclic ether groups such as an epoxy group and an oxetanyl group, alkoxymethyl groups such as a methoxymethyl group, and methylol groups.
A polymerizable group other than a group having an ethylenically unsaturated bond is preferably included, for example, in R ¹³¹ in a repeating unit represented by formula (4) described below.
The amount of the polymerizable group other than the group having an ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, preferably 0.001 to 0.05 mol / g. more preferred.

-Polarity conversion group-
The polyimide may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the polyimide is the same as the acid-decomposable group described for R ¹¹³ and R ¹¹⁴ in formula (2) above, and preferred embodiments are also the same.
Polar conversion groups are included, for example, at R ¹³¹ and R ¹³² in the repeating unit represented by formula (4) described later, the terminal of polyimide, and the like.

- Acid value -
When polyimide is subjected to alkali development, the acid value of polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and more preferably 70 mgKOH/g or more, from the viewpoint of improving developability. is more preferable.
Also, the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less.
Further, when the polyimide is subjected to development using a developer containing an organic solvent as a main component (for example, "solvent development" described later), the acid value of the polyimide is preferably 1 to 35 mgKOH/g, and 2 to 30 mgKOH. /g is more preferred, and 5 to 20 mgKOH/g is even more preferred.
The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.
The acid group contained in the polyimide preferably has a pKa of 0 to 10, more preferably 3 to 8, from the viewpoint of both storage stability and developability.
Considering the dissociation reaction in which hydrogen ions are released from an acid, the pKa is expressed by the negative common logarithm pKa of the equilibrium constant Ka. In this specification, unless otherwise specified, pKa is a value calculated by ACD/ChemSketch (registered trademark). Alternatively, it is possible to refer to the values listed in the Chemical Society of Japan, "Fifth Revised Edition, Chemistry Handbook, Fundamentals".
Also, when the acid group is a polyvalent acid such as phosphoric acid, the pKa is the first dissociation constant.
As such an acid group, the polyimide preferably contains at least one selected from the group consisting of a carboxy group and a phenolic hydroxy group, more preferably a phenolic hydroxy group.

-Phenolic hydroxy group-
The polyimide preferably has a phenolic hydroxy group from the viewpoint of making the development speed with an alkaline developer appropriate.
Polyimide may have a phenolic hydroxy group at the end of the main chain or in the side chain.
A phenolic hydroxy group is preferably contained in, for example, R ¹³² in a repeating unit represented by formula (4) described later or R ¹³¹ in a repeating unit represented by formula (4) described later.
The amount of phenolic hydroxy groups relative to the total weight of the polyimide is preferably 0.1-30 mol/g, more preferably 1-20 mol/g.

式（４）中、Ｒ^１３１は、２価の有機基を表し、Ｒ^１３２は、４価の有機基を表す。
重合性基を有する場合、重合性基は、Ｒ^１３１及びＲ^１３２の少なくとも一方に位置していてもよいし、下記式（４－１）又は式（４－２）に示すようにポリイミドの末端に位置していてもよい。
式（４－１）

式（４－１）中、Ｒ^１３３は重合性基であり、他の基は式（４）と同義である。
式（４－２）

Ｒ^１３４及びＲ^１３５の少なくとも一方は重合性基であり、重合性基でない場合は有機基であり、他の基は式（４）と同義である。 The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but it preferably contains a repeating unit represented by the following formula (4).

In formula (4), R ¹³¹ represents a divalent organic group and R ¹³² represents a tetravalent organic group.
When it has a polymerizable group, the polymerizable group may be located on at least one of R ¹³¹ and R ¹³² , and the terminal of the polyimide as shown in the following formula (4-1) or (4-2) may be located in
Formula (4-1)

In formula (4-1), R ¹³³ is a polymerizable group, and other groups are the same as in formula (4).
Formula (4-2)

At least one of R ¹³⁴ and R ¹³⁵ is a polymerizable group, and when it is not a polymerizable group, it is an organic group, and the other groups are as defined in formula (4).

Examples of the polymerizable group include the above-described groups containing an ethylenically unsaturated bond and crosslinkable groups other than the above-described groups having an ethylenically unsaturated bond.
R ¹³¹ represents a divalent organic group. Examples of the divalent organic group are the same as those of R ¹¹¹ in formula (2), and the preferred range is also the same.
R ¹³¹ also includes a diamine residue remaining after removal of the amino group of the diamine. Diamines include aliphatic, cycloaliphatic or aromatic diamines. A specific example is the example of R ¹¹¹ in formula (2) of the polyimide precursor.

R ¹³¹ is preferably a diamine residue having at least two alkylene glycol units in its main chain, from the viewpoint of more effectively suppressing the occurrence of warpage during baking. More preferably, it is a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and more preferably the above diamine, which does not contain an aromatic ring. is.

Diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule include Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, and EDR. -148, EDR-176, D-200, D-400, D-2000, D-4000 (trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy) propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, and the like.

R ¹³² represents a tetravalent organic group. Examples of the tetravalent organic group are the same as those for R ¹¹⁵ in formula (2), and the preferred range is also the same.
For example, four bonds of a tetravalent organic group exemplified as R ¹¹⁵ combine with four —C(═O)— moieties in the above formula (4) to form a condensed ring.

Further, R ¹³² includes, for example, a tetracarboxylic acid residue remaining after removal of an anhydride group from a tetracarboxylic dianhydride. A specific example is the example of R ¹¹⁵ in formula (2) of the polyimide precursor. From the viewpoint of strength of the organic film, R ¹³² is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

It is also preferred that at least one of R ¹³¹ and R ¹³² has an OH group. More specifically, R ¹³¹ is 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, and the above (DA-1) to (DA-18) are preferred examples. and more preferable examples of R ¹³² are the above (DAA-1) to (DAA-5).

It is also preferred that the polyimide has a fluorine atom in its structure. The content of fluorine atoms in the polyimide is preferably 10% by mass or more, and preferably 20% by mass or less.

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

In addition, in order to improve the storage stability of the resin composition, the main chain end of the polyimide is blocked with a terminal blocking agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound. preferably. Among these, it is more preferable to use monoamines, and preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7 -aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2 -hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6- Aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfone acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3- Aminothiophenol, 4-aminothiophenol and the like can be mentioned. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

-Imidation rate (ring closure rate)-
The imidization rate (also referred to as "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, from the viewpoint of the film strength, insulation properties, etc. of the resulting organic film. More preferably, it is 90% or more.
The upper limit of the imidization rate is not particularly limited, and may be 100% or less.
The imidization rate is measured, for example, by the method described below.
The infrared absorption spectrum of the polyimide is measured, and the peak intensity P1 near 1377 cm ⁻¹ , which is the absorption peak derived from the imide structure, is obtained. Next, after heat-treating the polyimide at 350° C. for 1 hour, the infrared absorption spectrum is measured again to obtain the peak intensity P2 near 1377 cm ⁻¹ . Using the obtained peak intensities P1 and P2, the imidization rate of the polyimide can be determined according to the following formula.
Imidation rate (%) = (peak intensity P1/peak intensity P2) x 100

The polyimide may contain repeating units represented by the above formula (4 ⁾ that all contain one type of R ¹³¹ or R ¹³² , and the ^above formula ( 4) may contain a repeating unit. Moreover, the polyimide may contain other types of repeating units in addition to the repeating units represented by the above formula (4). Other types of repeating units include, for example, repeating units represented by formula (2) above.

For polyimide, for example, a method of reacting a tetracarboxylic dianhydride and a diamine (partially replaced with a monoamine terminal blocker) at a low temperature, a method of reacting a tetracarboxylic dianhydride (partially with an acid anhydride) at a low temperature a monoacid chloride compound or a monoactive ester compound) and a diamine, a diester is obtained by a tetracarboxylic dianhydride and an alcohol, and then a diamine (a part of which is a monoamine A method of reacting in the presence of a condensing agent) with a condensing agent, a diester is obtained by tetracarboxylic acid dianhydride and alcohol, then the remaining dicarboxylic acid is acid chloride, diamine (part of which is a monoamine Using a method such as a method of reacting with a terminal blocking agent) to obtain a polyimide precursor, which is completely imidized using a known imidization reaction method, or an imidization reaction in the middle can be synthesized using a method of partially introducing an imide structure by stopping the , or a method of partially introducing an imide structure by blending a completely imidized polymer and its polyimide precursor. . Other known methods for synthesizing polyimide can also be applied.

The weight average molecular weight (Mw) of polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, still more preferably 15,000 to 40,000. By setting the weight average molecular weight to 5,000 or more, the folding resistance of the cured film can be improved. In order to obtain an organic film having excellent mechanical properties (e.g. elongation at break), the weight average molecular weight is particularly preferably 15,000 or more.
The number average molecular weight (Mn) of polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, still more preferably 4,000 to 20,000.
The polyimide has a molecular weight distribution of preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. Although the upper limit of the polyimide molecular weight dispersity is not particularly defined, for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
Moreover, when the resin composition contains a plurality of types of polyimide as the specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one type of polyimide are within the above ranges. It is also preferable that the weight-average molecular weight, the number-average molecular weight, and the degree of dispersion calculated using the above-mentioned plural kinds of polyimides as one resin are within the above ranges.

式（３）中、Ｒ^１２１は、２価の有機基を表し、Ｒ^１２２は、４価の有機基を表し、Ｒ^１２３及びＲ^１２４は、それぞれ独立に、水素原子又は１価の有機基を表す。 [Polybenzoxazole precursor]
Although the structure of the polybenzoxazole precursor used in the present invention is not particularly defined, it preferably contains a repeating unit represented by the following formula (3).

In formula (3), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group. show.

In formula (3), R ¹²³ and R ¹²⁴ each have the same meaning as R ¹¹³ in formula (2), and the preferred ranges are also the same. That is, at least one is preferably a polymerizable group.
In formula (3), R ¹²¹ represents a divalent organic group. As the divalent organic group, a group containing at least one of an aliphatic group and an aromatic group is preferred. As the aliphatic group, a linear aliphatic group is preferred. R ¹²¹ is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.

As the dicarboxylic acid residue, a dicarboxylic acid residue containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferable, and a dicarboxylic acid residue containing an aromatic group is more preferable.
The dicarboxylic acid containing an aliphatic group is preferably a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group, a linear or branched (preferably linear) aliphatic group and two -COOH A dicarboxylic acid consisting of is more preferred. The number of carbon atoms in the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, even more preferably 3 to 20, and 4 to 15 is more preferred, and 5-10 is particularly preferred. The linear aliphatic group is preferably an alkylene group.
Dicarboxylic acids containing linear aliphatic groups include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2, 2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberin acid, dodecanedioic acid, azelaic acid, sebacic acid, hexadecanedioic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid , octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, thoria Examples include contanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and dicarboxylic acids represented by the following formulas.

（式中、Ｚは炭素数１～６の炭化水素基であり、ｎは１～６の整数である。）

(Wherein, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.)

As the dicarboxylic acid containing an aromatic group, the following dicarboxylic acids having an aromatic group are preferable, and the following dicarboxylic acids consisting of only a group having an aromatic group and two —COOH are more preferable.

式中、Ａは－ＣＨ_２－、－Ｏ－、－Ｓ－、－ＳＯ_２－、－ＣＯ－、－ＮＨＣＯ－、－Ｃ（ＣＦ_３）_２－、及び、－Ｃ（ＣＨ_３）_２－からなる群から選択される２価の基を表し、＊はそれぞれ独立に、他の構造との結合部位を表す。

wherein A is -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, -C(CF ₃ ) ₂ -, and -C(CH ₃ ) ₂ - represents a divalent group selected from the group consisting of * independently represents a binding site to another structure.

Specific examples of dicarboxylic acids containing aromatic groups include 4,4'-carbonyl dibenzoic acid, 4,4'-dicarboxydiphenyl ether and terephthalic acid.

In formula (3), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same meaning as R ¹¹⁵ in the above formula (2), and the preferred range is also the same.
R ¹²² is also preferably a group derived from a bisaminophenol derivative. -diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis-(3-amino- 4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis- (4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone,3,3'-diamino-4,4'-dihydroxybenzophenone,4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4, 4′-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene and the like. These bisaminophenols may be used singly or in combination.

Among bisaminophenol derivatives, bisaminophenol derivatives having the following aromatic groups are preferred.

式中、Ｘ_１は、－Ｏ－、－Ｓ－、－Ｃ（ＣＦ_３）_２－、－ＣＨ_２－、－ＳＯ_２－、－ＮＨＣＯ－を表し、＊及び＃はそれぞれ、他の構造との結合部位を表す。Ｒは水素原子又は１価の置換基を表し、水素原子又は炭化水素基が好ましく、水素原子又はアルキル基がより好ましい。また、Ｒ^１２２は、上記式により表される構造であることも好ましい。Ｒ^１２２が、上記式により表される構造である場合、計４つの＊及び＃のうち、いずれか２つが式（３）中のＲ^１２２が結合する窒素原子との結合部位であり、かつ、別の２つが式（３）中のＲ^１２２が結合する酸素原子との結合部位であることが好ましく、２つの＊が式（３）中のＲ^１２２が結合する酸素原子との結合部位であり、かつ、２つの＃が式（３）中のＲ^１２２が結合する窒素原子との結合部位であるか、又は、２つの＊が式（３）中のＲ^１２２が結合する窒素原子との結合部位であり、かつ、２つの＃が式（３）中のＲ^１２２が結合する酸素原子との結合部位であることがより好ましく、２つの＊が式（３）中のＲ^１２２が結合する酸素原子との結合部位であり、かつ、２つの＃が式（３）中のＲ^１２２が結合する窒素原子との結合部位であることが更に好ましい。

In the formula, X ₁ represents -O-, -S-, -C(CF ₃ ) ₂ -, -CH ₂ -, -SO ₂ -, -NHCO-, and * and # respectively represent other structures and represents the binding site of R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group. R ¹²² is also preferably a structure represented by the above formula. When R ¹²² has a structure represented by the above formula, any two of the total four * and # are binding sites with the nitrogen atom to which R ¹²² in formula (3) binds, and Another two are preferably bonding sites with the oxygen atom to which R ¹²² in formula (3) is bonded, and two * are bonding sites with the oxygen atom to which R ¹²² in formula (3) is bonded. and two #s are binding sites to the nitrogen atom to which R ¹²² in formula (3) binds, or two * are binding sites to the nitrogen atom to which R ¹²² in formula (3) binds and two #s are more preferably binding sites to the oxygen atom to which R ¹²² in formula (3) binds, and two * are the oxygen to which R ¹²² in formula (3) binds. More preferably, it is a bonding site with an atom and two #s are bonding sites with a nitrogen atom to which R ¹²² in formula (3) is bonded.

The bisaminophenol derivative is also preferably a compound represented by Formula (As).

In formula (A-s), R ₁ is a hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, a single bond, or the following formula (A- It is an organic group selected from the group of sc). _R2 is a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different. _R3 is a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different.

（式（Ａ－ｓｃ）中、＊は上記式（Ａ－ｓ）で示されるビスアミノフェノール誘導体のアミノフェノール基の芳香環に結合することを示す。）

(In formula (A-sc), * indicates binding to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by formula (A-s) above.)

In the above formula (As), having a substituent at the ortho position of the phenolic hydroxy group, that is, at R ₃ is thought to bring the distance between the carbonyl carbon of the amide bond and the hydroxy group closer together. It is particularly preferable in that the effect of increasing the cyclization rate when cured is further increased.

Further, in the above formula (A-s), when R ₂ is an alkyl group and R ₃ is an alkyl group, high transparency to the i-line and high cyclization rate when cured at a low temperature are said to be obtained. The effect can be maintained, which is preferable.

Further, in formula (As) above, it is more preferred that R ₁ is alkylene or substituted alkylene. Specific examples of alkylene and substituted alkylene for R ₁ include linear or branched alkyl groups having 1 to 8 carbon atoms, among which —CH ₂ — and —CH(CH ₃ ) -, -C(CH ₃ ) ₂ - have sufficient solubility in solvents while maintaining the effect of high i-line transparency and high cyclization rate when cured at low temperature. It is more preferable in that a polybenzoxazole precursor having excellent properties can be obtained.

As a method for producing the bisaminophenol derivative represented by the above formula (A-s), for example, refer to paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of JP-A-2013-256506. , the contents of which are incorporated herein.

Specific examples of the structure of the bisaminophenol derivative represented by the above formula (A-s) include those described in paragraphs 0070 to 0080 of JP-A-2013-256506, the contents of which are incorporated herein. incorporated into. Of course, it goes without saying that they are not limited to these.

The polybenzoxazole precursor may also contain other types of repeating units in addition to the repeating units of formula (3) above.
The polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit in that warping due to ring closure can be suppressed.

式（ＳＬ）中、Ｚは、ａ構造とｂ構造を有し、Ｒ^１ｓは、水素原子又は炭素数１～１０の炭化水素基であり、Ｒ^２ｓは炭素数１～１０の炭化水素基であり、Ｒ^３ｓ、Ｒ^４ｓ、Ｒ^５ｓ、Ｒ^６ｓのうち少なくとも１つは芳香族基で、残りは水素原子又は炭素数１～３０の有機基で、それぞれ同一でも異なっていてもよい。ａ構造及び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部分のモル％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。

In formula (SL), 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, and R ^2s is a hydrocarbon group having 1 to 10 carbon atoms. At least one of R ^3s , R ^4s , R ^5s and R ^6s is an aromatic group, and the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different. Polymerization of a structure and b structure may be block polymerization or random polymerization. The mol % of the Z portion is 5 to 95 mol % for the a structure, 95 to 5 mol % for the b structure, and 100 mol % for a+b.

In formula (SL), preferred Z include those in which R ^5s and R ^6s in the b structure are phenyl groups. Further, the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the molecular weight in the above range, it is possible to more effectively lower the elastic modulus after dehydration ring closure of the polybenzoxazole precursor, and to achieve both the effect of suppressing warpage and the effect of improving solvent solubility.

When containing a diamine residue represented by formula (SL) as another type of repeating unit, further containing a tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic dianhydride as a repeating unit is also preferred. Examples of such tetracarboxylic acid residues include those of R ¹¹⁵ in formula (2).

The weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably 18,000 to 30,000, more preferably 20,000 to 29,000, still more preferably 22,000 to 28, 000. Also, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, still more preferably 9,200 to 11,200.
The molecular weight dispersity of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. Although the upper limit of the molecular weight dispersity of the polybenzoxazole precursor is not particularly defined, for example, it is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, and 2.3 or less. is more preferable, and 2.2 or less is even more preferable.
Further, when the resin composition contains a plurality of types of polybenzoxazole precursors as specific resins, the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one type of polybenzoxazole precursor are within the above ranges. preferable. It is also preferable that the weight-average molecular weight, the number-average molecular weight, and the degree of dispersion calculated from the plurality of types of polybenzoxazole precursors as one resin are within the ranges described above.

式（Ｘ）中、Ｒ^１３３は、２価の有機基を表し、Ｒ^１３４は、４価の有機基を表す。
重合性基又は酸分解性基等の極性変換基を有する場合、重合性基又は酸分解性基等の極性変換基は、Ｒ^１３３及びＲ^１３４の少なくとも一方に位置していてもよいし、下記式（Ｘ－１）又は式（Ｘ－２）に示すようにポリベンゾオキサゾールの末端に位置していてもよい。
式（Ｘ－１）

式（Ｘ－１）中、Ｒ^１３５及びＲ^１３６の少なくとも一方は、重合性基又は酸分解性基等の極性変換基であり、重合性基又は酸分解性基等の極性変換基でない場合は有機基であり、他の基は式（Ｘ）と同義である。
式（Ｘ－２）

式（Ｘ－２）中、Ｒ^１３７は重合性基又は酸分解性基等の極性変換基であり、他は置換基であり、他の基は式（Ｘ）と同義である。 [Polybenzoxazole]
Polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but it is preferably a compound represented by the following formula (X), and a compound represented by the following formula (X) and more preferably a compound having a polymerizable group. As the polymerizable group, a radically polymerizable group is preferred. Further, it may be a compound represented by the following formula (X) and having a polarity conversion group such as an acid-decomposable group.

In Formula (X), R ¹³³ represents a divalent organic group and R ¹³⁴ represents a tetravalent organic group.
In the case of having a polar conversion group such as a polymerizable group or an acid-decomposable group, the polar conversion group such as a polymerizable group or an acid-decomposable group may be positioned at least one of R ¹³³ and R ¹³⁴ . It may be positioned at the end of the polybenzoxazole as shown in formula (X-1) or formula (X-2).
Formula (X-1)

In formula (X-1), at least one of R ¹³⁵ and R ¹³⁶ is a polar conversion group such as a polymerizable group or an acid-decomposable group. It is an organic group, and other groups are as defined in formula (X).
Formula (X-2)

In formula (X-2), R ¹³⁷ is a polar conversion group such as a polymerizable group or an acid-decomposable group, the others are substituents, and the other groups are the same as in formula (X).

The polarity conversion group such as a polymerizable group or an acid-decomposable group is synonymous with the polymerizable group described above for the polymerizable group possessed by the polyimide precursor.

R ¹³³ represents a divalent organic group. Divalent organic groups include aliphatic groups and aromatic groups. A specific example is the example of R ¹²¹ in formula (3) of the polybenzoxazole precursor. Preferred examples thereof are the same as those of ^R121 .

R ¹³⁴ represents a tetravalent organic group. Tetravalent organic groups include examples of R ¹²² in the polybenzoxazole precursor formula (3). Moreover, the preferred examples thereof are the same as those of ^R122 .
For example, four bonds of a tetravalent organic group exemplified as R ¹²² combine with the nitrogen atom and oxygen atom in the above formula (X) to form a condensed ring. For example, when R ¹³⁴ is the following organic group, it forms the structure below. In the structures below, each * represents a bonding site with a nitrogen atom or an oxygen atom in formula (X).

Polybenzoxazole preferably has an oxazole conversion rate of 85% or more, more preferably 90% or more. The upper limit is not particularly limited, and may be 100%. When the oxazolization rate is 85% or more, film shrinkage due to ring closure that occurs during oxazolization by heating can be reduced, and the occurrence of warpage can be more effectively suppressed.
The oxazolization rate is measured, for example, by the method described below.
An infrared absorption spectrum of polybenzoxazole is measured to obtain a peak intensity Q1 near 1650 cm ⁻¹ which is an absorption peak derived from the amide structure of the precursor. Next, normalization is performed by the absorption intensity of the aromatic ring seen around 1490 cm ⁻¹ . After heat-treating the polybenzoxazole at 350° C. for 1 hour, the infrared absorption spectrum is measured again, the peak intensity Q2 near 1650 cm ⁻¹ is obtained, and the absorption intensity of the aromatic ring seen near 1490 cm ⁻¹ is normalized. do. Using the obtained standard values of the peak intensities Q1 and Q2, the oxazole conversion rate of polybenzoxazole can be obtained based on the following formula.
Oxazolization rate (%) = (standardized value of peak intensity Q1/standardized value of peak intensity Q2) x 100

The polybenzoxazole may contain repeating units of the above formula (X) that all contain one type of R ¹³¹ or R ¹³² , or may contain repeating units of the above formula (X) that contain two or more different types of R ¹³¹ or R ¹³² . ) repeating units. The polybenzoxazole may also contain other types of repeating units in addition to the repeating units of formula (X) above.

Polybenzoxazole is obtained by, for example, reacting a bisaminophenol derivative with a dicarboxylic acid containing R ¹³³ or a compound selected from dicarboxylic acid dichlorides and dicarboxylic acid derivatives of the above dicarboxylic acid to obtain a polybenzoxazole precursor. , which is obtained by oxazolating it using a known oxazolating reaction method.
In the case of a dicarboxylic acid, an active ester type dicarboxylic acid derivative obtained by pre-reacting 1-hydroxy-1,2,3-benzotriazole or the like may be used in order to increase the reaction yield.

