JP7277573B2 - Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device - Google Patents

Description

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

Polymer precursors such as polyimide resins and polybenzoxazole resins (hereinbelow, polyimide resin precursors and polybenzoxazole resin precursors are collectively referred to as "heterocyclic ring-containing polymer precursors") are cyclized and cured. has been applied to various applications due to its excellent heat resistance and insulating properties. The use is not particularly limited, but in the case of a semiconductor device for mounting, it can be used as a material for an insulating film or a sealing material, or as a protective film. It is also used as a base film or coverlay for flexible substrates.

For example, in the applications described above, the heterocycle-containing polymer precursor is used in the form of a curable resin composition containing the heterocycle-containing polymer precursor. Such a curable resin composition is applied to a substrate by, for example, coating, and then the heterocycle-containing polymer precursor is cyclized by heating or the like to form a cured resin on the substrate. can be done. Since the curable resin composition can be applied by a known coating method, for example, the shape, size, application position, etc. of the curable resin composition to be applied have a high degree of freedom in design. It can be said that it is excellent in adaptability. In addition to the high performance of polyimide resins and the like, from the viewpoint of such excellent manufacturing adaptability, industrial application development of curable resin compositions containing heterocyclic-containing polymer precursors is increasingly expected.

For example, in US Pat. No. 5,700,000, a containing space containing a polar liquid and a non-polar liquid that are immiscible with each other is defined between a first electrode layer stack and a second electrode layer stack, including a specific process. A method of manufacturing a septum is described.
Patent Document 2 describes a photosensitive polymer composition containing (a) a polyimide precursor and a polyimide, (b) a photopolymerization initiator, and (c) an aromatic diamine compound.

JP 2017-015811 A Japanese Patent Application Laid-Open No. 2006-201670

In the formation of a cured film obtained by curing a curable resin composition containing a heterocycle-containing polymer precursor such as a polyimide precursor, for example, a curable resin composition is further applied on the cured film and cured to form a laminate. , the previously formed cured film may come into contact with the developer or other composition.
Therefore, in the curable resin composition, for example, from the viewpoint of the resistance of the cured film to the developer or the suppression of dissolution of the cured film due to contact with other compositions, the cured film obtained has excellent chemical resistance. It is desired to provide a flexible resin composition.

The present invention provides a curable resin composition having excellent chemical resistance of a cured film obtained, a cured film obtained by curing the curable resin composition, a laminate containing the cured film, a method for producing the cured film, and An object of the present invention is to provide a semiconductor device comprising the cured film or the laminate.

式（１）又は式（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価の有機基を表し、Ｒ^１１３及びＲ^１１４の少なくとも一方は、置換されていてもよいビニル基が直接結合した芳香環を含み、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価の有機基を表し、Ｒ^１２３及びＲ^１２４の少なくとも一方は、置換されていてもよいビニル基が直接結合した芳香環を含む。
＜３＞ 上記置換されていてもよいビニル基が直接結合した芳香環を有する基として、下記式（Ｓ－１）により表される基を含む、＜１＞又は＜２＞に記載の硬化性樹脂組成物；

式（Ｓ－１）中、Ｒ^Ｓ１は水素原子又はメチル基を表し、Ｒ^Ｓ２は置換基を表し、Ｌ^Ｓ１は単結合又は２価の連結基を表し、ｎは０～４の整数を表し、＊は他の構造との結合部位を表す。
＜４＞ 上記ポリマー前駆体の全質量に対する、上記置換されていてもよいビニル基が直接結合した芳香環の量が、１～８ｍｏｌ／ｇである、＜１＞～＜３＞のいずれか１つに記載の硬化性樹脂組成物。
＜５＞ エチレン性不飽和基を分子内に２個以上有する化合物を更に含む、＜１＞～＜４＞のいずれか１つに記載の硬化性樹脂組成物。
＜６＞ 上記エチレン性不飽和基を分子内に２個以上有する化合物が、置換されていてもよいビニル基が直接結合した芳香環を分子内に２個以上有する化合物である、＜５＞に記載の硬化性樹脂組成物。
＜７＞ 上記置換されていてもよいビニル基が直接結合した芳香環を分子内に２個以上有する化合物が、下記式（１－１）で表される化合物である、＜６＞に記載の硬化性樹脂組成物；

式（１－１）中、Ｚは２価以上の飽和脂肪族炭化水素基、２価以上の不飽和脂肪族炭化水素基、２価以上の炭化水素環基、－Ｏ－、－Ｓ－、－Ｎ（Ｒ^Ａ）－、－Ｃ（＝Ｏ）－Ｏ－、－Ｃ（Ｒ^Ａ）＝Ｎ－、－Ｃ（＝Ｏ）－、－Ｓ（＝Ｏ）_２－、２価以上の複素環基、及び、これらが２以上結合した基よりなる群から選ばれたｍ価の連結基であり、Ｒ^Ａは水素原子、アルキル基又はアリール基を表し、Ｒ^Ａが複数存在する場合、複数のＲ^Ａは同一であっても異なっていてもよく、Ｒ^１はそれぞれ独