The weight average molecular weight (Mw) of polybenzoxazole is preferably from 5,000 to 70,000, more preferably from 8,000 to 50,000, even more preferably from 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the folding resistance of the cured film can be improved. In order to obtain an organic film having excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. Moreover, when two or more kinds of polybenzoxazole are contained, it is preferable that the weight average molecular weight of at least one kind of polybenzoxazole is within the above range.
Further, the number average molecular weight (Mn) of polybenzoxazole is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, still more preferably 9,200 to 11,200. be.
The polybenzoxazole has a molecular weight dispersity of preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. Although the upper limit of the polybenzoxazole molecular weight dispersity is not particularly defined, for example, it is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, and even more preferably 2.3 or less. Preferably, 2.2 or less is even more preferable.
Moreover, when the resin composition contains a plurality of types of polybenzoxazole as the specific resin, the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one type of polybenzoxazole are preferably within the above ranges. It is also preferable that the weight-average molecular weight, the number-average molecular weight, and the degree of dispersion calculated from the plurality of types of polybenzoxazole as one resin are within the ranges described above.

式（ＰＡＩ－２）中、Ｒ^１１７は３価の有機基を表し、Ｒ^１１１は２価の有機基を表し、Ａ^２は酸素原子又は－ＮＨ－を表し、Ｒ^１１３は水素原子又は１価の有機基を表す。 [Polyamideimide precursor]
The polyamideimide precursor preferably contains a repeating unit represented by the following formula (PAI-2).

In formula (PAI-2), R ¹¹⁷ represents a trivalent organic group, R ¹¹¹ represents a divalent organic group, A ² represents an oxygen atom or —NH—, R ¹¹³ represents a hydrogen atom or a monovalent represents an organic group.

In formula (PAI-2), R ¹¹⁷ is a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or two The above-linked groups are exemplified, straight-chain aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, and 6 to 20 carbon atoms. or a group in which two or more of these are combined by a single bond or a linking group is preferable, an aromatic group having 6 to 20 carbon atoms, or an aromatic group having 6 to 20 carbon atoms by a single bond or a linking group A group obtained by combining two or more of is more preferable.
The linking group includes -O-, -S-, -C(=O)-, -S(=O) ₂ -, an alkylene group, a halogenated alkylene group, an arylene group, or two or more of these linked groups. is preferred, and -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group in which two or more of these are linked is more preferred.
The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
As the halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable. Further, the halogen atom in the halogenated alkylene group includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable. The above halogenated alkylene group may have hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms be substituted with halogen atoms. Examples of preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group and the like.
The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1,3-phenylene group or a 1,4-phenylene group.

Also, R ¹¹⁷ is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated. Chlorination is preferable as the halogenation.
In the present invention, a compound having three carboxy groups is called a tricarboxylic acid compound.
Two of the three carboxy groups of the tricarboxylic acid compound may be anhydrided.
Examples of the optionally halogenated tricarboxylic acid compound used in the production of the polyamideimide precursor include branched aliphatic, cyclic aliphatic or aromatic tricarboxylic acid compounds.
Only one of these tricarboxylic acid compounds may be used, or two or more thereof may be used.

Specifically, the tricarboxylic acid compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and a Tricarboxylic acid compounds containing 6 to 20 aromatic groups or groups in which two or more of these are combined via a single bond or a linking group are preferred, and aromatic groups having 6 to 20 carbon atoms or carbon atoms via a single bond or linking group are preferred. More preferred are tricarboxylic acid compounds containing groups in which two or more aromatic groups of numbers 6 to 20 are combined.

Further, specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and phthalic acid. (or phthalic anhydride) and benzoic acid are a single bond, —O—, —CH ₂ —, —C(CH ₃ ) ₂ —, —C(CF ₃ ) ₂ —, —SO ₂ — or a phenylene group Linked compounds and the like are included.
These compounds may be compounds in which two carboxy groups are anhydrided (e.g., trimellitic anhydride), or compounds in which at least one carboxy group is halogenated (e.g., trimellitic anhydride chloride). There may be.

In formula (PAI-2), R ¹¹¹ , A ² and R ¹¹³ have the same meanings as R ¹¹¹ , A ² and R ¹¹³ in formula (2) above, and preferred embodiments are also the same.

Polyamideimide precursors may further comprise other repeating units.
Other repeating units include repeating units represented by the above formula (2) and repeating units represented by the following formula (PAI-1).

In formula (PAI-1), R ¹¹⁶ represents a divalent organic group and R ¹¹¹ represents a divalent organic group.
In formula (PAI-1), R ¹¹⁶ is a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or two The above-linked groups are exemplified, straight-chain aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, and 6 to 20 carbon atoms. or a group in which two or more of these are combined by a single bond or a linking group is preferable, an aromatic group having 6 to 20 carbon atoms, or an aromatic group having 6 to 20 carbon atoms by a single bond or a linking group A group obtained by combining two or more of is more preferable.
The linking group includes -O-, -S-, -C(=O)-, -S(=O) ₂ -, an alkylene group, a halogenated alkylene group, an arylene group, or two or more of these linked groups. is preferred, and -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group in which two or more of these are linked is more preferred.
The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
As the halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable. Further, the halogen atom in the halogenated alkylene group includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable. The above halogenated alkylene group may have hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms be substituted with halogen atoms. Examples of preferred halogenated alkylene groups include (ditrifluoromethyl)methylene groups and the like.
The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1,3-phenylene group or a 1,4-phenylene group.

Also, R ¹¹⁶ is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound.
In the present invention, a compound having two carboxy groups is called a dicarboxylic acid compound, and a compound having two halogenated carboxy groups is called a dicarboxylic acid dihalide compound.
The carboxy group in the dicarboxylic acid dihalide compound may be halogenated, but is preferably chlorinated, for example. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.
The optionally halogenated dicarboxylic acid compound or dicarboxylic acid dihalide compound used in the production of the polyamideimide precursor includes linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acids. Examples include acid dihalide compounds.
One of these dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used, or two or more thereof may be used.

Specifically, the dicarboxylic acid compound or dicarboxylic acid dihalide compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, and a cyclic aliphatic group having 3 to 20 carbon atoms. A dicarboxylic acid compound or dicarboxylic acid dihalide compound containing a group, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined via a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms. , or a dicarboxylic acid compound or a dicarboxylic acid dihalide compound containing a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined via a single bond or a linking group.

Specific examples of dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2- dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3, 3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecanedioic acid, azelaic acid, sebacic acid, hexadecanedioic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecane diacid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacontane diacid acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4′-biphenylcarboxylic acid, 4,4′-biphenylcarboxylic acid, 4,4′- dicarboxydiphenyl ether, benzophenone-4,4'-dicarboxylic acid and the like.
Specific examples of dicarboxylic acid dihalide compounds include compounds having a structure in which two carboxy groups in the above specific examples of dicarboxylic acid compounds are halogenated.

In formula (PAI-1), R ¹¹¹ has the same definition as R ¹¹¹ in formula (2) above, and preferred embodiments are also the same.

Also, the polyamideimide precursor preferably has a fluorine atom in its structure. The content of fluorine atoms in the polyamideimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

For the purpose of improving adhesion to the substrate, the polyamideimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Concretely, as the diamine component, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. are used.

As one embodiment of the polyamideimide precursor in the present invention, a repeating unit represented by the formula (PAI-2), a repeating unit represented by the formula (PAI-1), and a repeating unit represented by the formula (2) An aspect in which the total content of units is 50 mol % or more of all repeating units is exemplified. The total content is more preferably 70 mol % or more, still more preferably 90 mol % or more, and particularly preferably more than 90 mol %. The upper limit of the total content is not particularly limited, and all repeating units in the polyamideimide precursor excluding the terminal are repeating units represented by formula (PAI-2), represented by formula (PAI-1). It may be either a repeating unit or a repeating unit represented by formula (2).
Further, as another embodiment of the polyamideimide precursor in the present invention, the total content of repeating units represented by formula (PAI-2) and repeating units represented by formula (PAI-1) is An embodiment in which it is 50 mol % or more of all repeating units is mentioned. The total content is more preferably 70 mol % or more, still more preferably 90 mol % or more, and particularly preferably more than 90 mol %. The upper limit of the total content is not particularly limited, and all repeating units in the polyamideimide precursor excluding the terminal are repeating units represented by formula (PAI-2), or represented by formula (PAI-1) may be any of the repeating units provided.

The weight average molecular weight (Mw) of the polyamideimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, still more preferably 10,000 to 50,000. . Also, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, still more preferably 4,000 to 25,000.
The polyamidoimide precursor preferably has a molecular weight distribution of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. Although the upper limit of the molecular weight dispersity of the polyamideimide precursor is not particularly defined, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. Further, when the resin composition contains a plurality of types of polyamideimide precursors as specific resins, the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one type of polyamideimide precursor are preferably within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated from the plurality of types of polyamideimide precursors as one resin are within the ranges described above.

[Polyamideimide]
The polyamideimide used in the present invention may be an alkali-soluble polyamideimide or a polyamideimide soluble in a developer containing an organic solvent as a main component.
In this specification, the alkali-soluble polyamideimide refers to a polyamideimide that dissolves at 23° C. in an amount of 0.1 g or more in 100 g of a 2.38 mass % tetramethylammonium aqueous solution. A polyamideimide that dissolves 5 g or more is preferable, and a polyamideimide that dissolves 1.0 g or more is more preferable. Although the upper limit of the dissolved amount is not particularly limited, it is preferably 100 g or less.
Moreover, the polyamideimide is preferably a polyamideimide having a plurality of amide bonds and a plurality of imide structures in the main chain from the viewpoint of the film strength and insulating properties of the organic film to be obtained.

- Fluorine atom -
From the viewpoint of the film strength of the organic film to be obtained, the polyamideimide preferably has a fluorine atom.
A fluorine atom is preferably contained in, for example, R ¹¹⁷ or R ¹¹¹ in a repeating unit represented by formula (PAI-3) described later, and is preferably contained in a repeating unit represented by formula (PAI-3) described later It is more preferably contained in R ¹¹⁷ or R ¹¹¹ as a fluorinated alkyl group.
The amount of fluorine atoms is preferably 5% by mass or more and preferably 20% by mass or less with respect to the total mass of polyamideimide.

- Ethylenically unsaturated bond -
From the viewpoint of the film strength of the resulting organic film, the polyamideimide may have an ethylenically unsaturated bond.
The polyamideimide may have an ethylenically unsaturated bond at the end of the main chain or in a side chain, preferably in the side chain.
The ethylenically unsaturated bond preferably has radical polymerizability.
The ethylenically unsaturated bond is preferably contained in R ¹¹⁷ or R ¹¹¹ in the repeating unit represented by formula (PAI-3) described later, and the repeating unit represented by formula (PAI-3) described later. It is more preferably contained as a group having an ethylenically unsaturated bond in R ¹¹⁷ or R ¹¹¹ in .
Preferred embodiments of the group having an ethylenically unsaturated bond are the same as the preferred embodiments of the group having an ethylenically unsaturated bond in the polyimide described above.

The amount of ethylenically unsaturated bonds relative to the total mass of polyamideimide is preferably 0.0001 to 0.1 mol/g, more preferably 0.001 to 0.05 mol/g.

-Polymerizable group other than ethylenically unsaturated bond-
Polyamideimide may have a polymerizable group other than the ethylenically unsaturated bond.
Examples of the polymerizable groups other than the ethylenically unsaturated bond in the polyamideimide include the same groups as the polymerizable groups other than the ethylenically unsaturated bond in the polyimide described above.
A polymerizable group other than an ethylenically unsaturated bond is preferably included in R ¹¹¹ in a repeating unit represented by formula (PAI-3) described later, for example.
The amount of polymerizable groups other than ethylenically unsaturated bonds relative to the total mass of polyamideimide is preferably 0.05 to 10 mol/g, more preferably 0.1 to 5 mol/g.

-Polarity conversion group-
Polyamideimide may have a polarity converting group such as an acid-decomposable group. The acid-decomposable group in polyamideimide is the same as the acid-decomposable group described for R ¹¹³ and R ¹¹⁴ in formula (2) above, and preferred embodiments are also the same.

- Acid value -
When the polyamideimide is subjected to alkali development, the acid value of the polyamideimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, more preferably 70 mgKOH/g, from the viewpoint of improving developability. g or more is more preferable.
Also, the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less.
Further, when the polyamideimide is subjected to development using a developer containing an organic solvent as a main component (for example, "solvent development" described later), the acid value of the polyamideimide is preferably 2 to 35 mgKOH/g, 3 ~30 mg KOH/g is more preferred, and 5 to 20 mg KOH/g is even more preferred.
The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.
Moreover, as the acid group contained in the polyamideimide, the same groups as the acid group in the polyimide described above can be mentioned, and the preferred embodiments are also the same.

-Phenolic hydroxy group-
From the viewpoint of making the development speed with an alkaline developer appropriate, the polyamideimide preferably has a phenolic hydroxy group.
Polyamideimide may have a phenolic hydroxy group at the end of the main chain or in the side chain.
A phenolic hydroxy group is preferably included in, for example, R ¹¹⁷ or R ¹¹¹ in a repeating unit represented by formula (PAI-3) described later.
The amount of phenolic hydroxy groups relative to the total mass of polyamideimide is preferably 0.1 to 30 mol/g, more preferably 1 to 20 mol/g.

式（ＰＡＩ－３）中、Ｒ^１１１及びＲ^１１７はそれぞれ、式（ＰＡＩ－２）中のＲ^１１１及びＲ^１１７と同義であり、好ましい態様も同様である。
重合性基を有する場合、重合性基は、Ｒ^１１１及びＲ^１１７の少なくとも一方に位置していてもよいし、ポリアミドイミドの末端に位置していてもよい。 The polyamideimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure and an amide bond, but it preferably contains a repeating unit represented by the following formula (PAI-3).

In formula (PAI-3), R ¹¹¹ and R ¹¹⁷ have the same meanings as R ¹¹¹ and R ¹¹⁷ in formula (PAI-2), respectively, and preferred embodiments are also the same.
When having a polymerizable group, the polymerizable group may be located at least one of R ¹¹¹ and R ¹¹⁷ , or may be located at the end of the polyamideimide.

In addition, in order to improve the storage stability of the resin composition, the main chain end of the polyamideimide is blocked with a terminal blocker such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound. is preferred. Preferred aspects of the terminal blocker are the same as the preferred aspects of the terminal blocker in the polyimide described above.

-Imidation rate (ring closure rate)-
The imidization rate (also referred to as "ring closure rate") of polyamideimide is preferably 70% or more, more preferably 80% or more, from the viewpoint of the film strength, insulating properties, etc. of the resulting organic film. , more preferably 90% or more.
The upper limit of the imidization rate is not particularly limited, and may be 100% or less.
The imidization rate is measured by the same method as the ring closure rate of the polyimide described above.

Polyamideimide may contain repeating units represented by the above formula (PAI-3), all of which contain one type of R111 or R117, and the above formula (PAI-3) containing two or more different types of R131 or R132. -3) may contain a repeating unit. Moreover, the polyamideimide may contain other types of repeating units in addition to the repeating units represented by the above formula (PAI-3). Other types of repeating units include repeating units represented by the above formula (PAI-1) or formula (PAI-2).

Polyamideimide is, for example, a method of obtaining a polyamideimide precursor by a known method and completely imidizing it using a known imidization reaction method, or stopping the imidization reaction in the middle and partially imidizing the imide structure and a method of partially introducing an imide structure by blending a completely imidized polymer with its polyamideimide precursor.

The weight average molecular weight (Mw) of polyamideimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, even more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the folding resistance of the cured film can be improved. In order to obtain an organic film having excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more.
Further, the number average molecular weight (Mn) of the polyamideimide is preferably 800 to 250,000, more preferably 2,000 to 50,000, still more preferably 4,000 to 25,000. .
The polyamidoimide has a molecular weight distribution of preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. Although the upper limit of the polyamidoimide molecular weight dispersity is not particularly defined, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
Moreover, when the resin composition contains a plurality of types of polyamideimide as the specific resin, the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one type of polyamideimide are preferably within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated from the plurality of types of polyamideimide as one resin are within the above ranges.

[Method for producing polyimide precursor, etc.]
Polyimide precursors and the like, for example, a method of reacting a tetracarboxylic dianhydride and a diamine at a low temperature, a method of reacting a tetracarboxylic dianhydride and a diamine at a low temperature to obtain a polyamic acid, a condensing agent or an alkylating agent A method of esterification using a tetracarboxylic dianhydride and an alcohol to obtain a diester, followed by a reaction with a diamine in the presence of a condensing agent, a method of reacting a tetracarboxylic dianhydride and an alcohol to obtain a diester, After that, the remaining dicarboxylic acid can be acid-halogenated using a halogenating agent and reacted with a diamine. Among the above production methods, the method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and reacting it with a diamine is more preferable.
Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N'-disuccinimidyl carbonate, trifluoroacetic anhydride and the like can be mentioned.
Examples of the alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate and triethyl orthoformate.
Examples of the halogenating agent include thionyl chloride, oxalyl chloride, phosphorus oxychloride and the like.
In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent in the reaction. One type of organic solvent may be used, or two or more types may be used.
The organic solvent can be appropriately determined depending on the raw material, but pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, and the like. is exemplified.
In the method for producing a polyimide precursor or the like, it is preferable to add a basic compound during the reaction. One type of basic compound may be used, or two or more types may be used.
The basic compound can be appropriately determined depending on the raw material, but triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-amino Pyridine and the like are exemplified.

-Terminal blocking agent-
In the production method of polyimide precursors, etc., in order to further improve the storage stability, it is preferable to seal the carboxylic anhydride, acid anhydride derivative, or amino group remaining at the end of the resin such as polyimide precursors. When blocking carboxylic acid anhydrides and acid anhydride derivatives remaining at the ends of resins, terminal blocking agents include monoalcohols, phenols, thiols, thiophenols, monoamines, and the like. It is more preferable to use monoalcohols, phenols and monoamines from the viewpoint of their properties. Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol and furfuryl alcohol, and isopropanol. , 2-butanol, cyclohexyl alcohol, cyclopentanol and 1-methoxy-2-propanol, and tertiary alcohols such as t-butyl alcohol and adamantane alcohol. Preferable phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene. Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6- aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1- Carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-amino naphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4 -aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. are mentioned. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.
Moreover, when blocking the amino group at the terminal of the resin, it is possible to block with a compound having a functional group capable of reacting with the amino group. Preferred capping agents for amino groups are carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromide, sulfonic acid chlorides, sulfonic anhydrides, sulfonic acid carboxylic acid anhydrides, etc., more preferably carboxylic acid anhydrides and carboxylic acid chlorides. preferable. Preferred carboxylic anhydride compounds include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, and the like. are mentioned. Preferred compounds of carboxylic acid chlorides include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, and 1-adamantanecarbonyl chloride. , heptafluorobutyryl chloride, stearic acid chloride, benzoyl chloride, and the like.

-Solid precipitation-
A step of depositing a solid may be included in the production of the polyimide precursor or the like. Specifically, after filtering off the water absorption by-products of the dehydration condensation agent coexisting in the reaction solution as necessary, water, aliphatic lower alcohol, or a poor solvent such as a mixture thereof, the obtained A polyimide precursor or the like can be obtained by adding a polymer component and depositing the polymer component, depositing it as a solid, and drying it. In order to improve the degree of purification, operations such as redissolution, reprecipitation, drying, etc. of the polyimide precursor may be repeated. Furthermore, a step of removing ionic impurities using an ion exchange resin may be included.

〔Content〕
The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and 40% by mass or more with respect to the total solid content of the resin composition. is more preferable, and 50% by mass or more is even more preferable. Further, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, more preferably 98% by mass, based on the total solid content of the resin composition. % or less, more preferably 97 mass % or less, and even more preferably 95 mass % or less.
The resin composition of the present invention may contain only one type of specific resin, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

Also, the resin composition of the present invention preferably contains at least two resins.
Specifically, the resin composition of the present invention may contain a total of two or more of the specific resin and other resins described later, or may contain two or more of the specific resins. It is preferable to include two or more kinds.
When the resin composition of the present invention contains two or more specific resins, for example, two or more polyimides that are polyimide precursors and have different dianhydride-derived structures (R ¹¹⁵ in the above formula (2)) It preferably contains a precursor.

<Other resins>
The resin composition of the present invention may contain the specific resin described above and other resins different from the specific resin (hereinafter also simply referred to as "other resins").
Other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins. etc.
For example, by further adding a (meth)acrylic resin, a resin composition having excellent applicability can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained.
For example, instead of the polymerizable compound described later, or in addition to the polymerizable compound described later, a high polymerizable group value having a weight average molecular weight of 20,000 or less (for example, the molar amount of the polymerizable group in 1 g of the resin is 1×10 ⁻³ mol/g or more), the coating properties of the resin composition, the solvent resistance of the pattern (cured product), etc. can be improved. can.

When the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, and 0.05% by mass or more, relative to the total solid content of the resin composition. More preferably, it is more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and further preferably 10% by mass or more. More preferred.
In addition, the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, based on the total solid content of the resin composition. It is more preferably 60% by mass or less, even more preferably 50% by mass or less.
In addition, as a preferred embodiment of the resin composition of the present invention, the content of other resins may be low. In the above aspect, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and 10% by mass or less relative to the total solid content of the resin composition. is more preferable, 5% by mass or less is even more preferable, and 1% by mass or less is even more preferable. The lower limit of the content is not particularly limited as long as it is 0% by mass or more.
The resin composition of the present invention may contain only one kind of other resin, or may contain two or more kinds thereof. When two or more types are included, the total amount is preferably within the above range.

式（１－１）中、Ｒ^１はそれぞれ独立に、水素原子又は１価の有機基を表し、Ｒ^２はそれぞれ独立に、芳香族ヘテロ環を表し、Ｒ^３はそれぞれ独立に、水素原子又は１価の有機基を表し、Ｌ^１はそれぞれ独立に、２価の連結基を表し、ｎは１以上の整数を表し、Ｌ^２はｎ価の連結基を表す。 <Specific compound>
The resin composition of the present invention contains a compound (specific compound) represented by the following formula (1-1).

In formula (1-1), each R ¹ independently represents a hydrogen atom or a monovalent organic group, each R ² independently represents an aromatic heterocycle, and each R ³ independently represents a hydrogen atom or represents a monovalent organic group, each L ¹ independently represents a divalent linking group, n represents an integer of 1 or more, and L ² represents an n-valent linking group.

[R ¹ ]
In formula (1-1), each R ¹ is preferably independently a hydrogen atom.
Examples of organic groups for R ¹ include hydrocarbon groups such as alkyl groups, alkenyl groups, and aryl groups, with alkyl groups and aryl groups being preferred.
As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable.
As the alkenyl group, an alkenyl group having 2 to 10 carbon atoms is preferable, and an alkenyl group having 2 to 4 carbon atoms is more preferable.
The aryl group is preferably an aromatic hydrocarbon group, more preferably a phenyl group.
The above hydrocarbon group may further have a known substituent.

[ ^R2 ]
Hetero atoms that are ring members in the aromatic hetero ring for R ² include a nitrogen atom, an oxygen atom, a sulfur atom and the like, and it is preferred that at least a nitrogen atom be included as a ring member.
It is also a preferred embodiment that all the hetero atoms that are ring members in the aromatic hetero ring for R ² are nitrogen atoms.
The number of heteroatoms in the aromatic heterocycle is preferably 1-4, more preferably 2-4.

Further, when the heteroatom is a nitrogen atom, the nitrogen atom may be directly bonded to a hydrogen atom, a carbonyl group, a sulfonyl group, or a substituent having a thiocarbonyl group, a sulfonyl group, or , may be directly bonded to the thiocarbonyl group.
In the carbonyl group, the sulfonyl group, or the thiocarbonyl group, the group that is bonded to the side opposite to the nitrogen atom that is a ring member of the nitrogen-containing heterocycle is not particularly limited, but is not limited to a hydrocarbon group, or , a hydrocarbon group, and at least one structure selected from the group consisting of -O-, -C(=O)-, -S-, -S(=O) ₂ -, and -NR ^N - and preferably a hydrocarbon group.
Examples of the hydrocarbon group include an alkyl group, an alkenyl group, and an aryl group, and an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. are preferred, and alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and aromatic hydrocarbon groups having 6 to 10 carbon atoms are more preferred. These hydrocarbon groups may further have a substituent.
Specifically, the hydrocarbon group includes a straight-chain alkyl group such as a methyl group, an ethyl group and a propyl group, a branched alkyl group such as an isopropyl group, a t-butyl group and a 2-ethylhexyl group, a cyclopentanyl group, cyclic alkyl groups such as bornyl group, isobornyl group and adamantyl group; alkenyl groups such as methylvinyl group; aromatic hydrocarbon groups such as phenyl group, naphthyl group, 4-methylphenyl group and 2,6-methylphenyl group; be done.
^RN represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group.

Preferably, R ² contains an azole structure.
An azole structure refers to a five-membered heterocyclic ring structure containing at least one nitrogen atom as a ring member. The azole structure for R ² is preferably a five-membered heterocyclic ring structure containing two or more nitrogen atoms as ring members. For example, an imidazole structure, a triazole structure, or a tetrazole structure is preferred.
R ² preferably contains an imidazole structure, a triazole structure, a tetrazole structure, or a condensed ring structure of these rings and other rings, more preferably a purine structure.
R ² is also preferably an imidazole structure, a triazole structure, a tetrazole structure, or a condensed ring structure of these rings and other rings (e.g., benzene ring, pyrimidine ring, etc.), and a purine structure. is also more preferred.
When R ² is a purine structure, the binding site to the nitrogen atom to which R ¹ in formula (1-1) is bound in the purine structure is not particularly limited, but for example, it may be the 6-position carbon atom in the purine structure. is preferred.

Preferred embodiments of R ² include, but are not limited to, the following structures. In the following formula, * represents the bonding site with the nitrogen atom to which R ¹ in formula (1-1) is bonded.

[L ¹ ]
In formula (1-1), L ¹ is a hydrocarbon group, or a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O) ₂ -, and - A group represented by a combination with at least one structure selected from the group consisting of NR ^N — is preferred, and a hydrocarbon group is preferred.
The hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof, preferably an aliphatic hydrocarbon group, more preferably a saturated aliphatic hydrocarbon group. preferable.

式（Ｌ１－１）中、Ｌ^Ｌ１は２価の連結基を表し、＃は式（１－１）中のＲ^３が結合した窒素原子との結合部位を表し、＊は式（１－１）中のＲ¹が結合した窒素原子との結合部位を表す。 From the viewpoint of reliability, L ¹ preferably has a structure represented by the following formula (L1-1). According to such an aspect, it is considered that the phthalimide structure in the cured product described later becomes a stable structure.

In formula (L1-1), L ^L1 represents a divalent linking group, # represents a binding site to the nitrogen atom to which R ³ in formula (1-1) is bonded, * represents formula (1-1 ) represents the bonding site with the nitrogen atom to which R ¹ is bonded.

In formula (L1-1), L ^L1 is a hydrocarbon group, or a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O) ₂ -, and - A group represented by a combination of at least one structure selected from the group consisting of NR ^N - is preferred, and is selected from the group consisting of a hydrocarbon group or a hydrocarbon group and -O- and -S-. A group represented by a combination of at least one structure described above is preferred, and a hydrocarbon group is more preferred.
The hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof, but an alkylene group is preferred.
The alkylene group is preferably an alkylene group having 2 to 20 carbon atoms, more preferably an alkylene group having 2 to 10 carbon atoms, and even more preferably an alkylene group having 2 to 4 carbon atoms.

Preferred embodiments of L ¹ in formula (1-1) include, but are not limited to, the following structures. In the following formula, # represents the bonding site with the nitrogen atom to which R ³ in formula (1-1) is bonded, and * represents the bonding site with the nitrogen atom to which R ¹ in formula (1-1) is bonded. show.

[R ³ ]
In formula (1-1), R ³ is preferably a hydrogen atom.
In particular, from the viewpoint of reliability, it is preferable that L ¹ has a structure represented by the above formula (L1-1) and R ³ is a hydrogen atom. According to such a mode, it is believed that the phthalimide structure in the cured product described below is easily formed and the structure is stable.
Examples of organic groups for R ³ include hydrocarbon groups such as alkyl groups, alkenyl groups, and aryl groups, with alkyl groups and aryl groups being preferred.
As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable.
As the alkenyl group, an alkenyl group having 2 to 10 carbon atoms is preferable, and an alkenyl group having 2 to 4 carbon atoms is more preferable.
The aryl group is preferably an aromatic hydrocarbon group, more preferably a phenyl group.
The above hydrocarbon group may further have a known substituent.

[ ^L2 ]
In formula (1-1), L ² is a hydrocarbon group, or one or more hydrocarbon groups and a heterocyclic group, -O-, -C(=O)-, -S-, -S(=O ) ₂ — and —NR ^N — is preferably a group represented by a combination of at least one structure selected from the group consisting of a hydrocarbon group, or one or more hydrocarbon groups and —O—, A group represented by a combination of at least one structure selected from the group consisting of -S- and -NR ^N - is more preferred. As the heterocyclic group, a heteroaromatic ring group is preferable. Moreover, an oxygen atom, a sulfur atom, a nitrogen atom etc. are mentioned as a hetero atom contained in a heterocyclic group. ^RN represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group.
The hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof, but preferably contains at least an aromatic hydrocarbon group. A group represented by a combination of a hydrogen group and an aliphatic hydrocarbon group is more preferred.
The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably a group obtained by removing a plurality of hydrogen atoms from a benzene ring. Moreover, the aromatic hydrocarbon group may have a substituent, or may form a condensed ring with another ring structure.
The aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, more preferably a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, A saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms is particularly preferred.

From the viewpoint of base generation efficiency, ^L2 preferably contains an aromatic ring structure.
The aromatic ring structure for L ² includes the above-described aromatic hydrocarbon group and the above-described heteroaromatic ring group, and is preferably an aromatic hydrocarbon group.

It is also preferred that ^L2 contains a hydroxy group, a carboxy group or an alkoxycarbonyl group. The number of carbon atoms in the alkoxy group in the alkoxycarbonyl group is preferably 1-10, more preferably 1-4.
When L ² contains a hydroxy group, the ^number of ^atoms (linkage chain length) is preferably 3 to 6, more preferably 3 or 4.
When L ² contains a carboxy group or an alkoxycarbonyl group, the linking chain between the carboxy group or alkoxycarbonyl group in L ² and -C(=O)- to which L ² in formula (1-1) bonds The number of atoms (linking chain length) on the shortest path is preferably 2-5, more preferably 2 or 3.
In any of the above cases, L ² is an aromatic ring structure (preferably a phenylene group optionally having substituents or condensed rings, more preferably a 1,2-phenylene group optionally having substituents or condensed rings ), and preferably includes an aromatic ring structure on the shortest path.
Also, ^L2 preferably contains an oxygen atom or a sulfur atom on the shortest path.

From the viewpoint of chemical resistance, ^L2 preferably has a polymerizable group, more preferably a radically polymerizable group.
The radically polymerizable group includes a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyloxy group, a maleimide group, a (meth)acrylamide group and the like, and a (meth)acryloxy group, a (meth)acrylamide group, or , a vinylphenyl group are preferable, and from the viewpoint of reactivity, a (meth)acryloxy group is more preferable.
Further, when ^L2 has a radically polymerizable group, at least one of the cyclization resin or its precursor has a radically polymerizable group, or the resin composition contains a radical cross-linking agent to be described later, must be satisfied. is preferred.
According to this aspect, since the base generator is incorporated into the polymer formed by polymerization, for example, the distribution of the base generator in the composition becomes nearly uniform, and the elongation at break of the cured product and the pattern rectangularity are reduced. It is thought that the quality and other properties will be further improved.

式（Ｌ２－１）中、Ａｒは芳香族基を表し、Ｌ^Ｌ２は単結合又は２価の連結基を表し、Ｒ^Ｌ２は水素原子、ヒドロキシ基又は１価の有機基を表し、＊は式（１－１）中のカルボニル基との結合部位を表す。 Among them, in formula (1-1), it is preferable that n is 1 and L ² is a group represented by the following formula (L2-1).

In formula (L2-1), Ar represents an aromatic group, L ^L2 represents a single bond or a divalent linking group, R ^L2 represents a hydrogen atom, a hydroxy group or a monovalent organic group, * represents the formula represents the bonding site with the carbonyl group in (1-1).

In formula (L2-1), Ar may be an aromatic hydrocarbon group or a heteroaromatic ring group, but is preferably an aromatic hydrocarbon group.
The aromatic hydrocarbon group or heteroaromatic ring group for Ar includes the above-mentioned aromatic hydrocarbon group and the above-mentioned heteroaromatic ring group, and is preferably an aromatic hydrocarbon group.

In formula (L2-1), L ^{2 L2} and R ^{2 L2} are preferably positioned adjacent to the aromatic group represented by Ar.
Here, A and B are located at adjacent positions in the aromatic group, and the atom that is the ring member of the aromatic group to which A is bonded and the atom that is the ring member of the aromatic group to which B is bonded are aromatic It means the adjacent ring members in the aromatic group, and if the aromatic group is a benzene ring, it means the meta position.

In formula (L2-1), the divalent linking group in L ^L2 includes an alkylene group, or one or more alkylene groups and -O-, -C(=O)-, -S-, -S( =O) ₂ - and -NR ^N - is preferably a group represented by a combination of at least one structure selected from the group consisting of an alkylene group, or one or more alkylene groups and -O-, A group represented by a combination of at least one structure selected from the group consisting of -S- and -NR ^N - is more preferred.
^RN is as described above.
The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms, and even more preferably an alkylene group having 1 or 2 carbon atoms.

In formula (L2-1), examples of the monovalent organic group for R ^{2 L2} include a hydroxyalkyl group, an alkoxy group, a carboxy group, and an alkoxycarbonyl group.

上記構造中、Ｒ^１の一方は水素原子、他方は下記構造であり、Ｒ^２の一方は水素原子、他方は下記構造である。下記構造中、＃は上記構造における酸素原子との結合部位を表す。下記構造中、＊は式（１－１）中のカルボニル基との結合部位を表す。

Preferred embodiments of L ² in formula (1-1) include, but are not limited to, the following structures. In the following formula, * represents the bonding site with the carbonyl group in formula (1-1).

In the above structure, one of R ¹ is a hydrogen atom and the other has the following structure, and one of R ² has a hydrogen atom and the other has the following structure. In the structure below, # represents a bonding site with an oxygen atom in the above structure. In the structure below, * represents the bonding site with the carbonyl group in formula (1-1).

[n]
In formula (1-1), n represents an integer of 1 or more, preferably an integer of 1 to 4, more preferably 1 or 2. An embodiment in which n is 1 is also one of the preferred embodiments of the present invention.

The compound represented by formula (1-1) is preferably a compound that generates a base by the action of light or heat. Here, the compound represented by formula (1-1) is a nitrogen atom bonded to R ³ in formula (1-1) and a carbonyl group in formula (1-1) by the action of light or heat. is preferably cleaved between and to generate a base.
Also, the compound represented by formula (1-1) is preferably a compound that generates a base by the action of heat. Here, in the compound represented by formula (1-1), the nitrogen atom bonded to R ³ in formula (1-1) and the carbonyl group in formula (1-1) are combined by the action of heat. It is preferred to cleave between them to generate a base.

Specifically, the specific compound preferably generates a base by heating at 250°C, more preferably generates a base by heating at 230°C, and further preferably generates a base by heating at 220°C. It is more preferable to generate the base by heating at 200°C, particularly preferably to generate the base by heating to 190°C, and most preferably to generate the base by heating at 180°C. Although the lower limit of the temperature at which the base is generated is not particularly limited, it is preferably 100° C. or higher from the viewpoint of the storage stability of the composition.
Whether or not a certain compound A exhibits the property of generating a base at a certain temperature X° C. is judged by the following method.
When 1 mol of compound A is heated in a closed container under 1 atmosphere at X ° C. for 3 hours, the decomposition amount is quantified by a method such as HPLC (high performance liquid chromatography), and 0.01 mol or more of a base is generated. , compound A generates a base upon heating at X°C. Whether or not the generated compound is a base can be confirmed by using ¹ H-NMR, for example.
The amount of the base generated is preferably 0.1 mol or more, more preferably 0.5 mol or more. Although the upper limit of the amount of the generated base is not particularly limited, it can be, for example, 1000 mol or less.

Further, when the specific compound generates a base by light, a composition A is prepared by dissolving the specific compound in a solvent, and under the conditions of 1 atm and 25° C., broadband light having a wavelength of 190 to 800 nm is applied at an exposure illuminance of 25 W/ After irradiating for 30 seconds under the conditions of cm ² , the decomposition amount is quantified by a method such as HPLC (high performance liquid chromatography), and if 0.01 mol or more of the base is generated with respect to the total molar amount of the specific compound, the compound A is determined to generate a base by light. The amount of base generated is preferably 0.1 mol or more, more preferably 0.5 mol or more. The upper limit of the amount of generated base is not particularly limited, but it can be, for example, 1000 mol or less.
When the resin composition contains a solvent, the concentration of the specific compound in the composition A is the same as the concentration in the resin composition, and the solvent species in the composition is the same as the solvent contained in the resin composition. can be Further, when the resin composition does not contain a solvent, the concentration of the specific compound in composition A can be about 1.0% by mass with respect to the total mass of composition A, and the solvent species is N-methyl- 2-pyrrolidone and the like can be used.

式（２－１）中、Ｒ^１、Ｒ^２、Ｒ^３及びＬ^１はそれぞれ、式（１－１）中のＲ^１、Ｒ^２、Ｒ^３及びＬ^１と同義であり、好ましい態様も同様である。 The base generated from the specific compound is preferably a compound represented by the following formula (2-1).

In formula (2-1), R ¹ , R ² , R ³ and L ¹ have the same meanings as R ¹ , R ² , R ³ and L ¹ in formula (1-1), and preferred embodiments are also the same. is.

The molecular weight of the base generated from the specific compound is preferably 70-500, more preferably 80-300, even more preferably 90-220.
The base generated from the specific compound is preferably a base in which the pKa of the conjugate acid is 0 or more, more preferably 3 or more, and more preferably 6 or more. Although the upper limit of the pKa of the conjugate acid is not particularly limited, it is preferably 30 or less.
The pKa is a dissociation reaction in which hydrogen ions are released from an acid, and its equilibrium constant Ka is represented by its negative common logarithm pKa. In this specification, unless otherwise specified, pKa is a value calculated by ACD/ChemSketch (registered trademark).
When the conjugate acid has multiple pKa values, at least one preferably falls within the above range.
Further, from the viewpoint of storage stability of the composition, etc., the pKa of the conjugate acid of the specific compound (pKa of the conjugate acid of the specific compound before decomposition) is preferably 1.0 or less, and is 0.0 or less. is more preferable, and -0.5 or less is more preferable. Although the lower limit is not particularly limited, it may be -20 or more, for example.
When the conjugate acid has multiple pKa values, the maximum value is more preferably within the above range.

Specific examples of the generated base include, but are not limited to, bases having the following structures. In addition, for example, these bases in the composition undergo further structural changes such as elimination of substituents bonded to nitrogen atoms in azole structures (including azole structures contained in condensed rings such as purine ring structures). There may be

[Molecular weight]
The molecular weight of the specific compound is preferably from 150 to 1,000, more preferably from 180 to 800, even more preferably from 200 to 700.

[Synthesis method]
The specific compound can be synthesized, for example, by the synthetic method described in the examples below. In addition, it may be synthesized using other known synthesis methods, and the synthesis method is not particularly limited. For example, after combining the structure corresponding to R ² in formula (1-1) with the structure corresponding to L ¹ , the structure corresponding to L 2 may be further combined, or the structure corresponding to L ¹ may be combined with the structure corresponding to L ¹ After combining with the structure corresponding to ^L2 , the structure corresponding to ^R2 may be further combined with the structure corresponding to ^L1 .

Specific examples of specific compounds include, but are not limited to, F-1 to F-24 used in the Examples.

The content of the specific compound is preferably 0.05 to 10% by mass with respect to the total solid content of the resin composition of the present invention. More preferably, the lower limit is 0.1% by mass or more. The upper limit is more preferably 5% by mass or less, and even more preferably 2% by mass or less.
One of the specific compounds may be used alone, or two or more of them may be used in combination. When two or more are used in combination, the total amount is preferably within the above range.
In addition, the content of the specific compound in the resin composition of the present invention is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the specific resin.

<Primary amine>
The resin composition of the present invention preferably has a primary amine content of 1% by mass or less.
In the present invention, the primary amine refers to a compound in which one hydrogen atom of ammonia is substituted with an organic group.
The content of the primary amine is more preferably 0.1% by mass or less, and even more preferably 0.01% by mass or less. Moreover, the lower limit of the content is not particularly limited, and may be 0% by mass.
In the resin composition of the present invention, the primary amine content relative to the total mass of the specific compound is preferably 0.1% by mass or less, more preferably 0.01% by mass or less. Moreover, the lower limit of the content is not particularly limited, and may be 0% by mass.

<Polymerizable compound>
The resin composition of the present invention preferably contains a polymerizable compound.
Polymerizable compounds include radical cross-linking agents or other cross-linking agents.

[Radical cross-linking agent]
The resin composition of the present invention preferably contains a radical cross-linking agent.
A radical cross-linking agent is a compound having a radically polymerizable group. As the radically polymerizable group, a group containing an ethylenically unsaturated bond is preferred. Examples of the group containing an ethylenically unsaturated bond include groups containing an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group.
Among these, the group containing an ethylenically unsaturated bond is preferably a (meth)acryloyl group, a (meth)acrylamide group, or a vinylphenyl group, and more preferably a (meth)acryloyl group from the viewpoint of reactivity.

The radical cross-linking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more. The radical cross-linking agent may have 3 or more ethylenically unsaturated bonds.
The compound having two or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and 2 to 6. More preferred are compounds having
Further, from the viewpoint of the film strength of the resulting pattern (cured product), the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. It is also preferred to include

The molecular weight of the radical cross-linking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical cross-linking agent is preferably 100 or more.

Specific examples of the radical cross-linking agent include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, and amides. They are esters of saturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyhydric amine compounds. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxy group, an amino group, or a sulfanyl group with monofunctional or polyfunctional isocyanates or epoxies, or monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and halogeno groups Also suitable are substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as a tosyloxy group and monofunctional or polyfunctional alcohols, amines, and thiols. As another example, it is also possible to use a group of compounds in which the unsaturated carboxylic acid is replaced with unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an allyl ether, or the like. As specific examples, paragraphs 0113 to 0122 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated herein.

The radical cross-linking agent is also preferably a compound having a boiling point of 100° C. or higher under normal pressure. Examples include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(acryloyloxypropyl)ether, tri(acryloyloxyethyl)isocyanurate, glycerin, trimethylolethane, etc. Compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylated, described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Patent Publication No. 51-037193. Urethane (meth)acrylates such as those described in JP-A-48-064183, JP-B-49-043191, JP-B-52-030490, polyester acrylates, epoxy resins and (meth) Polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products with acrylic acid, and mixtures thereof can be mentioned. Compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Further, polyfunctional (meth)acrylate obtained by reacting polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth)acrylate and an ethylenically unsaturated bond can also be used.

Further, as preferred radical cross-linking agents other than those described above, JP-A-2010-160418, JP-A-2010-129825, JP-A-4364216, etc. have a fluorene ring and an ethylenically unsaturated bond. It is also possible to use compounds having two or more groups and cardo resins.

Furthermore, other examples include specific unsaturated compounds described in JP-B-46-043946, JP-B-01-040337, JP-B-01-040336, and JP-A-02-025493. vinyl phosphonic acid compounds and the like can also be mentioned. Compounds containing perfluoroalkyl groups described in JP-A-61-022048 can also be used. Furthermore, the journal of Japan Adhesive Association vol. 20, No. 7, pp. 300-308 (1984) as photopolymerizable monomers and oligomers can also be used.

In addition to the above, compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964, compounds described in paragraphs 0087 to 0131 of WO 2015/199219 can also be preferably used, the contents of which are herein incorporated into the book.

Further, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylated, which are described together with specific examples as formulas (1) and (2) in JP-A-10-062986, It can be used as a radical cross-linking agent.

Furthermore, the compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as radical cross-linking agents, the contents of which are incorporated herein.

As a radical cross-linking agent, dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; Nippon Kayaku Co., Ltd. ), A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) ) acrylate (as a commercial product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.), and their (meth)acryloyl groups via ethylene glycol residues or propylene glycol residues Structures that are linked together are preferred. These oligomeric types can also be used.

Examples of commercially available radical cross-linking agents include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer, SR-209, a bifunctional methacrylate having four ethyleneoxy chains, manufactured by Sartomer. 231, 239, Nippon Kayaku Co., Ltd. DPCA-60, a hexafunctional acrylate having 6 pentyleneoxy chains, TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS-10 , UAB-140 (manufactured by Nippon Paper Industries), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (Japan Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blenmer PME400 (manufactured by NOF Corporation), etc. mentioned.

Examples of radical cross-linking agents include urethane acrylates such as those described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, JP-B-02-016765, Urethane compounds having an ethylene oxide skeleton described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417 and JP-B-62-039418 are also suitable. Furthermore, as a radical cross-linking agent, 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-01-105238 are used. can also

The radical cross-linking agent may be a radical cross-linking agent having an acid group such as a carboxy group or a phosphoric acid group. A radical cross-linking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. is more preferable. Particularly preferably, in a radical cross-linking agent obtained by reacting an unreacted hydroxy group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give an acid group, the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol is a compound. Examples of commercially available products include polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd. such as M-510 and M-520.

The acid value of the radical cross-linking agent having an acid group is preferably 0.1-300 mgKOH/g, particularly preferably 1-100 mgKOH/g. If the acid value of the radical cross-linking agent is within the above range, the handleability in production is excellent, and furthermore the developability is excellent. Moreover, the polymerizability is good. The acid value is measured according to JIS K 0070:1992.

From the viewpoint of pattern resolution and film stretchability, the resin composition preferably uses a bifunctional methacrylate or acrylate.
Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, and PEG600 diacrylate. methacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6 hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, bisphenol A EO (ethylene oxide) adduct diacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO ( Propylene oxide) adduct diacrylate, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, other bifunctional acrylates having urethane bonds, Bifunctional methacrylates with urethane bonds can be used. These can be used in combination of two or more as needed.
For example, PEG200 diacrylate is a polyethylene glycol diacrylate having a polyethylene glycol chain formula weight of about 200.
In the resin composition of the present invention, a monofunctional radical cross-linking agent can be preferably used as the radical cross-linking agent from the viewpoint of suppressing warpage associated with the elastic modulus control of the pattern (cured product). Monofunctional radical cross-linking agents include n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, ) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc. (meth) Acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl glycidyl ether are preferably used. As the monofunctional radical cross-linking agent, a compound having a boiling point of 100° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
Other di- or higher functional radical cross-linking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

When a radical cross-linking agent is contained, its content is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the resin composition of the present invention. More preferably, the lower limit is 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

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

[Other cross-linking agents]
It is also preferable that the resin composition of the present invention contains another cross-linking agent different from the radical cross-linking agent described above.
In the present invention, the other cross-linking agent refers to a cross-linking agent other than the above-described radical cross-linking agent, and the above-described photoacid generator or photobase generator reacts with other compounds in the composition or reacts with them. It is preferable that the compound has a plurality of groups in the molecule that promote the reaction forming covalent bonds with the product, and covalent bonds are formed with other compounds in the composition or reaction products thereof. Compounds having a plurality of groups in the molecule, the reaction of which is promoted by the action of an acid or base, are preferred.
The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
As other cross-linking agents, compounds having at least one group selected from the group consisting of acyloxymethyl groups, methylol groups and alkoxymethyl groups are preferred, and the compounds are preferably selected from the group consisting of acyloxymethyl groups, methylol groups and alkoxymethyl groups. More preferred is a compound having a structure in which at least one group is directly bonded to a nitrogen atom.
Other cross-linking agents include, for example, an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, and benzoguanamine, which is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is converted to an acyloxymethyl group, methylol group, or A compound having a structure substituted with an alkoxymethyl group can be mentioned. The method for producing these compounds is not particularly limited as long as they have the same structure as the compounds produced by the above methods. Oligomers formed by self-condensation of methylol groups of these compounds may also be used.
As the amino group-containing compound, a melamine-based crosslinking agent is a melamine-based crosslinking agent, a glycoluril, urea or alkyleneurea-based crosslinking agent is a urea-based crosslinking agent, and an alkyleneurea-based crosslinking agent is an alkyleneurea-based crosslinking agent. A cross-linking agent using benzoguanamine is called a benzoguanamine-based cross-linking agent.
Among these, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based cross-linking agents and melamine-based cross-linking agents. More preferably, it contains at least one compound selected from the group consisting of agents.

As a compound containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention, an alkoxymethyl group or an acyloxymethyl group is directly substituted on the nitrogen atom of an aromatic group or the following urea structure, or on a triazine. can be given as structural examples.
The alkoxymethyl group or acyloxymethyl group of the above compound preferably has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms.
The total number of alkoxymethyl groups and acyloxymethyl groups in the above compound is preferably 1-10, more preferably 2-8, and particularly preferably 3-6.
The molecular weight of the compound is preferably 1500 or less, preferably 180-1200.

R ₁₀₀ represents an alkyl group or an acyl group.
R ₁₀₁ and R ₁₀₂ each independently represent a monovalent organic group and may combine with each other to form a ring.

Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group directly substitutes an aromatic group include compounds represented by the following general formula.

In the formula, X represents a single bond or a divalent organic group, each R ₁₀₄ independently represents an alkyl group or an acyl group, R ₁₀₃ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group , or a group that decomposes under the action of an acid to produce an alkali-soluble group (e.g., a group that leaves under the action of an acid, a group represented by —C(R ⁴ ) ₂ COOR ⁵ (R ⁴ is independently It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁵ represents a group that leaves under the action of an acid.)).
R ₁₀₅ each independently represents an alkyl group or alkenyl group, a, b and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3 , a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less.
For R ⁵ in the group represented by —C(R ⁴ ) ₂ COOR ⁵ , a group that is decomposed by the action of an acid to produce an alkali-soluble group, a group that is eliminated by the action of an acid, and —C(R ₃₆ )(R ₃₇ )(R ₃₈ ), —C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), —C(R ₀₁ )(R ₀₂ )(OR ₃₉ ), and the like.
In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, cycloalkyl group, aryl group, aralkyl group or alkenyl group. R ₃₆ and R ₃₇ may combine with each other to form a ring.
As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable.
The alkyl group may be linear or branched.
As the cycloalkyl group, a cycloalkyl group having 3 to 12 carbon atoms is preferable, and a cycloalkyl group having 3 to 8 carbon atoms is more preferable.
The cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring.
The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably a phenyl group.
As the aralkyl group, an aralkyl group having 7 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 16 carbon atoms is more preferable.
The aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as the preferred embodiments of the alkyl and aryl groups described above.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, more preferably an alkenyl group having 3 to 16 carbon atoms.
Moreover, these groups may further have a known substituent within the range in which the effects of the present invention can be obtained.

R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

The group that is decomposed by the action of an acid to form an alkali-soluble group or the group that is eliminated by the action of an acid is preferably a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, or the like. More preferred are tertiary alkyl ester groups and acetal groups.

Specific examples of compounds having an alkoxymethyl group include the following structures. Examples of the compound having an acyloxymethyl group include compounds obtained by changing the alkoxymethyl group of the following compounds to an acyloxymethyl group. Compounds having an alkoxymethyl group or acyloxymethyl in the molecule include, but are not limited to, the following compounds.

As the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group, a commercially available one or a compound synthesized by a known method may be used.
From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring are preferred.

Specific examples of melamine-based cross-linking agents include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.

Specific examples of urea-based cross-linking agents include monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, and dimethoxymethylated glycol. Uril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, diethoxymethylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril , dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, or tetrabutoxymethylated glycoluril glycoluril-based crosslinkers such as uril;
urea-based cross-linking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea;
monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxymethylated ethyleneurea, monoethoxymethylated ethyleneurea, diethoxymethylated ethyleneurea, monopropoxymethylated ethyleneurea, dipropoxymethyl ethylene urea-based cross-linking agents such as ethylene urea, monobutoxymethyl ethylene urea, or dibutoxymethyl ethylene urea;
Monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethyl propylene urea-based cross-linking agents such as propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea;
1,3-di(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone and the like.

Specific examples of benzoguanamine-based cross-linking agents include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, and trimethoxymethylated benzoguanamine. , tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetra propoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, and the like.

In addition, the compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group includes at least one group selected from the group consisting of a methylol group and an alkoxymethyl group on an aromatic ring (preferably a benzene ring). Compounds to which a seed group is directly attached are also preferably used.
Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate. , bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl) Benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4′,4″-ethylidene tris[2,6-bis(methoxymethyl)phenol], 5 ,5′-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3′,5,5′-tetrakis ( methoxymethyl)-1,1'-biphenyl-4,4'-diol and the like.

Commercial products may be used as other cross-linking agents, and suitable commercial products include 46DMOC, 46DMOEP (manufactured by Asahi Organic Chemicals Industry Co., Ltd.), DML-PC, DML-PEP, DML-OC, and DML-OEP. , DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP -Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML -BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (Honshu Chemical Industry Co., Ltd.), Nikalac (registered trademark, hereinafter the same) MX-290, Nikalac MX-280, Nikalac MX-270, Nikalac MX-279, Nikalac MW-100LM, Nikalac MX-750LM (manufactured by Sanwa Chemical Co., Ltd.) ) and the like.

Moreover, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds as another cross-linking agent.

- 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 less and does not undergo a dehydration reaction resulting from the cross-linking, so film shrinkage does not easily occur. Therefore, containing an epoxy compound is effective for low-temperature curing and suppression of warpage of the resin composition of the present invention.

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

Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether. , alkylene glycol type epoxy resins such as trimethylolpropane triglycidyl ether or polyhydric alcohol hydrocarbon type epoxy resins; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; epoxy groups such as polymethyl (glycidyloxypropyl) siloxane Examples include, but are not limited to, containing silicones and the like. Specifically, Epiclon (registered trademark) 850-S, Epiclon (registered trademark) HP-4032, Epiclon (registered trademark) HP-7200, Epiclon (registered trademark) HP-820, Epiclon (registered trademark) HP-4700, Epiclon (registered trademark) HP-4770, Epiclon (registered trademark) EXA-830LVP, Epiclon (registered trademark) EXA-8183, Epiclon (registered trademark) EXA-8169, Epiclon (registered trademark) N-660, Epiclon (registered trademark) N-665-EXP-S, Epiclon (registered trademark) N-740 (trade name, manufactured by DIC Corporation), Ricaresin (registered trademark) BEO-20E, Ricaresin (registered trademark) BEO-60E, Ricaresin (registered trademark) ) HBE-100, Ricaresin (registered trademark) DME-100, Ricaresin (registered trademark) L-200 (trade name, manufactured by Shin Nippon Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (Trade names above, manufactured by ADEKA Co., Ltd.), Celoxide (registered trademark) 2021P, Celoxide (registered trademark) 2081, Celoxide (registered trademark) 2000, EHPE3150, Epolead (registered trademark) GT401, Epolead (registered trademark) PB4700, Epolead (registered trademark) PB3600 (trade name, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L , NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020 , EPPN-201, BREN-S, and BREN-10S (these are trade names, manufactured by Nippon Kayaku Co., Ltd.). The following compounds are also preferably used.

In the formula, n is an integer of 1-5 and m is an integer of 1-20.

Among the above structures, it is preferable that n is 1 to 2 and m is 3 to 7 from the viewpoint of achieving both heat resistance and elongation improvement.

-Oxetane compound (compound having an oxetanyl group)-
Examples of oxetane compounds 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, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester and the like can be mentioned. As a specific example, Aron oxetane series manufactured by Toagosei Co., Ltd. (eg, OXT-121, OXT-221) can be suitably used, and these can be used alone or in combination of two or more. good.

-Benzoxazine compound (compound having a benzoxazolyl group)-
A benzoxazine compound is preferable because it is a cross-linking reaction derived from a ring-opening addition reaction, so that degassing does not occur during curing, and thermal shrinkage is reduced to suppress warping.

Preferable examples of benzoxazine compounds include Pd-type benzoxazine, Fa-type benzoxazine (these are trade names, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resins, phenol novolac-type dihydrobenzoxazines, oxazine compounds. These may be used alone or in combination of two or more.

The content of the other cross-linking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. It is more preferably 5 to 15% by mass, particularly preferably 1.0 to 10% by mass. Other cross-linking agents may be contained alone, or may be contained in two or more. When two or more other cross-linking agents are contained, the total is preferably within the above range.

[Polymerization initiator]
The resin composition of the present invention preferably contains a polymerization initiator capable of initiating polymerization by light and/or heat. In particular, it preferably contains a photopolymerization initiator.
The photopolymerization initiator is preferably a photoradical polymerization initiator. The radical photopolymerization initiator is not particularly limited and can be appropriately selected from known radical photopolymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferred. It may also be an activator that produces an active radical by producing some action with a photoexcited sensitizer.

The radical photopolymerization initiator contains at least one compound having a molar extinction coefficient of at least about 50 L·mol ⁻¹ ·cm ⁻¹ within the wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). is preferred. The molar extinction coefficient of a compound can be measured using known methods. For example, it is preferably measured at a concentration of 0.01 g/L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

As the radical photopolymerization initiator, any known compound can be used. For example, halogenated hydrocarbon derivatives (e.g., 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, etc. oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, and the like. For details of these, paragraphs 0165 to 0182 of JP-A-2016-027357 and paragraphs 0138 to 0151 of WO 2015/199219 can be referred to, the contents of which are incorporated herein. In addition, paragraphs 0065 to 0111 of JP-A-2014-130173, compounds described in Japanese Patent No. 6301489, MATERIAL STAGE 37-60p, vol. 19, No. 3, the peroxide photopolymerization initiator described in 2019, the photopolymerization initiator described in International Publication No. 2018/221177, the photopolymerization initiator described in International Publication No. 2018/110179, JP 2019-043864 The photopolymerization initiator described in JP-A-2019-044030, the photopolymerization initiator described in JP-A-2019-167313, and the peroxide-based initiator described in JP-A-2019-167313. incorporated into the specification.

Examples of ketone compounds include compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated herein. As a commercial product, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

In one embodiment of the present invention, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be preferably used as the radical photopolymerization initiator. More specifically, for example, aminoacetophenone-based initiators described in JP-A-10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used. incorporated.

Examples of α-hydroxyketone initiators include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, and IRGACURE. -2959 and IRGACURE 127 (trade names: both manufactured by BASF) can be used.

Examples of α-aminoketone initiators include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all BASF company) can be used.

As an aminoacetophenone-based initiator, the compound described in JP-A-2009-191179, whose maximum absorption wavelength is matched to a wavelength light source such as 365 nm or 405 nm, can also be used, the contents of which are incorporated herein.

Acylphosphine oxide initiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and the like. Also, Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), IRGACURE-819 and IRGACURE-TPO (trade names: all manufactured by BASF) can be used.

Examples of metallocene compounds include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF) and Keycure VIS 813 (manufactured by King Brother Chem).

As the radical photopolymerization initiator, an oxime compound is more preferable. By using an oxime compound, the exposure latitude can be improved more effectively. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.

Specific examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, J. Am. C. S. Compounds described in Perkin II (1979, pp. 1653-1660), J. Am. C. S. Perkin II (1979, pp.156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232), compounds described in JP-A-2000-066385, Compounds described in JP-A-2004-534797, compounds described in JP-A-2017-019766, compounds described in Patent No. 6065596, compounds described in WO 2015/152153, WO 2017 / 051680, compounds described in JP-A-2017-198865, compounds described in paragraphs 0025 to 0038 of WO 2017/164127, compounds described in WO 2013/167515, etc. , the contents of which are incorporated herein.

Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxy iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one , and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. In the resin composition of the present invention, it is particularly preferable to use an oxime compound (an oxime-based radical photopolymerization initiator) as the radical photopolymerization initiator. The oxime-based radical photopolymerization initiator has 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 (manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA Co., Ltd., the light described in JP-A-2012-014052 A radical polymerization initiator 2) is also preferably used. In addition, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Tenryu Electric New Materials Co., Ltd.), Adeka Arkles NCI-730, NCI-831 and Adeka Arkles NCI-930 (manufactured by ADEKA Co., Ltd.) are also used. be able to. Also, DFI-091 (manufactured by Daito Chemix Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can be used. Also, an oxime compound having the following structure can be used.

An oxime compound having a fluorene ring can also be used as the radical photopolymerization initiator. Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466 and compounds described in Japanese Patent No. 06636081, the contents of which are incorporated herein.

As the radical photopolymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in WO2013/083505, the contents of which are incorporated herein.

It is also possible to use oxime compounds having fluorine atoms. Specific examples of such oxime compounds 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. and compound (C-3) described in paragraph 0101 of JP-A-164471, the contents of which are incorporated herein.

An oxime compound having a nitro group can be used as the photopolymerization initiator. The oxime compound having a nitro group is also preferably a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraph numbers 0031 to 0047 of JP-A-2013-114249 and paragraph numbers 0008-0012 and 0070-0079 of JP-A-2014-137466; Included are compounds described in paragraphs 0007-0025 of Japanese Patent No. 4223071, the contents of which are incorporated herein. Further, the oxime compound having a nitro group also includes ADEKA Arkles NCI-831 (manufactured by ADEKA Co., Ltd.).

An oxime compound having a benzofuran skeleton can also be used as the radical photopolymerization initiator. Specific examples include OE-01 to OE-75 described in WO 2015/036910.

As the radical photopolymerization initiator, an oxime compound in which a substituent having a hydroxy group is bonded to a carbazole skeleton can also be used. Such photoinitiators include compounds such as those described in WO2019/088055, the contents of which are incorporated herein.

As the photopolymerization initiator, an oxime compound having an aromatic ring group Ar ^{2 OX1} in which an electron-withdrawing group is introduced into the aromatic ring (hereinafter also referred to as oxime compound OX) can be used. Examples of the electron-withdrawing group possessed by the aromatic ring group Ar ^OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group. An acyl group and a nitro group are preferred, an acyl group is more preferred, and a benzoyl group is even more preferred because a film having excellent light resistance can be easily formed. A benzoyl group may have a substituent. Examples of substituents include halogen atoms, cyano groups, nitro groups, hydroxy groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, heterocyclic oxy groups, alkenyl groups, alkylsulfanyl groups, arylsulfanyl groups, It is preferably an acyl group or an amino group, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group or an amino group. A sulfanyl group or an amino group is more preferred.

式中、Ｒ^Ｘ１は、アルキル基、アルケニル基、アルコキシ基、アリール基、アリールオキシ基、複素環基、複素環オキシ基、アルキルスルファニル基、アリールスルファニル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、アシル基、アシルオキシ基、アミノ基、ホスフィノイル基、カルバモイル基またはスルファモイル基を表し、
Ｒ^Ｘ２は、アルキル基、アルケニル基、アルコキシ基、アリール基、アリールオキシ基、複素環基、複素環オキシ基、アルキルスルファニル基、アリールスルファニル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、アシルオキシ基またはアミノ基を表し、
Ｒ^Ｘ３～Ｒ^Ｘ１４は、それぞれ独立して水素原子または置換基を表す。
ただし、Ｒ^Ｘ１０～Ｒ^Ｘ１４のうち少なくとも一つは、電子求引性基である。 The oxime compound OX is preferably at least one selected from the compounds represented by the formula (OX1) and the compounds represented by the formula (OX2), more preferably the compound represented by the formula (OX2). preferable.

In the formula, R ^X1 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl a group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group or a sulfamoyl group,
R ^X2 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, aryl represents a sulfonyl group, an acyloxy group or an amino group,
R ^X3 to R ^X14 each independently represent a hydrogen atom or a substituent.
However, at least one of R ^X10 to R ^X14 is an electron-withdrawing group.

In the above formula, R ^X12 is an electron-withdrawing group, and R ^X10 , R ^X11 , R ^X13 and R ^X14 are preferably hydrogen atoms.

Specific examples of the oxime compound OX include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein.

The most preferable oxime compounds include oxime compounds having specific substituents shown in JP-A-2007-269779 and oxime compounds having a thioaryl group shown in JP-A-2009-191061. incorporated herein.

From the viewpoint of exposure sensitivity, photoradical polymerization initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl selected from the group consisting of imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds; are preferred.

More preferred radical photopolymerization 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, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferred, and metallocene compounds or oxime compounds are even more preferred. .

Further, the photoradical polymerization initiator includes benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone such as N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), 2-benzyl -aromatic ketones such as 2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, alkylanthraquinones, etc. quinones condensed with the aromatic ring of , benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, and benzyl derivatives such as benzyl dimethyl ketal can also be used. A compound represented by the following formula (I) can also be used.

In formula (I), R ¹⁰⁰ 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 alkoxy group having 1 to 12 carbon atoms, a phenyl group, Alternatively, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, a carbon number interrupted by one or more oxygen atoms a phenyl group or a biphenyl group substituted with at least one of an alkyl group having 2 to 18 carbon atoms and an alkyl group having 1 to 4 carbon atoms, and R ^I01 is a group represented by formula (II); R ¹⁰² to R ¹⁰⁴ are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 ^to 12 carbon atoms, or a halogen atom.

In the formula, R ¹⁰⁵ to R ¹⁰⁷ are the same as R ¹⁰² to R ¹⁰⁴ in formula (I) above.

Further, as the photoradical polymerization initiator, compounds described in paragraphs 0048 to 0055 of WO 2015/125469 can also be used, the contents of which are incorporated herein.

As the radical photopolymerization initiator, a difunctional or trifunctional or higher radical photopolymerization initiator may be used. By using such a radical photopolymerization initiator, two or more radicals are generated from one molecule of the radical photopolymerization initiator, so good sensitivity can be obtained. In addition, when a compound having an asymmetric structure is used, the crystallinity is lowered, the solubility in a solvent or the like is improved, and precipitation becomes difficult over time, and the stability over time of the resin composition can be improved. . Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. 2015/004565, and Japanese Patent Publication No. 2016-532675. Paragraph numbers 0407 to 0412, dimers of oxime compounds described in paragraph numbers 0039 to 0055 of International Publication No. 2017/033680, compound (E) and compounds described in JP-A-2013-522445 ( G), Cmpd1 to 7 described in International Publication No. 2016/034963, oxime ester photoinitiators described in paragraph number 0007 of JP 2017-523465, JP 2017-167399 Photoinitiators described in paragraph numbers 0020 to 0033, photoinitiators (A) described in paragraph numbers 0017 to 0026 of JP-A-2017-151342, described in Japanese Patent No. 6469669 and oxime ester photoinitiators, the contents of which are incorporated herein.

When a photopolymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. , More preferably 0.5 to 15% by mass, still 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 photopolymerization initiators are contained, the total amount is preferably within the above range.
In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, the crosslinking by the photopolymerization initiator may be further advanced by heating with an oven, a hot plate, or the like.

[Sensitizer]
The resin composition may contain a sensitizer. A sensitizer absorbs specific actinic radiation and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and causes electron transfer, energy transfer, heat generation, or the like. As a result, the thermal radical polymerization initiator and the photoradical polymerization initiator undergo chemical changes and are decomposed to generate radicals, acids or bases.
Usable sensitizers include benzophenones, Michler's ketones, coumarins, pyrazole azos, anilinoazos, triphenylmethanes, anthraquinones, anthracenes, anthrapyridones, benzylidenes, oxonols, and pyrazolotriazole azos. , pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, penzopyran, and indigo compounds.
Sensitizers include, for example, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal) Cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyl denindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)iso naphthothiazole, 1,3-bis(4′-dimethylaminobenzal)acetone, 1,3-bis(4′-diethylaminobenzal)acetone, 3,3′-carbonyl-bis(7-diethylaminocoumarin), 3 -acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylamino coumarin (ethyl 7-(diethylamino)coumarin-3-carboxylate), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethyl) aminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4 '-dimethylacetanilide and the like.
Other sensitizing dyes may also be used.
For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP-A-2016-027357 can be referred to, the contents of which are incorporated herein.

When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, preferably 0.1 to 15% by mass, based on the total solid content of the resin composition. more preferably 0.5 to 10% by mass. The sensitizers may be used singly or in combination of two or more.

[Chain transfer agent]
The resin composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in Kobunshi Jiten, 3rd edition (edited by Kobunshi Gakkai, 2005), pp. 683-684. Chain transfer agents include, for example, a group of compounds having —S—S—, —SO ₂ —S—, —NO—, SH, PH, SiH, and GeH in the molecule, RAFT (Reversible Addition Fragmentation chain Transfer ) Dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds and the like having a thiocarbonylthio group used for polymerization are used. They can either donate hydrogen to less active radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals. In particular, thiol compounds can be preferably used.

In addition, the chain transfer agent can also use compounds described in paragraphs 0152 to 0153 of WO 2015/199219, the contents of which are incorporated herein.

When the resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, preferably 0.01 to 20 parts by mass, based on 100 parts by mass of the total solid content of the resin composition of the present invention. 1 to 10 parts by mass is more preferable, and 0.5 to 5 parts by mass is even more preferable. One type of chain transfer agent may be used, or two or more types may be used. When two or more chain transfer agents are used, the total is preferably within the above range.

<Base generator>
The resin composition of the present invention may contain a base generator. Here, the base generator is a compound capable of generating a base by physical or chemical action. Preferred base generators for the resin composition of the present invention include thermal base generators and photobase generators.
However, the base generator corresponding to the above-mentioned specific compound shall not correspond to the base generator mentioned here.
In particular, when the resin composition contains a cyclized resin precursor, the resin composition preferably contains a base generator. By containing a thermal base generator in the resin composition, the cyclization reaction of the precursor can be promoted, for example, by heating, and the cured product has good mechanical properties and chemical resistance. Performance as an interlayer insulating film for wiring layers is improved.
The base generator may be an ionic base generator or a non-ionic base generator. Examples of bases generated from base generators include secondary amines and tertiary amines.
There are no particular restrictions on the base generator used in the present invention, and known base generators can be used. Examples of known base generators include carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, and amine imides. compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amineimide compounds, phthalimide derivative compounds, acyloxyimino compounds, and the like can be used.
Specific compounds of the nonionic base generator include compounds represented by Formula (B1), Formula (B2), or Formula (B3).

In Formula (B1) and Formula (B2), Rb ¹ , Rb ² and Rb ³ are each independently an organic group having no tertiary amine structure, a halogen atom or a hydrogen atom. However, Rb ¹ and Rb ² are not hydrogen atoms at the same time. Also, none of Rb ¹ , Rb ² and Rb ³ has a carboxy group. In this specification, the tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when forming an amide group together with the nitrogen atom, this is not the case.

In formulas (B1) and (B2), at least one of Rb ¹ , Rb ² and Rb ³ preferably contains a cyclic structure, and more preferably at least two of them contain a cyclic structure. The cyclic structure may be either a single ring or a condensed ring, preferably a single ring or a condensed ring in which two single rings are condensed. The monocyclic ring is preferably a 5- or 6-membered ring, more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring and a benzene ring, more preferably a cyclohexane ring.

More specifically, Rb ¹ and Rb ² are a hydrogen atom, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, even more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms). , more preferably 2 to 18, more preferably 3 to 12), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, even more preferably 6 to 10), or an arylalkyl group (7 carbon atoms to 25 are preferred, 7 to 19 are more preferred, and 7 to 12 are even more preferred). These groups may have substituents to the extent that the effects of the present invention are exhibited. Rb ¹ and Rb ² may combine with each other to form a ring. The ring to be formed is preferably a 4- to 7-membered nitrogen-containing heterocyclic ring. Rb ¹ and Rb ² are particularly linear, branched or cyclic alkyl groups (having preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms) which may have a substituent. is preferably a cycloalkyl group optionally having a substituent (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms), and more preferably a cycloalkyl group having a substituent A cyclohexyl group, which may be

Rb ³ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 10 are more preferred), alkenyl groups (preferably 2 to 24 carbon atoms, more preferably 2 to 12, more preferably 2 to 6), arylalkyl groups (preferably 7 to 23 carbon atoms, more preferably 7 to 19 preferably 7 to 12), arylalkenyl groups (preferably 8 to 24 carbon atoms, more preferably 8 to 20, more preferably 8 to 16), alkoxyl groups (preferably 1 to 24 carbon atoms, 2 to 18 is more preferred, and 3 to 12 are even more preferred), an aryloxy group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12), or an arylalkyloxy group (preferably 7 to 12 carbon atoms). 23 is preferred, 7 to 19 are more preferred, and 7 to 12 are even more preferred). Among them, a cycloalkyl group (having preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferred. Rb ³ may further have a substituent as long as the effects of the present invention are exhibited.

The compound represented by formula (B1) is preferably a compound represented by formula (B1-1) or formula (B1-2) below.

In the formula, Rb ¹¹ and Rb ¹² and Rb ³¹ and Rb ³² are respectively the same as Rb ¹ and Rb ² in formula (B1).
Rb ¹³ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19, 7 to 12 are more preferable), and may have a substituent within the range in which the effects of the present invention are exhibited. Among them, Rb ¹³ is preferably an arylalkyl group.

Rb ³³ and Rb ³⁴ each independently represents a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms , more preferably 2 to 8, more preferably 2 to 3), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 10), an arylalkyl group (7 to 23 is preferred, 7 to 19 are more preferred, and 7 to 11 are even more preferred), and a hydrogen atom is preferred.

Rb ³⁵ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, even more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 , 7 to 12 are more preferred), and aryl groups are preferred.

The compound represented by formula (B1-1) is also preferably the compound represented by formula (B1-1a).

Rb ¹¹ and Rb ¹² have the same definitions as Rb ¹¹ and Rb ¹² in formula (B1-1).
Rb ¹⁵ and Rb ¹⁶ are hydrogen atoms, alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 6, even more preferably 1 to 3), alkenyl groups (preferably 2 to 12 carbon atoms, 2 to 6 more preferably 2 to 3), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, even more preferably 6 to 10), an arylalkyl group (preferably 7 to 23 carbon atoms, 7 to 19 are more preferred, and 7 to 11 are even more preferred), and a hydrogen atom or a methyl group is preferred.
Rb ¹⁷ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19, 7 to 12 are more preferable), and aryl groups are particularly preferable.

In formula (B3), L is a divalent hydrocarbon group having a saturated hydrocarbon group on a connecting chain route connecting adjacent oxygen atoms and carbon atoms, wherein the number of atoms on the connecting chain route is represents a hydrocarbon group of 3 or more. ^RN1 and ^RN2 each independently represent a monovalent organic group.

As used herein, the term “connected chain” refers to the shortest (minimum number of atoms) of atomic chains on a path connecting two atoms or groups of atoms to be connected. For example, in the compound represented by the following formula, L is composed of a phenylene ethylene group, has an ethylene group as a saturated hydrocarbon group, the linking chain is composed of four carbon atoms, and on the route of the linking chain The number of atoms of (that is, the number of atoms constituting the linking chain, hereinafter also referred to as "linking chain length" or "linking chain length") is 4.

The number of carbon atoms in L (including carbon atoms other than the carbon atoms in the connecting chain) in formula (B3) is preferably 3-24. The upper limit is more preferably 12 or less, still more preferably 10 or less, and particularly preferably 8 or less. More preferably, the lower limit is 4 or more. From the viewpoint of rapid progress of the intramolecular cyclization reaction, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and 5 The following are particularly preferred. In particular, the linking chain length of L is preferably 4 or 5, most preferably 4. Specific preferred compounds of the base generator include, for example, compounds described in paragraphs 0102 to 0168 of WO2020/066416, and compounds described in paragraphs 0143 to 0177 of WO2018/038002. mentioned.

Further, the base generator preferably contains a compound represented by the following formula (N1).

In formula (N1), R ^N1 and R ^N2 each independently represent a monovalent organic group, RC1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

L is a divalent linking group, preferably a divalent organic group. The linking chain length of the linking group is preferably 1 or more, more preferably 2 or more. The upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The linking chain length is the number of atoms present in the atomic arrangement that provides the shortest path between two carbonyl groups in the formula.

In formula (N1), R ^N1 and R ^N2 each independently represent a monovalent organic group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, more preferably 3 to 12 carbon atoms), and a hydrocarbon group ( preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms), specifically, an aliphatic hydrocarbon group (preferably 1 to 24 carbon atoms, 1 to 12 is more preferable, 1 to 10 is more preferable) or an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 10), and an aliphatic hydrocarbon groups are preferred. It is preferable to use an aliphatic hydrocarbon group as R ^N1 and R ^N2 because the generated base is highly basic. In addition, the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group are in the aliphatic hydrocarbon chain or in the aromatic ring, You may have an oxygen atom in the substituent. In particular, an aspect in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain is exemplified.

Aliphatic hydrocarbon groups constituting R ^N1 and R ^N2 include linear or branched chain alkyl groups, cyclic alkyl groups, groups related to combinations of chain alkyl groups and cyclic alkyl groups, and oxygen atoms in the chains. Alkyl groups having The linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms. Linear or branched chain alkyl groups are, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl group, isobutyl group, secondary butyl group, tertiary butyl group, isopentyl group, neopentyl group, tertiary pentyl group, isohexyl group and the like.
The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. Cyclic alkyl groups include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.
Groups associated with a combination of a chain alkyl group and a cyclic alkyl group preferably have 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, and even more preferably 4 to 12 carbon atoms. Groups related to combinations of chain alkyl groups and cyclic alkyl groups include, for example, a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, and an ethylcyclohexylethyl group.
The alkyl group having an oxygen atom in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms. An alkyl group having an oxygen atom in the chain may be chain or cyclic, and may be linear or branched.
Among them, from the viewpoint of raising the boiling point of the decomposition base described later, R ^{1 N1} and R ^{2 N2} are preferably alkyl groups having 5 to 12 carbon atoms. However, in a prescription that emphasizes adhesion when laminating with a metal (eg, copper) layer, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable.

^RN1 and ^RN2 may be linked to each other to form a ring structure. In forming the cyclic structure, the chain may have an oxygen atom or the like. The cyclic structure formed by R ^N1 and R ^N2 may be a monocyclic ring or a condensed ring, but is preferably a monocyclic ring. The cyclic structure to be formed is preferably a 5- or 6-membered ring containing a nitrogen atom in formula (N1), such as pyrrole ring, imidazole ring, pyrazole ring, pyrroline ring, pyrrolidine ring, imidazolidine ring, A pyrazolidine ring, a piperidine ring, a piperazine ring, a morpholine ring and the like can be mentioned, and a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring and a morpholine ring are preferably mentioned.

R ^C1 represents a hydrogen atom or a protecting group, preferably a hydrogen atom.

The protecting group is preferably a protecting group that is decomposed by the action of an acid or a base, and preferably includes a protecting group that is decomposed by an acid.

Specific examples of protecting groups include chain or cyclic alkyl groups or chain or cyclic alkyl groups having an oxygen atom in the chain. Chain or cyclic alkyl groups include methyl group, ethyl group, isopropyl group, tert-butyl group, cyclohexyl group and the like. The chain alkyl group having an oxygen atom in the chain specifically includes an alkyloxyalkyl group, more specifically a methyloxymethyl (MOM) group, an ethyloxyethyl (EE) group, and the like. mentioned. Cyclic alkyl groups having an oxygen atom in the chain include epoxy group, glycidyl group, oxetanyl group, tetrahydrofuranyl group, tetrahydropyranyl (THP) group and the like.

The divalent linking group constituting L is not particularly defined, but is preferably a hydrocarbon group, more preferably an aliphatic hydrocarbon group. The hydrocarbon group may have substituents and may have atoms of types other than carbon atoms in the hydrocarbon chain. More specifically, it is preferably a divalent hydrocarbon linking group which may have an oxygen atom in the chain, and a divalent aliphatic hydrocarbon which may have an oxygen atom in the chain group, a divalent aromatic hydrocarbon group, or a group related to a combination of a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group, A divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain is more preferred. These groups preferably have no oxygen atoms.
The divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms. A group related to a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (eg, an arylene alkyl group) preferably has 7 to 22 carbon atoms, more preferably 7 to 18, and 7 to 10 is more preferred.

Specific examples of the linking group L include a linear or branched chain alkylene group, a cyclic alkylene group, a group related to a combination of a chain alkylene group and a cyclic alkylene group, and an alkylene group having an oxygen atom in the chain. , a linear or branched chain alkenylene group, a cyclic alkenylene group, an arylene group and an arylene alkylene group are preferable.
The linear or branched chain alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms.
The cyclic alkylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.
The group associated with the combination of a chain alkylene group and a cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 4 to 6 carbon atoms.
An alkylene group having an oxygen atom in the chain may be chain or cyclic, and may be linear or branched. The alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms.

The linear or branched chain alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 3 carbon atoms. The linear or branched chain alkenylene group preferably has 1 to 10 C═C bonds, more preferably 1 to 6, even more preferably 1 to 3.
The cyclic alkenylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. The number of C═C bonds in the cyclic alkenylene group is preferably 1-6, more preferably 1-4, even more preferably 1-2.
The arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms.
The arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms.
Among them, a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkenylene group, an arylene group, and an arylene alkylene group are preferable, and a 1,2-ethylene group and a propanediyl group (especially 1, 3-propanediyl group), cyclohexanediyl group (especially 1,2-cyclohexanediyl group), vinylene group (especially cis-vinylene group), phenylene group (1,2-phenylene group), phenylenemethylene group (especially 1,2-phenylene methylene group) and ethyleneoxyethylene group (especially 1,2-ethyleneoxy-1,2-ethylene group) are more preferable.

Examples of the base generator include the following examples, but the present invention should not be construed as being limited thereto.

The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

Specific preferred compounds of the ionic base generator also include, for example, compounds described in paragraphs 0148 to 0163 of WO 2018/038002.

Specific examples of ammonium salts include the following compounds, but the present invention is not limited thereto.

Specific examples of iminium salts include the following compounds, but the present invention is not limited thereto.

When the resin composition of the present invention contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the resin in the resin composition of the present invention. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or may be 4 parts by mass or less.
One or two or more base generators can be used. When two or more kinds are used, the total amount is preferably within the above range.
In addition, the resin composition of the present invention can also be in an aspect in which it does not substantially contain a base generator other than the specific compound.
Specifically, the content of the base generator other than the specific compound is preferably 1% by mass or less, more preferably 0.5% by mass or less, relative to the total mass of the resin composition. It is more preferably 0.1% by mass or less. The lower limit is not particularly limited, and may be 0% by mass.

<Solvent>
The resin composition of the present invention preferably contains a solvent.
Any known solvent can be used as the solvent. The solvent is preferably an organic solvent. Organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas and alcohols.

Esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone , ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetates (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g. methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, 3-methoxypropionic acid ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionate alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl propyl oxypropionate (e.g., 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 (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvate Ethyl acetate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate and the like are preferred. .

Examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene 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 dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol Preferred examples include monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, dipropylene glycol dimethyl ether, and the like.

Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone and the like.

Preferred examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene.

Suitable sulfoxides include, for example, dimethyl sulfoxide.

As amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, Suitable examples include 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine and the like.

Suitable ureas include N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and the like.

Alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, Diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, diacetone alcohol and the like.

From the viewpoint of improving the properties of the coating surface, it is also preferable to mix two or more solvents.

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- 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, levoglucosenone, dihydrolevoglucosenone; Alternatively, a mixed solvent composed of two or more kinds is preferable. A combination of dimethyl sulfoxide and γ-butyrolactone or a combination of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred.

From the viewpoint of coating properties, the content of the solvent is preferably an amount such that the total solid concentration of the resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass. More preferably, the amount is from 10 to 70% by mass, and even more preferably from 20 to 70% by mass. The solvent content may be adjusted according to the desired thickness of the coating and the method of application.

The resin composition of the present invention may contain only one type of solvent, or may contain two or more types. When two or more solvents are contained, the total is preferably within the above range.

<Metal adhesion improver>
The resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used for electrodes, wiring, and the like. Examples of metal adhesion improvers include alkoxysilyl group-containing silane coupling agents, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, and β-ketoesters. compounds, amino compounds, and the like.

〔Silane coupling agent〕
Examples of the silane coupling agent include compounds described in paragraph 0167 of WO 2015/199219, compounds described in paragraphs 0062 to 0073 of JP 2014-191002, and paragraphs of WO 2011/080992. Compounds described in 0063-0071, compounds described in paragraphs 0060-0061 of JP-A-2014-191252, compounds described in paragraphs 0045-0052 of JP-A-2014-041264, International Publication No. 2014/097594 Compounds described in paragraph 0055, compounds described in paragraphs 0067 to 0078 of JP-A-2018-173573, the contents of which are incorporated herein. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. Moreover, it is also preferable to use the following compound as a silane coupling agent. In the following formulas, Me represents a methyl group and Et represents an ethyl group.

Other silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, sidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltri Methoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N- 2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine , N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- Examples include isocyanatopropyltriethoxysilane and 3-trimethoxysilylpropylsuccinic anhydride. These can be used singly or in combination of two or more.

[Aluminum Adhesion Aid]
Examples of aluminum-based adhesion aids include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), ethylacetoacetate aluminum diisopropylate, and the like.

In addition, as other metal adhesion improvers, compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and sulfide compounds described in paragraphs 0032-0043 of JP-A-2013-072935 can be used. can also be used, the contents of which are incorporated herein.

The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.01 to 30 parts by mass with respect to 100 parts by mass of the specific resin. 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 pattern and the metal layer is improved, and when it is at most the above upper limit value, the heat resistance and mechanical properties of the pattern are improved. One type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, the total is preferably within the above range.

<Migration inhibitor>
The resin composition of the present invention preferably further contains a migration inhibitor. By including the migration inhibitor, it becomes possible to effectively suppress the migration of metal ions derived from the metal layer (metal wiring) into the film.

Migration inhibitors are not particularly limited, but heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring, or condensed ring such as purine ring), thioureas and sulfanyl groups , hindered phenol-based compounds, salicylic acid derivative-based compounds, and hydrazide derivative-based compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 1H-tetrazole, 5- Tetrazole compounds such as phenyltetrazole and 5-amino-1H-tetrazole can be preferably used.

Alternatively, an ion trapping agent that traps anions such as halogen ions can be used.

Other migration inhibitors include rust inhibitors described in paragraph 0094 of JP-A-2013-015701, compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, and JP-A-2011-059656. The compound described in paragraph 0052, the compound described in paragraphs 0114, 0116 and 0118 of JP-A-2012-194520, the compound described in paragraph 0166 of WO 2015/199219, etc. can be used, and these The contents are incorporated herein.

Specific examples of migration inhibitors include the following compounds.

When the resin composition of the present invention 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 resin composition of the present invention. , more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass.
An aspect in which the resin composition of the present invention does not substantially contain a migration inhibitor is also one of the preferred aspects of the present invention.
“Substantially free of migration inhibitor” means that the content of the migration inhibitor is less than 0.01% by mass with respect to the total solid content of the resin composition of the present invention.

Only one type of migration inhibitor may be used, or two or more types may be used. When two or more migration inhibitors are used, the total is preferably within the above range.

<Polymerization inhibitor>
The resin composition of the present invention preferably contains a polymerization inhibitor. Polymerization inhibitors include phenol compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, metal compounds and the like.

Specific compounds of polymerization inhibitors include p-hydroquinone, o-hydroquinone, o-methoxyphenol, 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-nitrosophenyl hydroxylamine cerium salt, N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic 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, 1,3,5-tris(4- t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6, 6-tetramethylpiperidine 1-oxyl free radical, 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenothiazine, phenoxazine, 1,1-diphenyl-2-picrylhydrazyl, dibutyldithiocarbanate Copper (II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. are preferably used. In addition, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817, and the compounds described in paragraphs 0031 to 0046 of WO 2015/125469 can also be used, the contents of which are herein incorporated.

When the resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass with respect to the total solid content of the resin composition of the present invention. It is more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass.

One type of polymerization inhibitor may be used, or two or more types may be used. When two or more polymerization inhibitors are used, the total is preferably within the above range.

<Other additives>
The resin composition of the present invention may optionally contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, as long as the effects of the present invention can be obtained. Organic titanium compounds, antioxidants, anti-agglomerating agents, phenolic compounds, other polymer compounds, plasticizers and other auxiliaries (eg, antifoaming agents, flame retardants, etc.), etc. can be blended. Properties such as film physical properties can be adjusted by appropriately containing these components. These components are, for example, described in JP 2012-003225, paragraph number 0183 and later (corresponding US Patent Application Publication No. 2013/0034812, paragraph number 0237), JP 2008-250074 paragraph The descriptions of numbers 0101 to 0104, 0107 to 0109, etc. can be referred to, and the contents thereof are incorporated herein. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the resin composition of the present invention.

[Surfactant]
As the surfactant, various surfactants such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants can be used. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

By including a surfactant in the photosensitive resin composition of the present invention, the liquid properties (especially fluidity) when prepared as a coating liquid are further improved, and the uniformity of coating thickness and liquid saving are further improved. can do. That is, when a film is formed using a coating liquid to which a composition containing a surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the wettability to the surface to be coated is improved. , the coatability to the surface to be coated is improved. Therefore, it is possible to more preferably form a film having a uniform thickness with little unevenness in thickness.

Examples of fluorosurfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, RS-72-K (manufactured by DIC Corporation), Florado FC430, FC431, FC171, Novec FC4430, FC4432 (manufactured by 3M Japan Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (above , Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA), and the like. Fluorinated surfactants, compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327, compounds described in paragraphs 0117-0132 of JP-A-2011-132503 can also be used, the contents of which are incorporated herein. A block polymer can also be used as the fluorosurfactant, and specific examples thereof include compounds described in JP-A-2011-89090, the contents of which are incorporated herein.
The fluorosurfactant has a repeating unit derived from a (meth)acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meta) A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as fluorine-based surfactants used in the present invention.

The weight average molecular weight of the above compound is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.
A fluorine-containing polymer having an ethylenically unsaturated group in a side chain can also be used as a fluorine-based surfactant. Specific examples include compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, the contents of which are incorporated herein. Commercially available products include Megafac RS-101, RS-102 and RS-718K manufactured by DIC Corporation.

The fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorosurfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and saving liquid, and has good solubility in the composition.

Examples of silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (the above, Toray Dow Corning Co., Ltd. ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP-341, KF6001, KF6002 (manufactured by Shin-Etsu Silicone Co., Ltd. ), BYK307, BYK323, and BYK330 (manufactured by BYK Chemie Co., Ltd.).

Hydrocarbon surfactants include, for example, Pionin A-76, Nucalgen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, Pionin D-6112, Pionin D-2104-D, Pionin D-212, Pionin D-931, Pionin D-941, Pionin D-951, Pionin E-5310, Pionin P-1050-B, Pionin P-1028-P, Pionin P-4050-T and the like (manufactured by Takemoto Oil & Fat Co., Ltd.), and the like.

Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Examples include polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester. Commercially available products include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000. (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), Pionin D-6112, D-6112-W, D-6315 (Takemoto oil Co., Ltd.), OLFINE E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.).

Specific examples of cationic surfactants include organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 77, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like.

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

Only one type of surfactant may be used, or two or more types may be used in combination.
The surfactant content is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.

[Higher Fatty Acid Derivative]
In the resin composition of the present invention, a higher fatty acid derivative such as behenic acid or behenic acid amide is added in order to prevent polymerization inhibition caused by oxygen. may be unevenly distributed on the surface of the

In addition, as the higher fatty acid derivative, the compound described in paragraph 0155 of WO 2015/199219 can also be used, the content of which is incorporated herein.

When the resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass based on the total solid content of the resin composition of the present invention. Only one type of higher fatty acid derivative may be used, or two or more types thereof may be used. When two or more higher fatty acid derivatives are used, the total is preferably within the above range.

[Thermal polymerization initiator]
The resin composition of the present invention may contain a thermal polymerization initiator, particularly a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or accelerates the polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can be advanced, so that the solvent resistance can be further improved. Moreover, the photopolymerization initiator described above may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.

Specific examples of thermal radical polymerization initiators include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated herein.

When a thermal polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. , more preferably 0.5 to 15% by mass. One type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more thermal polymerization initiators are contained, the total amount is preferably within the above range.

[Inorganic particles]
The resin composition of the present invention may contain inorganic particles. Specific examples of inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.

The average particle diameter of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, still more preferably 0.03 to 1.0 μm, and 0.04 to 0.5 μm. Especially preferred.
The average particle size of the inorganic particles is the primary particle size and the volume average particle size. The volume average particle size can be measured by a dynamic light scattering method using Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.).
If the above measurement is difficult, the centrifugal sedimentation light transmission method, X-ray transmission method, or laser diffraction/scattering method can be used.

[Ultraviolet absorber]
The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used.
Examples of salicylate-based UV absorbers include phenyl salicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate, and the like. Examples of benzophenone-based UV absorbers include 2,2'-dihydroxy-4- Methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2- and hydroxy-4-octoxybenzophenone. Examples of benzotriazole-based UV absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3 '-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-( 2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2 -(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5' -(1,1,3,3-tetramethyl)phenyl]benzotriazole and the like.

Examples of substituted acrylonitrile UV absorbers include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Furthermore, examples of triazine-based UV absorbers include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl )-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl) -mono(hydroxyphenyl)triazine compounds such as 1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl -4-propyloxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2 bis(hydroxyphenyl)triazine compounds such as ,4-dimethylphenyl)-1,3,5-triazine; 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl )-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4 tris(hydroxyphenyl)triazine compounds such as -(3-butoxy-2-hydroxypropyloxy)phenyl]-1,3,5-triazine;

In the present invention, the above various ultraviolet absorbers may be used singly or in combination of two or more.
The composition of the present invention may or may not contain an ultraviolet absorber, but when it does, the content of the ultraviolet absorber is 0.001% by mass with respect to the total solid mass of the composition of the present invention. It is preferably at least 1% by mass, more preferably at least 0.01% by mass and not more than 0.1% by mass.

[Organic titanium compound]
The resin composition of this embodiment may contain an organic titanium compound. By including the organic titanium compound in the resin composition, it is possible to form a resin layer having excellent chemical resistance even when cured at a low temperature.

Organotitanium compounds that can be used include those in which organic groups are attached to titanium atoms through covalent or ionic bonds.
Specific examples of organotitanium compounds are shown below in I) to VII):
I) Titanium chelate compound: Among them, a titanium chelate compound having two or more alkoxy groups is more preferable because the storage stability of the resin composition is good and a good curing pattern can be obtained. Specific examples are titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate ), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), and the like.
II) Tetraalkoxytitanium compounds: for example titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide , titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl) butoxide}] and the like.
III) Titanocene compounds: for example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2, 4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium and the like.
IV) Monoalkoxy titanium compounds: for example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, and the like.
V) Titanium oxide compounds: for example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide and the like.
VI) Titanium tetraacetylacetonate compounds: such as titanium tetraacetylacetonate.
VII) Titanate coupling agent: For example, isopropyltridodecylbenzenesulfonyl titanate and the like.

Among them, as the organotitanium compound, at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds provides better chemical resistance. It is preferable from the viewpoint of performance. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide) and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H) -pyrrol-1-yl)phenyl)titanium is preferred.

When the organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin. When the amount is 0.05 parts by mass or more, the resulting cured pattern exhibits good heat resistance and chemical resistance more effectively. Excellent.

〔Antioxidant〕
The compositions of the present invention may contain antioxidants. By containing an antioxidant as an additive, it is possible to improve the elongation properties of the cured film and the adhesion to metal materials. Antioxidants include phenol compounds, phosphite ester compounds, thioether compounds and the like. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred. A substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable as the above substituent. The antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule. Phosphorus-based antioxidants can also be suitably used as antioxidants. As a phosphorus antioxidant, tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6 -yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl ) oxy]ethyl]amine, ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite, and the like. Examples of commercially available antioxidants include Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (manufactured by ADEKA Corporation) and the like. In addition, as the antioxidant, compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used, the contents of which are incorporated herein. The composition of the present invention may also contain latent antioxidants, if desired. The latent antioxidant is a compound in which the site functioning as an antioxidant is protected with a protective group, and is heated at 100 to 250°C, or heated at 80 to 200°C in the presence of an acid/base catalyst. A compound that functions as an antioxidant by removing the protective group by the reaction is exemplified. Examples of latent antioxidants include compounds described in WO 2014/021023, WO 2017/030005, and JP 2017-008219, the contents of which are incorporated herein. Commercially available latent antioxidants include ADEKA Arkles GPA-5001 (manufactured by ADEKA Co., Ltd.).
Examples of preferred antioxidants include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and compounds of formula (3).

In general formula (3), R ⁵ represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), and R ⁶ represents alkylene having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). represents a group. R ⁷ represents a monovalent to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), an oxygen atom and a nitrogen atom. k represents an integer of 1 to 4;

The compound represented by formula (3) suppresses oxidative deterioration of the aliphatic group and phenolic hydroxyl group of the resin. In addition, metal oxidation can be suppressed by the antirust action on the metal material.

More preferably, k is an integer of 2 to 4 because it can act on the resin and the metal material at the same time. ^R7 includes an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, -O-, -NH-, -NHNH-, combinations thereof, and the like, which may further have a substituent. Among these, it is preferable to have an alkyl ether group, -NH-, from the viewpoint of solubility in a developer and metal adhesion. more preferred.

Examples of the compound represented by formula (3) include the following, but are not limited to the following structure.

The amount of the antioxidant to be added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on the resin. By making the addition amount 0.1 parts by mass or more, the effect of improving elongation characteristics and adhesion to metal materials can be easily obtained even in a high-temperature and high-humidity environment. The interaction with the agent improves the sensitivity of the resin composition. Only one kind of antioxidant may be used, or two or more kinds thereof may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.

[Anti-aggregation agent]
The resin composition of the present embodiment may contain an anti-aggregation agent as necessary. Anti-aggregation agents include sodium polyacrylate and the like.

In the present invention, the aggregation inhibitor may be used alone or in combination of two or more.
The composition of the present invention may or may not contain an anti-aggregating agent, but when it is included, the content of the anti-aggregating agent is 0.01% by mass with respect to the total solid mass of the composition of the present invention. It is preferably at least 10% by mass, more preferably at least 0.02% by mass and not more than 5% by mass.

[Phenolic compound]
The resin composition of the present embodiment may contain a phenolic compound as necessary. Examples of phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X (these are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR -BIPC-F (these are trade names, manufactured by Asahi Organic Chemicals Industry Co., Ltd.) and the like.

In the present invention, one type of phenolic compound may be used alone, or two or more types may be used in combination.
The composition of the present invention may or may not contain a phenolic compound, but if it does, the content of the phenolic compound is 0.01% by mass relative to the total solid mass of the composition of the present invention. It is preferably at least 30% by mass, more preferably at least 0.02% by mass and not more than 20% by mass.

[Other polymer compounds]
Other polymer compounds include siloxane resins, (meth)acrylic polymers obtained by copolymerizing (meth)acrylic acid, novolac resins, resole resins, polyhydroxystyrene resins, and copolymers thereof. Other polymer compounds may be modified products into which cross-linking groups such as methylol groups, alkoxymethyl groups and epoxy groups have been introduced.

In the present invention, other polymer compounds may be used singly or in combination of two or more.
The composition of the present invention may or may not contain other polymer compounds, but if it does, the content of the other polymer compound is 0 relative to the total solid mass of the composition of the present invention. It is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less.

<Characteristics of resin composition>
The viscosity of the resin composition of the present invention can be adjusted by adjusting the solid content concentration of the resin composition. From the viewpoint of coating film thickness, it is preferably 1,000 mm ² /s to 12,000 mm ² /s, more preferably 2,000 mm ² /s to 10,000 mm ² /s, and 2,500 mm ² /s to 8,000 mm. ² /s is more preferred. If it is the said range, it will become easy to obtain a coating film with high uniformity. If it is 1,000 mm ² /s or more, it is easy to apply the film with a film thickness required, for example, as an insulating film for rewiring ^. A coating is obtained.

<Restrictions on Substances Contained in Resin Composition>
The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved.
Methods for maintaining the moisture content include adjusting the humidity in the storage conditions and reducing the porosity of the storage container during storage.

From the viewpoint of insulation, the metal content of the 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 metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but metals contained as complexes of organic compounds and metals are excluded. When multiple metals are included, the total of these metals is preferably within the above range.

In addition, as a method for reducing metal impurities unintentionally contained in the resin composition of the present invention, a raw material having a low metal content is selected as a raw material constituting the resin composition of the present invention. For example, the raw material constituting the product is filtered through a filter, or the inside of the apparatus is lined with polytetrafluoroethylene or the like to perform distillation under conditions in which contamination is suppressed as much as possible.

Considering the use of the resin composition of the present invention as a semiconductor material, the content of halogen atoms is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and less than 200 ppm by mass from the viewpoint of wiring corrosion. is more preferred. Among them, those present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Halogen atoms include chlorine and bromine atoms. It is preferable that the total amount of chlorine atoms and bromine atoms or chlorine ions and bromine ions is within the above ranges.
As a method for adjusting the content of halogen atoms, ion exchange treatment and the like are preferably mentioned.

A conventionally known container can be used as the container for the resin composition of the present invention. In addition, as the storage container, for the purpose of suppressing the contamination of the raw materials and the resin composition of the present invention, the inner wall of the container is a multi-layer bottle composed of 6 types and 6 layers of resin, and 6 types of resin are used. It is also preferred to use bottles with a seven-layer structure. Examples of such a container include the container described in JP-A-2015-123351.

<Cured product of resin composition>
By curing the resin composition of the present invention, a cured product of this resin composition can be obtained.
The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention.
Curing of the resin composition is preferably by heating, and the heating temperature is more preferably in the range of 120°C to 400°C, more preferably in the range of 140°C to 380°C, and 170°C. It is particularly preferred to be in the range of -350°C.

The form of the cured product of the present invention is not particularly limited, and can be selected from film-like, rod-like, spherical, pellet-like, etc. according to the application. In the present invention, this cured product is preferably in the form of a film. In addition, pattern processing of the resin composition can be used to form protective films on walls, form via holes for conduction, adjust impedance, capacitance or internal stress, and impart heat dissipation functions. You can also choose the shape. The film thickness of the cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less.
The shrinkage ratio when the resin composition of the present invention is cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage ratio refers to the percentage change in volume of the resin composition before and after curing, and can be calculated from the following formula.
Shrinkage rate [%] = 100 - (volume after curing / volume before curing) x 100

<Characteristics of Cured Product of Resin Composition>
The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or higher, more preferably 80% or higher, and even more preferably 90% or higher. If it is 70% or more, a cured product having excellent mechanical properties may be obtained.
The elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.
The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180° C. or higher, more preferably 210° C. or higher, and even more preferably 230° C. or higher.

式（ＰＨ－１）中、Ｒ^１はそ水素原子又は１価の有機基を表し、Ｒ^２は芳香族ヘテロ環を表し、Ｌ^１は２価の連結基を表し、Ｒはそれぞれ独立に、水素原子又は他の構造との結合部位を表す。 Moreover, the cured product preferably has a phthalimide structure.
As the phthalimide structure in the cured product, a phthalimide structure represented by the following formula (PH-1) is preferred.

In formula (PH-1), R ¹ represents a hydrogen atom or a monovalent organic group, R ² represents an aromatic heterocycle, L ¹ represents a divalent linking group, and each R is independently Represents a hydrogen atom or a bonding site with another structure.

Preferred embodiments of R ¹ , R ² and L ¹ in formula (PH-1) are the same as preferred embodiments of R ¹ , R ² and L ¹ in formula (1-1).

In formula (PH-1), at least one of R preferably represents a binding site with another structure.

The phthalimide structure represented by formula (PH-1) is preferably contained in the resin in the cured product.
For example, when the resin composition of the present invention contains a polyimide precursor or polyimide, the phthalic acid structure or phthalate ester structure present at the end of the polyimide precursor or polyimide reacts with the base generated from the specific compound, It is preferred to form a phthalimide structure.

Specific examples of the phthalimide structure contained in the cured product are shown below, but the present invention is not limited thereto. In the structures below, * represents a binding site with another structure, n represents an integer of 1 to 4, preferably 1 or 2, more preferably 1. Also herein, a bond crossing a side of a ring structure indicates that any hydrogen atom in the ring structure may be substituted. In addition, for example, these bases in the composition undergo further structural changes such as elimination of substituents bonded to nitrogen atoms in azole structures (including azole structures contained in condensed rings such as purine ring structures). There are cases.

The molar amount of the phthalimide structure (in particular, the molar amount of the phthalimide structure represented by the formula (PH-1)) in 1 g of the cured product is preferably 0.0001 to 5 mmol/g, more preferably 0.0002 to 2 mmol/g. g, more preferably 0.001 to 1 mmol/g.

<Preparation of resin composition>
The resin composition of the present invention can be prepared by mixing the components described above. The mixing method is not particularly limited, and conventionally known methods can be used.
Mixing can be performed by mixing with a stirring blade, mixing with a ball mill, mixing by rotating the tank itself, or the like.
The temperature during mixing is preferably 10-30°C, more preferably 15-25°C.

Moreover, it is preferable to perform filtration using a filter for the purpose of removing foreign matters such as dust and fine particles in the resin composition of the present invention. The filter pore size is, for example, 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. HDPE (high density polyethylene) is more preferable when the material of the filter is polyethylene. A filter that has been pre-washed with an organic solvent may be used. In the filter filtration step, multiple types of filters may be connected in series or in parallel for use. When multiple types of filters are used, filters with different pore sizes or materials may be used in combination. As a connection mode, for example, a mode in which an HDPE filter with a pore size of 1 μm is connected in series as a first stage and an HDPE filter with a pore size of 0.2 μm as a second stage are connected in series. Also, various materials may be filtered multiple times. When filtering multiple times, circulation filtration may be used. Moreover, you may filter by pressurizing. When performing filtration under pressure, the pressure to be applied may be, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, and more preferably 0.05 MPa or more and 0.7 MPa or less. , more preferably 0.05 MPa or more and 0.5 MPa or less.
In addition to filtration using a filter, impurities may be removed using an adsorbent. You may combine filter filtration and the impurity removal process using an adsorbent. A known adsorbent can be used as the adsorbent. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
Furthermore, after filtration using a filter, the resin composition filled in the bottle may be subjected to a degassing step under reduced pressure.

(Manufacturing method of cured product)
The method for producing a cured product of the present invention preferably includes a film forming step of applying the resin composition onto a substrate to form a film.
Further, the method for producing a cured product of the present invention includes the film forming step, an exposure step of selectively exposing the film formed in the film forming step, and developing the film exposed in the exposure step using a developer. It is more preferable to include a developing step of forming a pattern by
The method for producing a cured product of the present invention includes the film forming step, the exposing step, the developing step, and a heating step of heating the pattern obtained by the developing step, and after development of exposing the pattern obtained by the developing step. It is particularly preferred to include at least one of the exposure steps.
Moreover, the manufacturing method of the present invention preferably includes the film forming step and the step of heating the film.
Details of each step will be described below.

<Film forming process>
The resin composition of the present invention can be used in a film-forming step in which a film is formed by applying it onto a substrate.
The method for producing a cured product of the present invention preferably includes a film forming step of applying the resin composition onto a substrate to form a film.

〔Base material〕
The type of base material can be appropriately determined according to the application, and includes semiconductor manufacturing base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, Magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metals, and substrates having metal layers formed by plating, vapor deposition, etc.) ), paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, mold substrates, plasma display panel (PDP) electrode plates, etc., and are not particularly limited. In the present invention, a semiconductor fabrication substrate is particularly preferable, and a silicon substrate, a Cu substrate and a mold substrate are more preferable.
In addition, these substrates may be provided with a layer such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) or the like on the surface.
Further, the shape of the substrate is not particularly limited, and may be circular or rectangular.
As for the size of the substrate, if it is circular, the diameter is, for example, 100 to 450 mm, preferably 200 to 450 mm. In the case of a rectangular shape, the short side length is, for example, 100 to 1000 mm, preferably 200 to 700 mm.
As the base material, for example, a plate-like base material (substrate), preferably a panel-like base material (substrate) is used.

Moreover, when a film is formed by applying a resin composition to the surface of a resin layer (for example, a layer made of a cured product) or the surface of a metal layer, the resin layer or the metal layer serves as the base material.

Coating is preferable as a means for applying the resin composition of the present invention onto a substrate.

Specific means to be applied include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, An inkjet method and the like are exemplified. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating, or inkjet method is more preferable, and spin coating from the viewpoint of uniformity of film thickness and productivity. and slit coating methods are preferred. A film having a desired thickness can be obtained by adjusting the solid content concentration and application conditions of the resin composition according to the method. In addition, the coating method can be appropriately selected depending on the shape of the substrate. Spin coating, spray coating, ink jet method, etc. are preferable for circular substrates such as wafers, and slit coating and spray coating are preferable for rectangular substrates. method, inkjet method, and the like are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes.
Alternatively, a method of transferring a coating film, which is formed on a temporary support in advance by the above application method, onto a base material can also be applied.
As for the transfer method, the manufacturing methods described in paragraphs 0023 and 0036 to 0051 of JP-A-2006-023696 and paragraphs 0096-0108 of JP-A-2006-047592 can also be suitably used in the present invention.
Also, a step of removing excess film at the edge of the substrate may be performed. Examples of such processes include edge bead rinsing (EBR), back rinsing, and the like.
A pre-wetting process may also be employed in which the substrate is coated with various solvents before the resin composition is applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.

<Drying process>
The film may be subjected to a step of drying the formed film (layer) to remove the solvent (drying step) after the film forming step (layer forming step).
That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed by the film forming step.
Moreover, the drying step is preferably performed after the film formation step and before the exposure step.
The drying temperature of the film in the drying step is preferably 50 to 150°C, more preferably 70 to 130°C, even more preferably 90 to 110°C. Moreover, you may dry by pressure reduction. The drying time is exemplified from 30 seconds to 20 minutes, preferably from 1 minute to 10 minutes, more preferably from 2 minutes to 7 minutes.

<Exposure process>
The film may be subjected to an exposure step that selectively exposes the film.
That is, the method for producing a cured product of the present invention may include an exposure step of selectively exposing the film formed in the film forming step.
Selectively exposing means exposing a portion of the film. Also, by selectively exposing, the film is formed with exposed regions (exposed portions) and non-exposed regions (non-exposed portions).
The amount of exposure is not particularly defined as long as the resin composition of the present ^invention can be cured ^. is more preferred.

The exposure wavelength can be appropriately determined in the range of 190 to 1,000 nm, preferably 240 to 550 nm.

In relation to the light source, the exposure wavelength is as follows: (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm) ), _F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet; EUV (wavelength 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, etc. mentioned. For the resin composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferred, and exposure with i-line is particularly preferred. Thereby, particularly high exposure sensitivity can be obtained.
The method of exposure is not particularly limited as long as at least a part of the film made of the resin composition of the present invention is exposed. mentioned.

<Post-exposure heating process>
The film may be subjected to a step of heating after exposure (post-exposure heating step).
That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the exposed film in the exposure step.
The post-exposure heating step can be performed after the exposure step and before the development step.
The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, more preferably 60°C to 120°C.
The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.
The heating rate in the post-exposure heating step is preferably 1 to 12° C./min, more preferably 2 to 10° C./min, still more preferably 3 to 10° C./min, from the temperature at the start of heating to the maximum heating temperature.
Also, the rate of temperature increase may be appropriately changed during heating.
The heating means in the post-exposure heating step is not particularly limited, and known hot plates, ovens, infrared heaters and the like can be used.
It is also preferable to perform the heating in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.

<Development process>
The film after exposure may be subjected to a development step in which the film is developed using a developer to form a pattern.
That is, the method for producing a cured product of the present invention may include a development step of developing a film exposed in the exposure step with a developer to form a pattern.
By performing development, one of the exposed and non-exposed portions of the film is removed to form a pattern.
Here, development in which the unexposed portion of the film is removed by the development process is called negative development, and development in which the exposed portion of the film is removed by the development process is called positive development.

[Developer]
Examples of the developer used in the development process include an aqueous alkaline solution and a developer containing an organic solvent.

When the developer is an alkaline aqueous solution, basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. , TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine , dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide , butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, Pyrrole and piperidine are preferred, and TMAH is more preferred. The content of the basic compound in the developer, for example, when TMAH is used, is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, more preferably 0.3 to 3% by mass, based on the total mass of the developer. is more preferred.

When the developer contains an organic solvent, the organic solvent may be an ester such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, Methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetate (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g. methyl methoxyacetate, ethyl methoxyacetate , butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionate alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., 3-methoxy methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionate alkyl esters (e.g. methyl 2-alkyloxypropionate, 2- ethyl alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionic acid ethyl)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g. methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate ethyl, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., and ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene Glycol Monoethyl Ether Acetate, Propylene Glycol Recol monopropyl ether acetate and the like, and ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and cyclic hydrocarbons such as aromatic hydrocarbons such as toluene, xylene and anisole; cyclic terpenes such as limonene; dimethyl sulfoxide as sulfoxides; Propylene glycol, methyl isobutyl carbinol, triethylene glycol and the like, and amides preferably include N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide and the like.

When the developer contains an organic solvent, the organic solvent can be used singly or in combination of two or more. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethylsulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, and cyclopentanone and γ-butyrolactone. and dimethylsulfoxide is more preferred, and a developer containing cyclopentanone is most preferred.

When the developer contains an organic solvent, the content of the organic solvent relative to the total weight of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, and 80% by mass or more. is more preferable, and 90% by mass or more is particularly preferable. Moreover, the content may be 100% by mass.

The developer may further contain other components.
Other components include, for example, known surfactants and known antifoaming agents.

[Method of supplying developer]
The method of supplying the developer is not particularly limited as long as the desired pattern can be formed, and a method of immersing the substrate on which the film is formed in the developer, and supplying the developer to the film formed on the substrate using a nozzle. There is a method of puddle development or a method of continuously supplying developer. The type of nozzle is not particularly limited, and straight nozzles, shower nozzles, spray nozzles and the like can be mentioned.
From the viewpoint of permeability of the developer, removability of the non-image area, and efficiency in production, a method of supplying the developer with a straight nozzle or a method of continuously supplying the developer with a spray nozzle is preferable. From the viewpoint of permeability, the method of supplying with a spray nozzle is more preferable.
In addition, after continuously supplying the developer with a straight nozzle, the substrate is spun to remove the developer from the substrate. A step of removing from above may be employed, and this step may be repeated multiple times.
The method of supplying the developer in the development process includes a process in which the developer is continuously supplied to the base material, a process in which the developer is kept substantially stationary on the base material, and a process in which the developer exceeds the developer on the base material. A process of vibrating with sound waves or the like and a process of combining them can be employed.

The development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

In the developing step, after the processing using the developer, the pattern may be washed (rinsed) with a rinse. Alternatively, a method of supplying the rinse liquid before the developer in contact with the pattern is completely dried may be adopted.

[Rinse liquid]
When the developer is an alkaline aqueous solution, water, for example, can be used as the rinse. When the developer contains an organic solvent, a solvent different from the solvent contained in the developer (for example, water, an organic solvent different from the organic solvent contained in the developer) is used as the rinse liquid. be able to.

When the rinse solution contains an organic solvent, the organic solvent includes esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, and butyl butyrate. , methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetates (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g. methyl methoxyacetate, methoxyacetate ethyl, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionate alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., 3- methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionate alkyl esters (e.g. methyl 2-alkyloxypropionate, 2 -ethyl alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionate ethyl acid)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g. methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate ethyl acetate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., and ethers such as diethylene glycol dimethyl ether, tetrahydrofuran , ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), Propylene Glycol Monoethyl Ether Acetate, Pro Pyrene glycol monopropyl ether acetate and the like, and ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and cyclic hydrocarbons such as , Toluene, xylene, aromatic hydrocarbons such as anisole, cyclic terpenes such as limonene, dimethyl sulfoxide as sulfoxides, and methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol as alcohols. , propylene glycol, methyl isobutyl carbinol, triethylene glycol, and amides such as N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, and the like.

When the rinse liquid contains an organic solvent, the organic solvent can be used alone or in combination of two or more. In the present invention, cyclopentanone, γ-butyrolactone, dimethylsulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA and PGME are particularly preferred, cyclopentanone, γ-butyrolactone, dimethylsulfoxide, PGMEA and PGME are more preferred, and cyclohexanone and PGMEA are more preferred. More preferred.

When the rinse liquid contains an organic solvent, the rinse liquid is preferably 50% by mass or more of the organic solvent, more preferably 70% by mass or more of the organic solvent, and 90% by mass or more of the organic solvent. is more preferred. Further, 100% by mass of the rinse liquid may be an organic solvent.

The rinse solution may further contain other components.
Other components include, for example, known surfactants and known antifoaming agents.

[Method of supplying rinse solution]
The method of supplying the rinse solution is not particularly limited as long as the desired pattern can be formed, and includes a method of immersing the base material in the rinse solution, a method of supplying the rinse solution to the base material by piling up the base material, and a method of supplying the rinse solution to the base material by showering. and a method of continuously supplying the rinsing liquid onto the substrate by means of a straight nozzle or the like.
From the viewpoint of the permeability of the rinse liquid, the removability of the non-image areas, and the efficiency in manufacturing, there are methods of supplying the rinse liquid using a shower nozzle, a straight nozzle, a spray nozzle, etc., and a continuous supply method using a spray nozzle is preferable. From the viewpoint of the permeability of the rinsing liquid to the image area, the method of supplying the rinsing liquid with a spray nozzle is more preferable. The type of nozzle is not particularly limited, and straight nozzles, shower nozzles, spray nozzles and the like can be mentioned.
That is, the rinsing step is preferably a step of supplying the rinse liquid to the film after exposure through a straight nozzle or a step of continuously supplying the same, and more preferably a step of supplying the rinse liquid through a spray nozzle.
The method of supplying the rinse liquid in the rinse step includes a process in which the rinse liquid is continuously supplied to the base material, a process in which the rinse liquid is kept substantially stationary on the base material, and a process in which the rinse liquid is kept on the base material in a substantially stationary state. A process of vibrating with sound waves or the like and a process of combining them can be employed.

The rinse time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinsing liquid during rinsing is not particularly specified, but is preferably 10 to 45°C, more preferably 18 to 30°C.

<Heating process>
The pattern obtained by the development step (the pattern after rinsing when the rinsing step is performed) may be subjected to a heating step of heating the pattern obtained by the development.
That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained by the developing step.
Moreover, the method for producing a cured product of the present invention may include a heating step of heating a pattern obtained by another method without performing the developing step or a film obtained by the film forming step.
In the heating step, a resin such as a polyimide precursor is cyclized into a resin such as polyimide.
In addition, cross-linking of unreacted cross-linkable groups in the specific resin or a cross-linking agent other than the specific resin also progresses.
The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, still more preferably 150 to 250°C, even more preferably 160 to 250°C, particularly 160 to 230°C. preferable.

The heating step is preferably a step of promoting the cyclization reaction of the polyimide precursor in the pattern by the action of the base generated from the base generator by heating.

Heating in the heating step is preferably carried out at a temperature rising rate of 1 to 12° C./min from the temperature at the start of heating to the maximum heating temperature. The rate of temperature increase is more preferably 2 to 10°C/min, still more preferably 3 to 10°C/min. By setting the temperature increase rate to 1°C/min or more, it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity. The residual stress of the object can be relaxed.
In addition, in the case of an oven capable of rapid heating, it is preferable to increase the temperature from the temperature at the start of heating to the maximum heating temperature at a rate of 1 to 8 ° C./sec, more preferably 2 to 7 ° C./sec, and 3 to 6 °C/sec is more preferred.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, 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 up to the maximum heating temperature is started. For example, when the resin composition of the present invention is applied onto a substrate and then dried, the temperature of the film (layer) after drying is, for example, the boiling point of the solvent contained in the resin composition of the present invention. Also, it is preferable to raise the temperature from a temperature lower by 30 to 200°C.

The heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, even more preferably 15 to 240 minutes.

Especially when forming a multilayer laminate, the heating temperature is preferably 30° C. or higher, more preferably 80° C. or higher, further preferably 100° C. or higher, from the viewpoint of adhesion between layers. 120° C. or higher is particularly preferred.
The upper limit of the heating temperature is preferably 350° C. or lower, more preferably 250° C. or lower, and even more preferably 240° C. or lower.

Heating may be done in stages. As an example, the temperature is raised from 25° C. to 120° C. at 3° C./min, held at 120° C. for 60 minutes, heated from 120° C. to 180° C. at 2° C./min, and held at 180° C. for 120 minutes. , may be performed. It is also preferable to carry out the treatment while irradiating ultraviolet rays as described in US Pat. No. 9,159,547. Such a pretreatment process can improve the properties of the film. The pretreatment step is preferably performed for 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 first pretreatment step may be performed in the range of 100 to 150°C, and then the second pretreatment step may be performed in the range of 150 to 200°C. good.
Further, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5°C/min.

The heating step is preferably carried out in an atmosphere of low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium or argon, or under reduced pressure, in order to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.
A heating means in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared furnace, an electric heating oven, a hot air oven, an infrared oven and the like.

<Post-development exposure process>
The pattern obtained by the development step (the pattern after rinsing when the rinsing step is performed) is subjected to a post-development exposure step of exposing the pattern after the development step instead of or in addition to the heating step. may be provided.
That is, the method for producing a cured product of the present invention may include a post-development exposure step of exposing the pattern obtained by the development step. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step.
In the post-development exposure step, for example, a reaction in which cyclization of a polyimide precursor or the like proceeds by exposure of a photobase generator, or a reaction in which elimination of an acid-decomposable group proceeds by exposure of a photoacid generator is promoted. can do.
In the post-development exposure step, at least part of the pattern obtained in the development step may be exposed, but it is preferable that the entire pattern be exposed.
The exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ/cm ² , more preferably 100 to 15,000 mJ/cm ² in terms of exposure energy at the wavelength to which the photosensitive compound is sensitive. preferable.
The post-development exposure step can be performed using, for example, the light source used in the exposure step described above, and broadband light is preferably used.

<Metal layer forming step>
The pattern obtained by the development step (preferably subjected to at least one of the heating step and the post-development exposure step) may be subjected to a metal layer forming step of forming a metal layer on the pattern.
That is, the method for producing a cured product of the present invention includes a metal layer forming step of forming a metal layer on the pattern obtained by the developing step (preferably subjected to at least one of the heating step and the post-development exposure step). is preferred.

The metal layer is not particularly limited, and existing metal species can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. copper and aluminum are more preferred, and copper is even more preferred.

The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, use the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, JP-A-2004-101850, US Pat. can do. For example, photolithography, PVD (Physical Vapor Deposition), CVD (Chemical Vapor Deposition), lift-off, electroplating, electroless plating, etching, printing, and a combination thereof can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electroplating can be used. A preferred embodiment of plating is electroplating using a copper sulfate or copper cyanide plating solution.

The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm, at the thickest portion.

<Application>
Fields to which the cured product of the present invention can be applied include insulating films for electronic devices, interlayer insulating films for rewiring layers, and stress buffer films. In addition, pattern formation by etching of a sealing film, a substrate material (a base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above can be used. For these applications, for example, Science & Technology Co., Ltd. "High Functionality and Application Technology of Polyimide" April 2008, Masaaki Kakimoto / supervised, CMC Technical Library "Basics and Development of Polyimide Materials" November 2011 Published by the Japan Polyimide and Aromatic Polymer Research Group/Edited, "Latest Polyimide Fundamentals and Applications", NTS, August 2010, etc. can be referred to.

The method for producing the cured product of the present invention or the cured product of the present invention can also be used for the production of plates such as offset plates or screen plates, for etching molded parts, for protective lacquers and dielectrics in electronics, especially microelectronics. It can also be used for the production of layers and the like.

(Laminate and method for manufacturing the laminate)
The laminate of the present invention refers to a structure having a plurality of layers made of the cured product of the present invention.
The laminate of the present invention is a laminate containing two or more layers made of a cured product, and may be a laminate in which three or more layers are laminated.
Of the two or more layers of the cured product contained in the laminate, at least one is a layer made of the cured product of the present invention, and the shrinkage of the cured product, or the deformation of the cured product due to the shrinkage, etc. From the viewpoint of suppression, it is also preferable that all the layers made of the cured product contained in the laminate are layers made of the cured product of the present invention.

That is, the method for producing a laminate of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes repeating the method for producing a cured product of the present invention multiple times.

It is preferable that the laminate of the present invention includes two or more layers made of the cured material and a metal layer between any of the layers made of the cured material. The metal layer is preferably formed by the metal layer forming step.
That is, it is preferable that the method for producing the laminate of the present invention further includes a metal layer forming step of forming a metal layer on the layer made of the cured product between the production methods for the cured product that are performed multiple times. Preferred aspects of the metal layer forming step are as described above.
As the laminate, for example, a laminate containing at least a layer structure in which three layers of a layer made of the first cured product, a metal layer, and a layer made of the second cured product are laminated in this order is preferable. be done.
It is preferable that both the layer comprising the first cured product and the layer comprising the second cured product are layers comprising the cured product of the present invention. The resin composition of the present invention used for forming the layer comprising the first cured product and the resin composition of the present invention used for forming the layer comprising the second cured product have the same composition. It may be a product or a composition having a different composition. The metal layer in the laminate of the present invention is preferably used as a metal wiring such as a rewiring layer.

<Lamination process>
It is preferable that the method for manufacturing the laminate of the present invention includes a lamination step.
The lamination step means that the surface of the pattern (resin layer) or metal layer is again subjected to (a) film formation step (layer formation step), (b) exposure step, (c) development step, (d) heating step and development It is a series of steps including performing at least one of the post-exposure steps in this order. However, at least one of (a) the film forming step and (d) the heating step and the post-development exposure step may be repeated. Moreover, after at least one of the (d) heating step and the post-development exposure step, (e) a metal layer forming step may be included. Needless to say, the lamination step may further include the drying step and the like as appropriate.

After the lamination step, when the lamination step is further performed, after the exposure step, after the heating step, or after the metal layer forming step, a surface activation treatment step may be further performed. A plasma treatment is exemplified as the surface activation treatment. Details of the surface activation treatment will be described later.

The lamination step is preferably performed 2 to 20 times, more preferably 2 to 9 times.
For example, a configuration of 2 to 20 resin layers such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer is preferable, and a configuration of 2 to 9 layers is more preferable. .
Each of the layers described above may have the same composition, shape, film thickness, etc., or may differ from each other.

In the present invention, it is particularly preferable to form a cured product (resin layer) of the resin composition of the present invention so as to cover the metal layer after providing the metal layer. Specifically, (a) the film forming step, (b) the exposure step, (c) the developing step, (d) at least one of the heating step and the post-development exposure step, and (e) the metal layer forming step are repeated in this order. Alternatively, (a) the film forming step, (d) at least one of the heating step and the post-development exposure step, and (e) the metal layer forming step are repeated in this order. By alternately performing the lamination step of laminating the resin composition layer (resin layer) of the present invention and the metal layer forming step, it is possible to alternately laminate the resin composition layer (resin layer) of the present invention and the metal layer. can.

(Surface activation treatment step)
The method for producing a laminate of the present invention preferably includes a surface activation treatment step of subjecting at least part of the metal layer and the resin composition layer to surface activation treatment.
The surface activation treatment step is usually performed after the metal layer formation step, but after the development step (preferably after at least one of the heating step and the post-development exposure step), the resin composition layer is subjected to surface activation treatment. After performing the steps, the metal layer forming step may be performed.
The surface activation treatment may be performed only on at least part of the metal layer, may be performed only on at least part of the resin composition layer after exposure, or may be performed on the metal layer and the resin composition layer after exposure. Both may be done at least partially, respectively. The surface activation treatment is preferably performed on at least part of the metal layer, and it is preferable to perform the surface activation treatment on part or all of the area of the metal layer on which the resin composition layer is formed. By subjecting the surface of the metal layer to the surface activation treatment in this manner, the adhesiveness to the resin composition layer (film) provided on the surface can be improved.
In addition, it is preferable to perform the surface activation treatment on a part or the whole of the resin composition layer (resin layer) after exposure. By subjecting the surface of the resin composition layer to the surface activation treatment in this way, it is possible to improve the adhesion with the metal layer or the resin layer provided on the surface that has been subjected to the surface activation treatment. In particular, when the resin composition layer is cured, such as in the case of negative development, it is less likely to be damaged by surface treatment, and the adhesion is likely to be improved.
Specific examples of the surface activation treatment include plasma treatment of various source gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, and CF ₄ /O _{2 .} , NF ₃ /O ₂ , SF ₆ , NF ₃ , NF ₃ /O ₂ etching treatment, surface treatment by ultraviolet (UV) ozone method, immersion in hydrochloric acid aqueous solution to remove the oxide film, and then amino groups and thiol groups. The treatment is selected from immersion treatment in an organic surface treatment agent containing at least one compound and mechanical surface roughening treatment using a brush. Plasma treatment is preferred, and oxygen plasma treatment using oxygen as a raw material gas is particularly preferred. In the case of corona discharge treatment, the energy is preferably 500-200,000 J/m ² , more preferably 1000-100,000 J/m ² , most preferably 10,000-50,000 J/m ² .

(Semiconductor device and its manufacturing method)
The present invention also discloses a semiconductor device comprising the cured product of the present invention or the laminate of the present invention.
Moreover, this invention also discloses the manufacturing method of the semiconductor device containing the manufacturing method of the hardened|cured material of this invention, or the manufacturing method of the laminated body of this invention.
Specific examples of a semiconductor device using the resin composition of the present invention for forming an interlayer insulating film for a rewiring layer can refer to the description of paragraphs 0213 to 0218 of JP-A-2016-027357 and the description of FIG. The contents of which are incorporated herein.

式（１－１）中、Ｒ^１はそれぞれ独立に、水素原子又は１価の有機基を表し、Ｒ^２はそれぞれ独立に、芳香族ヘテロ環を表し、Ｒ^３はそれぞれ独立に、水素原子又は１価の有機基を表し、Ｌ^１はそれぞれ独立に、２価の連結基を表し、ｎは１以上の整数を表し、Ｌ^２はｎ価の連結基を表す。 (Compound)
The compound of the present invention is a compound represented by the following formula (1-1).

In formula (1-1), each R ¹ independently represents a hydrogen atom or a monovalent organic group, each R ² independently represents an aromatic heterocycle, and each R ³ independently represents a hydrogen atom or represents a monovalent organic group, each L ¹ independently represents a divalent linking group, n represents an integer of 1 or more, and L ² represents an n-valent linking group.

Preferred aspects of the compound of the present invention are the same as the preferred aspects of the specific compound contained in the resin composition of the present invention described above.

EXAMPLES The present invention will be described more specifically with reference to examples below. The materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. "Parts" and "%" are based on mass unless otherwise specified.

<Synthesis Example 1: Synthesis of polybenzoxazole precursor PBO-1 from 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 4,4-oxydibenzoyl chloride>
28.0 g (76.4 mmol) of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was dissolved in 200 g of N-methylpyrrolidone with stirring. Subsequently, 12.1 g (153 mmol) of pyridine was added, and 20.7 g (70.1 mmol) of 4,4'-oxydibenzoyl chloride was added to 75 g of N-methylpyrrolidone while maintaining the temperature at -10 to 0°C. The dissolved solution was added dropwise over 1 hour. After stirring for 30 minutes, 1.00 g (12.7 mmol) of acetyl chloride was added and stirred for an additional 60 minutes. The polybenzoxazole precursor resin was then precipitated in 6 liters of water and the water-polybenzoxazole precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes. The polybenzoxazole precursor resin was filtered off, stirred again in 6 liters of water for 30 minutes and filtered again. The obtained polybenzoxazole precursor resin was then dried under reduced pressure at 45° C. for 3 days to obtain polybenzoxazole precursor PBO-1. This polybenzoxazole precursor PBO-1 had Mw (weight average molecular weight)=21,500.
The structure of the polybenzoxazole precursor PBO-1 is presumed to be the structure represented by the following formula (PBO-1).

<Synthesis Example 2: Synthesis of polyimide precursor PI-1 from pyromellitic 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, 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 10 hours. An additional 0.84 g (6.45 mmol) of 2-hydroxyethyl methacrylate was added and stirred for 2 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to -10.degree. C. and 16.12 g (135.5 mmol) of _SOCl.sub.2 was added over 10 minutes while maintaining the temperature at -10.+-.4.degree. Viscosity increased during SOCl ₂ addition. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. A solution of 11.08 g (58.7 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was then added dropwise to the reaction mixture at -5 to 0°C over 20 minutes. After reacting the reaction mixture at 0° C. for 1 hour, 70 g of ethanol was added and stirred overnight at room temperature. The polyimide precursor was then precipitated in 5 liters of water and the water-polyimide precursor mixture was stirred at a speed of 5,000 rpm (revolutions per minute) for 15 minutes. The polyimide precursor was obtained by filtration, 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 to obtain polyimide precursor PI-1. The weight average molecular weight of this polyimide precursor PI-1 was 19,000. The obtained polyimide precursor PI-1 is presumed to contain a repeating unit represented by the following formula (PI-1).

<Synthesis Example 3: Synthesis of polyimide precursor (PI-2) from 3,3′,4,4′-biphenyltetracarboxylic anhydride, 4,4′-diaminodiphenyl ether and 2-hydroxyethyl methacrylate>
20.0 g (64.5 mmol) of 3,3′,4,4′-biphenyltetracarboxylic anhydride (dried at 140° C. for 12 hours) and 16.8 g (129 mmol) of 2-hydroxyethyl Methacrylate, 0.05 g hydroquinone, 20.4 g (258 mmol) pyridine and 100 g diglyme (water content 88 ppm) were mixed and stirred at a temperature of 60° C. for 10 hours. An additional 0.84 g (6.45 mmol) of 2-hydroxyethyl methacrylate was added and stirred for 2 hours to produce a diester of 3,3′,4,4′-biphenyltetracarboxylic acid and 2-hydroxyethyl methacrylate. bottom. Then, after chlorinating the resulting diester with SOCl ₂ , it was converted to a polyimide precursor with 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example 2, and polyimide precursor PI was obtained in the same manner as in Synthesis Example 2. -2 was obtained. The weight average molecular weight of this polyimide precursor PI-2 was 20,000. The obtained polyimide precursor PI-2 is presumed to contain a repeating unit represented by the following formula (PI-2).

<Synthesis Example 4: Synthesis of polyimide precursor (PI-3) 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 diglyme were mixed and stirred at a temperature of 60° C. for 10 hours. An additional 0.84 g (6.45 mmol) of 2-hydroxyethyl methacrylate was added and stirred for 2 hours to produce a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Then, after chlorinating the resulting diester with SOCl ₂ , it was converted to a polyimide precursor with 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example 2, and the polyimide precursor was obtained in the same manner as in Synthesis Example 2. Obtained. The weight average molecular weight of this polyimide precursor was 18,000. The obtained polyimide precursor PI-3 is presumed to contain a repeating unit represented by the following formula (PI-3).

<Synthesis Example 5: Synthesis of polyimide precursor (PI-4) from 4,4′-oxydiphthalic anhydride, 4,4′-diamino-2,2′-dimethylbiphenyl (orthotolidine) 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 pyridine (258 mmol) and 100 g diglyme (water content 67 ppm) were mixed and stirred at a temperature of 60° C. for 10 hours. An additional 0.84 g (6.45 mmol) of 2-hydroxyethyl methacrylate was added and stirred for 2 hours to produce a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The resulting diester was then chlorinated with SOCl ₂ and then converted to a polyimide precursor with 4,4′-diamino-2,2′-dimethylbiphenyl in the same manner as in Synthesis Example 2. Polyimide precursor PI-4 was obtained by the method of. The weight average molecular weight of this polyimide precursor PI-4 was 19,000. The obtained polyimide precursor PI-4 is presumed to contain a repeating unit represented by the following formula (PI-4).

<Synthesis Example: Synthesis of polyimide PBI-1>
22.2 g (50 mmol) of 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 2 , 2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was dissolved in 100.0 g of N-methylpyrrolidone (NMP). Then, 11.9 g (45 millimoles) of diamine (AA-1) described later was added, stirred at 25°C for 3 hours, and further stirred at 45°C for 3 hours. Then, 15.8 g (200 mmol) of pyridine, 12.8 g (125 mmol) of acetic anhydride and 50 g of N-methylpyrrolidone (NMP) are added, stirred at 80° C. for 3 hours, and 50 g of N-methylpyrrolidone (NMP) are added. was added and diluted.
The reaction was precipitated in 1 liter of methanol and stirred at a speed of 3000 rpm for 15 minutes. The resin was filtered off, stirred again in 1 liter of methanol for 30 minutes and filtered again. The resulting resin was dried under reduced pressure at 40° C. for one day to obtain polyimide PBI-1. The molecular weight of PBI-1 was Mw=19,000.
The structure of polyimide PBI-1 is presumed to be represented by the following formula (PBI-1).

<Synthesis Example AA-1: Synthesis of diamine (AA-1)>
In a flask equipped with a condenser and stirrer, 26.0 g (0.2 mol) of 2-hydroxyethyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), dehydrated pyridine (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) ) was dissolved in 78 g of ethyl acetate and cooled to below 5°C. Next, 48.4 g (0.21 mol) of 3,5-dinitrobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 145 g of ethyl acetate, and this solution was added to the flask over 1 hour using a dropping funnel. dripped into. After completion of dropping, the mixture was stirred at 10°C or lower for 30 minutes, heated to 25°C, and stirred for 3 hours. Then, the reaction solution was diluted with 600 mL of ethyl acetate (CH ₃ COOEt), transferred to a separating funnel, and washed with 300 mL of water, 300 mL of saturated aqueous sodium bicarbonate, 300 mL of dilute hydrochloric acid, and 300 mL of saturated brine in that order. After separation and washing, the extract was dried with 30 g of magnesium sulfate, concentrated using an evaporator, and dried in a vacuum to obtain 61.0 g of dinitro compound (A-1).
A flask equipped with a condenser and a stirrer was charged with 27.9 g (500 mmol) of reduced iron (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) and 5.9 g (110 mmol) of ammonium chloride (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.). ), acetic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 3.0 g (50 mmol), 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.03 g was weighed out, 200 mL of isopropyl alcohol (IPA) and 30 mL of pure water were added and stirred.
Then, 16.2 g of dinitro compound (A-1) was added little by little over 1 hour and stirred for 30 minutes. Next, the external temperature was raised to 85° C., the mixture was stirred for 2 hours, cooled to 25° C. or lower, and then filtered using Celite (registered trademark). The filtrate was concentrated on a rotary evaporator and dissolved in 800 mL of ethyl acetate. This was transferred to a separating funnel, washed twice with 300 mL of saturated sodium bicarbonate water, and washed with 300 mL of water and 300 mL of saturated brine in this order. After separation and washing, the residue was dried with 30 g of magnesium sulfate, concentrated using an evaporator, and dried in a vacuum to obtain 11.0 g of diamine (AA-1). It was confirmed from the NMR spectrum that it was diamine (AA-1).
¹ H-NMR data (deuterated chloroform, 400 MHz, internal standard: tetramethylsilane)
δ (ppm) = 1.95 (s, 3H), 3.68 (s, 4H), 4.45-4.47 (m, 2H), 4.50-4.53 (m, 2H), 5 .58 (s, 1H), 6.14 (s, 1H), 6.19-6.20 (t, 1H), 6.77-6.78 (d, 2H)

<Examples and Comparative Examples>
In each example, each resin composition was obtained by mixing the components shown in the table below. In addition, in Comparative Examples, the components shown in the table below were mixed to obtain comparative compositions.
Specifically, the content (compounding amount) of each component described in the table other than the solvent was the amount (parts by mass) described in the "parts by mass" column of each column of the table.
The content (blended amount) of the solvent is such that the solid content concentration of the composition is the value (% by mass) of "solid content concentration" in the table, and the ratio of the content of each solvent to the total mass of the solvent (mass The ratio) was set to the ratio described in the "ratio" column in the table.
The resulting resin composition and comparative composition were filtered under pressure using a polytetrafluoroethylene filter with a pore width of 0.8 μm.
In the table, the description of "-" indicates that the composition does not contain the corresponding component.

The details of each component described in the table are as follows.

[Resin (cyclized resin or its precursor)]
Resins PI-1 to PI-4, PBO-1, PBI-1: PI-1 to PI-4, PBO-1, PBI-1 obtained by the above synthesis examples

[Thermal base generator]
· B-1 to B-5: compounds represented by the following formulas (B-1) to (B-5)

[Polymerization initiator]
・ C-1: IRGACURE OXE 01 (manufactured by BASF)
・C-2: IRGACURE OXE 02 (manufactured by BASF)
・ C-3: IRGACURE 369 (manufactured by BASF)
· C-4: a compound having the following structure

[Polymerizable compound]
・ D-1: A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)
・ D-2: SR-209 (manufactured by Sartomer, a compound having the following structure)
・ D-3: A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[Polymerization inhibitor]
・ E-1: 2-nitroso-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ E-2: parabenzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ E-3: Para-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)
· E-4: a compound having the following structure

上記Ｆ－２２におけるＲ^１の一方は水素原子、他方は下記構造であり、Ｒ^２の一方は水素原子、他方は下記構造である。下記構造中、＊はＦ－２２における酸素原子との結合部位を表す。

[Specific compound or migration inhibitor]
- F-1 to F-21: compounds having the following structures. F-1 to F-21 are compounds corresponding to the above-mentioned specific compounds.
- CF-1 to CF-2: compounds having the following structures. CF-1 to CF-2 are compounds that do not correspond to the above specific compounds.

One of R ¹ in the above F-22 is a hydrogen atom and the other has the following structure, and one of R ² has a hydrogen atom and the other has the following structure. In the structure below, * represents a bonding site with an oxygen atom in F-22.

次に三口フラスコ内に３，４－ジヒドロクマリン ５．２９ｇ（３５．７ｍｍｏｌ、東京化成工業（株））、Ｆ－１ａ ７．００ｇ（３９．３ｍｍｏｌ）、水 １０５ｍLを混合した。６０℃で６時間反応を続けた。反応終了後、析出した白色粉体を濾過操作により回収した。白色粉体をフラスコ中、水２００ｍLで１時間撹拌およびジイソプロピルエーテル２００ｍＬで１時間撹拌による洗浄操作を繰り返すことで白色粉体Ｆ－１ ８．２７ｇ（収率７１％）を得た。Ｆ－１の^１Ｈ－ＮＭＲデータを以下に示す。^１Ｈ－ＮＭＲ：δ(ppm,DMSO-d6)：１２．７（１H、s）、９．３７（１H、ｓ）、８．１９（１H、ｓ）、８．１０（１H、ｓ）、７．９９（１H、ｔ）、７．７０－７．４３（１H）、７．１０－６．９０（２H）、６．８１－６．７１（１H、ｄ）、６．７０－６．５９（１H、ｔ）、３．３５－３．２０（４H）、２．７８－２．６５（２H、ｔ）、２．３９－２．２６（２H、ｔ） <Synthesis Example F-1>
In a three-necked flask, 30 g (0.19 mol, Tokyo Chemical Industry Co., Ltd.) of 6-chloropurine, 600 mL of 1-butanol, and 100 mL of water were mixed. After dissolution by stirring at room temperature, 130 mL of ethylenediamine (Tokyo Chemical Industry Co., Ltd.) was added dropwise to the flask over 1 hour. After completion of dropping, the reaction was continued at 80° C. for 2 hours. After completion of the reaction, the mixture was cooled to room temperature and concentrated using a rotary evaporator. After concentration, crystals were precipitated by adding a mixed solvent of 390 mL of diisopropyl ether and 90 mL of methanol. 28.3 g (yield 82%) of pale yellow powder F-1a (CF-1) was obtained. ¹ H-NMR data of F-1a is shown below. ¹ H-NMR (BRUKER, AVANCE NEO 400): δ (ppm, DO) 7.98 (1H, s), 7.91 (1H, s), 3.65-3.57 (2H, t), 3 .10-3.00 (2H, t)

Next, 5.29 g (35.7 mmol, Tokyo Chemical Industry Co., Ltd.) of 3,4-dihydrocoumarin, 7.00 g (39.3 mmol) of F-1a, and 105 mL of water were mixed in a three-necked flask. The reaction was continued at 60°C for 6 hours. After completion of the reaction, the precipitated white powder was collected by filtration. White powder F-1 was washed in a flask with 200 mL of water for 1 hour with stirring and with diisopropyl ether with 200 mL of diisopropyl ether for 1 hour. ¹ H-NMR data of F-1 is shown below. ¹ H-NMR: δ (ppm, DMSO-d6): 12.7 (1H, s), 9.37 (1H, s), 8.19 (1H, s), 8.10 (1H, s), 7.99 (1H, t), 7.70-7.43 (1H), 7.10-6.90 (2H), 6.81-6.71 (1H, d), 6.70-6. 59 (1H, t), 3.35-3.20 (4H), 2.78-2.65 (2H, t), 2.39-2.26 (2H, t)

<Synthesis Examples F-2, F-3>
The ethylenediamine used in the synthesis of intermediate F-1a in Synthesis Example F-1 is 1,4-diaminobutane (Tokyo Chemical Industry Co., Ltd.) or 1,2-bis(2-aminoethoxy)ethane (Tokyo Chemical Industry Co., Ltd. F-2 and F-3 were obtained in the same manner as in the synthesis of F-1, except that the strain was changed to )).

<Synthesis Example F-4>
F-4 was obtained in the same manner as in the synthesis of F-1, except that 3,4-dihydrocoumarin used in Synthesis Example F-1 was changed to 2-coumaranone (Tokyo Chemical Industry Co., Ltd.).

<Synthesis Example F-5>
4.89 g (15.0 mmol) of F-1 and 30 mL of methacrylic anhydride (Tokyo Chemical Industry Co., Ltd.) were mixed in a three-necked flask. The reaction was continued at 80°C for 10 hours. After completion of the reaction, the reaction solution was added dropwise to 200 mL of diisopropyl ether, stirred for 1 hour, and filtered by suction to obtain 3.27 g of white powder F-5 (yield: 55%). ¹ H-NMR data of F-5 are shown below. ¹ H-NMR: δ (ppm, DMSO-d6): 9.34 (1H, s), 8.18 (1H, s), 8.10 (1H, s), 7.99 (1H, t), 7.70-7.43 (1H), 7.10-6.90 (2H), 6.81-6.71 (1H, d), 6.70-6.59 (1H, t), 6. 06 (1H), 6.00 (1H), 3.35-3.20 (4H), 2.78-2.65 (2H, t), 2.39-2.26 (5H)

<Synthesis Examples F-6, F-7, F-8>
Except that 6-chloropurine used in the synthesis of intermediate F-1a in Synthesis Example F-1 was changed to 2-chloropyridine, 5-chloro-2H-tetrazole, or 3-chloro-1,2,4-triazole obtained F-6, F-7 and F-8 in a similar manner.

<Synthesis Examples F-9, F-11, F-12>
The 3,4-dihydrocoumarin used in Synthesis Example F-1 is δ-valerolactone (Tokyo Chemical Industry Co., Ltd.), 3-isochromanone (Tokyo Chemical Industry Co., Ltd.), or phthalide (Tokyo Chemical Industry Co., Ltd.) ), F-9, F-11 and F-12 were obtained in the same manner as in the synthesis of F-1.

<Synthesis Example F-10>
6.34 g (35.2 mmol, Tokyo Kasei Kogyo Co., Ltd.) of 3-(2-methoxyphenyl)propionic acid, 7.0 g (39.3 mmol) of F-1a, and 100 mL of methanol were mixed in a three-necked flask. 10.9 g (38.5 mmol) of 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride into the flask while stirring at room temperature, Tokyo Kasei Kogyo ( was added.The reaction was continued at room temperature for 6 hours.After completion of the reaction, 100 mL of aqueous hydrochloric acid (1.0 N) and 100 mL of ethyl acetate were added to separate the layers.The organic layer was concentrated under reduced pressure. , and 200 mL of diisopropyl ether were used for washing with stirring in a flask to obtain 5.3 g (yield 48.5%) of pale yellow powder F- ^10.1 H-NMR data of F-10 was obtained. ¹ H-NMR: δ (ppm, DMSO-d6): 12.7 (1H, s), 8.19 (1H, s), 8.10 (1H, s), 7.99 (1H , t), 7.70-7.43 (1H), 7.10-6.90 (2H), 6.81-6.71 (1H, d), 6.70-6.59 (1H, t ), 3.90-3.72 (3H, s), 3.35-3.20 (4H), 2.78-2.65 (2H, t), 2.39-2.26 (2H, t )

<Synthesis Example F-13>
F-13 was obtained in the same manner as in the synthesis of F-5 except that the methacrylic anhydride used in Synthesis Example F-5 was changed to isobutyric anhydride (Tokyo Kasei Kogyo Co., Ltd.).

<Synthesis Example F-14>
F-14 was obtained in the same manner as in the synthesis of F-1, except that the 3,4-dihydrocoumarin used in Synthesis Example F-1 was changed to 3-isochromanone, and the ethylenediamine was changed to 1,4-diaminobutane. rice field.

<Synthesis Example F-15>
F-1 used in Synthesis Example F-5 was changed to F-11, and methacrylic anhydride was changed to acetic anhydride (Tokyo Chemical Industry Co., Ltd.) in the same manner as in the synthesis of F-5. 15 was obtained.

<Synthesis Example F-16>
In the same manner as in the synthesis of F-1 except that the ethylenediamine used in the synthesis of intermediate F-1a in Synthesis Example F-1 was changed to 2,2'-oxybis(ethylamine) (Tokyo Chemical Industry Co., Ltd.) obtained the F-16.

<Synthesis Example F-17>
F-17 was obtained in the same manner as in the synthesis of F-5 except that F-1 was changed to F-4 and methacrylic anhydride was changed to isobutyric anhydride in Synthesis Example F-5.

<Synthesis Example F-18>
In a three-necked flask, 3.0 g (13.1 mmol) of (2-hydroxyphenyl)methyl N-(2-chloroethyl)carbamate, 1.8 g (13.1 mmol) of adenine, 35 mL of dimethylformamide, and 15 mL of water were mixed. The reaction was continued at 80°C for 12 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and added dropwise to 100 mL of an 8% by mass saturated sodium hydrogen carbonate aqueous solution. The obtained white powder was collected by filtration and washed with stirring using 200 mL of diisopropyl ether. 2.1 g of white powder F-18 was obtained (yield 48.8%). ¹ H-NMR data of F-18 are shown below. ¹ H-NMR: δ (ppm, DMSO-d6): 12.7 (1H, s), 9.37 (1H, s), 8.19 (1H, s), 8.10 (1H, s), 7.50-7.23 (2H), 7.10-6.90 (2H), 6.81-6.71 (1H, d), 6.70-6.59 (1H, t), 4. 75-4.50 (2H), 2.78-2.65 (2H, t), 2.39-2.26 (2H, t)

<Synthesis Example F-19>
10.0 g (56.1 mmol) of F-1a and 150 mL of dichloromethane were mixed in a three-necked flask. 12.7 g (112.2 mmol, Tokyo Kasei Kogyo Co., Ltd.) of chloroacetyl chloride was added dropwise into the flask over 1 hour while stirring at 0-5°C or lower. After completion of dropping, the reaction was continued for 4 hours at room temperature. After completion of the reaction, the reaction solution was added to 200 mL of water, and the organic layer was recovered. Furthermore, after performing liquid separation operation with water, the organic layer was concentrate|evaporated under reduced pressure using the rotary evaporator. After decompression, the obtained white powder was washed with stirring using 200 mL of diisopropyl ether. 11.5 g (yield 80.4%) of white powder was obtained.
Next, 5.0 g (19.6 mmol) of the white powder, 7.86 g (44.1 mmol) of 3,4-dihydroxystyrene, 2.98 g (21.6 mmol) of potassium carbonate, and 150 mL of acetone were mixed in a three-necked flask. The reaction was continued at 40°C for 6 hours. After completion of the reaction, 200 mL of aqueous hydrochloric acid (1.0N) and 200 mL of ethyl acetate were added to separate the layers. The organic layer was concentrated under reduced pressure using a rotary evaporator. After decompression, the obtained white powder was washed with stirring using 200 mL of diisopropyl ether. 5.3 g (yield 76.3%) of white powder was obtained. ¹ H-NMR data of F-19 are shown below. ¹ H-NMR: δ (ppm, DMSO-d6): 12.7 (1H, s), 9.57 (1H, s), 8.19 (1H, s), 8.10 (1H, s), 7.99 (1H, t), 7.25-6.95 (3H), 6.60-6.41 (2H), 5.90-5.75 (1H), 5.35-5.15 ( 1H) 4.45-4.20 (2H), 2.78-2.65 (2H, t), 2.39-2.26 (2H, t)

<Synthesis Example F-20>
F-20 was obtained in the same manner as in the synthesis of F-1, except that 3,4-dihydrocoumarin used in Synthesis Example F-1 was changed to coumarin (Tokyo Chemical Industry Co., Ltd.).

<Synthesis Example F-21>
10.0 g (67.5 mmol) of 3,4-dihydrocoumarin and 250 mL of ethanol were mixed in a three-necked flask. While stirring at room temperature, 15.0 g (202.5 mmol, Tokyo Kasei Kogyo Co., Ltd.) of N-methylethylenediamine was added dropwise into the flask over 1 hour. The reaction was continued for 6 hours at room temperature. After completion of the reaction, 100 mL of aqueous hydrochloric acid (1.0 N) and 200 mL of ethyl acetate were added to separate the layers. After the organic layer was concentrated under reduced pressure, it was washed with stirring in a flask using 200 mL of diisopropyl ether. 10.4 g (yield 74.1%) of white powder was obtained.
Next, 5.0 g (24.0 mmol) of the obtained white powder, 3.37 g (21.8 mmol) of 6-chloropurine, 150 mL of 1-butanol, and 25 mL of water were mixed in a three-necked flask. The reaction was continued at 80°C for 12 hours. After completion of the reaction, the precipitated white powder was collected by filtration under reduced pressure. The recovered powder was suspended and washed with a mixed solvent of 200 mL of ethyl acetate and 200 mL of hexane, and then suspended and washed with 300 mL of diisopropyl ether to obtain 5.5 g (74.1%) of F-21. ¹ H-NMR data of F-21 are shown below. ¹ H-NMR: δ (ppm, DMSO-d6): 12.7 (1H, s), 9.37 (1H, s), 8.19 (1H, s), 8.10 (1H, s), 7.99 (1H, t), 7.10-6.90 (2H), 6.81-6.71 (1H, d), 6.70-6.59 (1H, t), 3.35- 3.20 (7H), 2.78-2.65 (2H, t), 2.39-2.26 (2H, t)

<Synthesis Example F-22>
The 3,4-dihydroxystyrene used in Synthesis Example F-19 was replaced with 5,5′,6,6′-tetrahydroxy-3,3,3′,3′-tetramethyl-1,1′-spirobisindane ( F-22 was obtained in the same manner as in the synthesis of F-19, except that it was changed to Tokyo Kasei Kogyo Co., Ltd.).

<Synthesis Example F-23>
10.0 g (55.5 mmol) of 2-carboxyphenylacetic acid, 6.6 g (55.5 mmol) of thionyl chloride, 8.99 g (50.5 mmol) of F-1a, and 250 mL of toluene were mixed in a three-necked flask. 5.11 g (55.5 mmol) of triethylamine was dropped into the flask while stirring at room temperature. The reaction was continued at 90°C for 3 hours. After completion of the reaction, toluene was distilled off by concentration under reduced pressure. 200 mL of methanol was added into the flask, 10.6 g (55.5 mmol) of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride was added, and the reaction was continued at room temperature for 7 hours. After completion of the reaction, 100 mL of aqueous hydrochloric acid (1.0 N) and 200 mL of ethyl acetate were added to separate the layers. After the organic layer was concentrated under reduced pressure, it was washed with stirring in a flask using 200 mL of diisopropyl ether. 9.2 g (yield 51.4%) of white powder was obtained. ¹ H-NMR data of F-23 are shown below. ¹ H-NMR: δ (ppm, DMSO-d6): 12.7 (1H, s), 8.19 (1H, s), 8.10 (1H, s), 7.99 (1H, t), 7.70-7.43 (1H), 7.10-6.90 (2H), 6.81-6.71 (1H, d), 6.70-6.59 (1H, t), 4. 10-3.75 (5H), 2.78-2.65 (2H, t), 2.39-2.26 (2H, t)

<Synthesis Example F-24>
F-24 was prepared in the same manner as in the synthesis of F-1 except that the ethylenediamine used in the synthesis of intermediate F-1a in Synthesis Example F-1 was changed to p-xylylenediamine (Tokyo Chemical Industry Co., Ltd.). got

In F-1 to F-24, the pKa of the conjugate acid before and after decomposition (before decomposition: pKa of the conjugate acid of the specific compound itself, after decomposition: pKa of the conjugate acid of the base generated by decomposition) was calculated using ACD/labs software. Calculated using ACD pKa (ver 8.0). The calculation results are shown in the table below.

[Silane coupling agent (metal adhesion improver)]
- G-1 to G-4: compounds having the following structures. In the structural formulas below, Et represents an ethyl group.

[Other additives]
· I-1: a compound represented by the following formula (I-1) · I-2: N-phenyldiethanolamine

〔solvent〕
・NMP: N-methyl-2-pyrrolidone ・EL: ethyl lactate ・DMSO: dimethyl sulfoxide ・GBL: γ-butyrolactone

<Evaluation>
[Evaluation of storage stability]
The viscosity (day 0) was measured using an E-type viscometer for each resin composition or comparative composition in each example or comparative example. After allowing the resin composition to stand in a sealed container under the conditions of 25° C. and light shielding for 14 days, the viscosity (14 days) was measured again using the E-type viscometer. The viscosity fluctuation rate (%) was calculated from the following formula. Based on the obtained viscosity fluctuation rate, evaluation was performed according to the following evaluation criteria, and the evaluation results were described in the column of "storage stability" in the table. The lower the viscosity fluctuation rate, the higher the storage stability.
Viscosity fluctuation rate (%) = |100 × {1-(viscosity (14 days)/viscosity (0 days))}|
The viscosity was measured at 25° C., and other conditions were in accordance with JIS Z 8803:2011.
-Evaluation criteria-
A: Viscosity fluctuation rate was 10% or less.
B: Viscosity fluctuation rate exceeded 10% and was 15% or less.
C: Viscosity fluctuation rate exceeded 15%.

[Breaking elongation]
In each example and comparative example, each resin composition or comparative composition was applied in layers on a silicon wafer by spin coating to form a resin composition layer or comparative composition layer. The silicon wafer to which the obtained resin composition layer or comparative composition layer is applied is dried on a hot plate at 100 ° C. for 5 minutes, and a uniform resin composition layer or comparative composition layer having a thickness of 20 μm is formed on the silicon wafer. A composition layer was formed. The resin composition layer or the comparative composition layer on the silicon wafer was exposed with an exposure energy of 500 mJ/cm ² using a stepper (Nikon NSR 2005 i9C). The exposed resin composition layer or comparative composition layer was heated in a nitrogen atmosphere at a heating rate of 10° C./min to reach the temperature indicated in the “Cure temperature (° C.)” column of the table. After that, this temperature was maintained for the time described in "Cure time (min)" in the table to obtain a cured resin layer. The cured resin layer was immersed in a 4.9% by mass hydrofluoric acid solution, and the resin layer was peeled off from the silicon wafer to obtain resin film 1 .
The elongation at break of the resin film 1 was measured using a tensile tester (Tensilon) with a crosshead speed of 300 mm/min, a sample width of 10 mm, and a sample length of 50 mm. The elongation at break was measured according to JIS-K6251:2017 below. The elongation at break is E _b (%) = (L _b - L ₀ )/L ₀ × 100 (E _b : elongation at break, L ₀ : length of test piece before test, L _b : test piece cut It was calculated by the length of the test piece when The evaluation was performed by measuring the elongation at break in the longitudinal direction 10 times, and using the arithmetic mean value of the elongation at break (E _b ) of a total of 10 samples as an index value. Evaluation was performed according to the following evaluation criteria. It can be said that the larger the value of _Eb , the better the elongation at break. The evaluation results are described in the column of "elongation at break" in the table.
-Evaluation criteria-
A: The above index value exceeded 60%.
B: The above index value exceeded 40% and was 60% or less.
C: The index value was 40% or less.

[Evaluation of metal adhesion]
A resin composition layer or a comparative composition layer was formed by applying the resin composition or the comparative composition prepared in each example and comparative example in a layered manner on a copper substrate by spin coating, respectively. The resulting copper substrate on which the resin composition layer or the comparative composition layer was formed was dried on a hot plate at 100° C. for 5 minutes, and the film thickness (μm) shown in the column “Thickness (μm)” of the table was applied to the copper substrate. A resin composition layer or a comparative composition layer having a uniform thickness was used. The resin composition layer or the comparative composition layer on the copper substrate was exposed using a stepper (Nikon NSR 2005 i9C) at an exposure energy of 500 mJ/cm ² to form a photomask having a square non-mask portion of 100 μm square. , then developed for 60 seconds with the developer described in the "Developer" column of the table, and rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a 100 μm square area. A square-shaped resin layer was obtained. Furthermore, under a nitrogen atmosphere, the resin is heated using a heating oven at the temperature described in the "Cure temperature (°C)" column of the table for the time described in the "Cure time (min)" column of the table. A layer (pattern) was formed.
Using a bond tester (CondorSigma, manufactured by XYZTEC), shear force was measured on a 100 μm square resin layer on a copper substrate in an environment of 25° C. and 65% relative humidity (RH). . It can be said that the greater the shear force, the better the metal adhesion (copper adhesion) of the cured film. The shear force exceeded 30 gf in all the examples and comparative examples.

[Evaluation of adhesion after HTS (High Temperature Storage-test)]
After heating the resin layer and the copper substrate at the temperature described in the "Cure temperature (°C)" column of the table for the time described in the "Cure time (min)" column of the table, The shear force was measured and the metal adhesion after heating was evaluated according to the same evaluation method as in the evaluation of the metal adhesion described above, except that 1000 hours had passed within. Based on the measured shear force, evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in the column of "adhesion strength after HTS" in the table. It can be said that the greater the shear force, the better the metal adhesion (copper adhesion) of the cured film. It can be said that peeling is less likely to occur between
-Evaluation criteria-
A: Shearing force exceeded 30 gf.
B: Shearing force exceeded 25 gf and was 30 gf or less.
C: Shear force was 25 gf or less.
Also, 1 gf is 0.00980665N.

[Evaluation of void amount after HTS]
A square-shaped resin layer of 100 μm square was formed on a copper substrate by the same evaluation method as in the evaluation of metal adhesion described above.
After heating the resin layer and the copper substrate at the temperature described in the "Cure temperature (°C)" column of the table for the time described in the "Cure time (min)" column of the table, After 1000 hours, cross-sectional SEM (scanning microscope) measurement was performed to evaluate the void area ratio between the copper substrate and the resin layer. The void area ratio was calculated by the following formula.
Void area ratio (%) = (area of voids observed by SEM measurement)/(total area of resin layer) x 100
Evaluation was performed according to the following evaluation criteria from the value of the obtained void area ratio. The evaluation results are shown in the column of "Amount of voids after HTS" in the table. It can be said that the smaller the void area ratio, the better the reliability of the cured film after HTS, and that voids are less likely to occur between the metal layer and the cured product even after a long period of time.
-Evaluation criteria-
A: The void area ratio was 0.5% or less.
B: The void area ratio exceeded 0.5% and was 2% or less.
C: The void area ratio exceeded 2%.

(Example 101)
A film was formed under the same conditions as in Example 1 except that an infrared lamp heating device (RTP-6, manufactured by Advance Riko Co., Ltd.) was used as a curing means.
The same results as in Example 1 were obtained with respect to storage stability, elongation at break, adhesion after HTS, and amount of voids after HTS.

(Example 102)
In Example 8, the resin was changed to a resin consisting of repeating units represented by the following formula (PI-5), and the thermal base generator B-1 was changed to the following photobase generator B-7, respectively, to obtain a curable resin composition. prepared. Using the obtained curable resin composition, storage stability evaluation, post-HTS adhesion strength, and post-HTS void amount were evaluated.
Storage stability was evaluated by the same method as in Example 8.
Adhesion and void amount evaluation after HTS were performed by changing the photomask to a photomask having a square mask portion of 100 μm square, and developing with a 2.38% by mass tetramethylammonium hydroxide aqueous solution for 30 seconds. and rinsed with pure water to form a pattern.
When the same evaluation as in Example 8 was conducted, similar results were obtained for storage stability, adhesion after HTS, and amount of voids even in the positive type.

(Example 103)
In Example 1, except that the polymerization initiator C-1, the polymerization inhibitor E-2 and the silane coupling agent G-1 were excluded, and the amount of the resin PI-3 was changed from 80 parts by mass to 86.7 parts by mass. prepared a resin composition in the same manner as in Example 1.
Using the above resin composition, evaluation of storage stability, evaluation of post-HTS adhesion strength, and evaluation of post-HTS void amount were performed in the same manner as in Example 1. Similar results were obtained.

From the above results, it can be seen that the resin composition of the present invention provides a cured product with excellent reliability.
The comparative composition in Comparative Example 1 does not contain the specific compound. In such an embodiment, it can be seen that the reliability of the resulting cured product is poor.

<Example 201>
The resin composition used in Example 1 was applied in a layer by spin coating to the surface of the thin copper layer of the resin substrate having the thin copper layer formed on the surface, and dried at 100° C. for 5 minutes to obtain a film thickness. After forming a photosensitive film of 20 μm, it was exposed using a stepper (NSR1505 i6 manufactured by Nikon Corporation). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-and-space pattern and a line width of 10 μm). After the above exposure, the film was developed with cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern.
Next, in a nitrogen atmosphere, the temperature was raised at a rate of 10° C./min, reaching 230° C., and then maintained at 230° C. for 180 minutes to form an interlayer insulating film for rewiring layers. This interlayer insulating film for rewiring layer was excellent in insulating properties.
Moreover, when a semiconductor device was manufactured using these interlayer insulating films for rewiring layers, it was confirmed that the device operated without any problem.

Claims (18)

at least one resin selected from the group consisting of cyclized resins and precursors thereof;
A resin composition comprising a compound represented by the following formula (1-1).

In formula (1-1), each R ¹ independently represents a hydrogen atom or a monovalent organic group, each R ² independently represents an aromatic heterocycle, and each R ³ independently represents a hydrogen atom or represents a monovalent organic group, each L ¹ independently represents a divalent linking group, n represents an integer of 1 or more, and L ² represents an n-valent linking group. The resin composition according to claim 1, wherein R ² in formula (1-1) contains an azole structure. 3. The resin composition according to claim 1, wherein R ² in formula (1-1) contains a purine structure. The resin composition according to any one of claims 1 to 3, wherein n in formula (1-1) is 1, and ^L2 is a group represented by formula (L2-1) below. .

In formula (L2-1), Ar represents an aromatic group, L ^L2 represents a single bond or a divalent linking group, R ^L2 represents a hydrogen atom, a hydroxy group or a monovalent organic group, * represents the formula represents the bonding site with the carbonyl group in (1-1). 5. The resin composition according to any one of claims 1 to 4, wherein R ³ in formula (1-1) is a hydrogen atom. The resin composition according to any one of claims 1 to 5, wherein L ¹ in formula (1-1) has a structure represented by formula (L1-1) below.

In formula (L1-1), L ^L1 represents a divalent linking group, # represents a binding site to the nitrogen atom to which R ³ in formula (1-1) is bonded, * represents formula (1-1 ) represents the bonding site with the nitrogen atom to which R ¹ is bonded. The resin composition according to any one of claims 1 to 6, wherein the compound represented by formula (1-1) is a compound that generates a base by the action of light or heat. The resin composition according to any one of claims 1 to 7, wherein the resin is at least one resin selected from polyimides and polyimide precursors. 9. The resin composition according to any one of claims 1 to 8, which is used for forming an interlayer insulating film for rewiring layers. A cured product obtained by curing the resin composition according to any one of claims 1 to 9. A laminate comprising two or more layers comprising the cured product according to claim 10 and a metal layer between any of the layers comprising the cured product. A method for producing a cured product, comprising a film forming step of applying the resin composition according to any one of claims 1 to 9 onto a substrate to form a film. 13. The method for producing a cured product according to claim 12, comprising an exposure step of selectively exposing the film and a developing step of developing the film with a developer to form a pattern. The method for producing a cured product according to claim 12 or 13, comprising a heating step of heating the film at 50 to 450°C. A method for producing a laminate, comprising the method for producing a cured product according to any one of claims 12 to 14. A method for producing a semiconductor device, comprising the method for producing a cured product according to any one of claims 12 to 14 or the method for producing a laminate according to claim 15. A semiconductor device comprising the cured product according to claim 10 or the laminate according to claim 11 . A compound represented by the following formula (1-1).

In formula (1-1), each R ¹ independently represents a hydrogen atom or a monovalent organic group, each R ² independently represents an aromatic heterocycle, and each R ³ independently represents a hydrogen atom or represents a monovalent organic group, each L ¹ independently represents a divalent linking group, n represents an integer of 1 or more, and L ² represents an n-valent linking group.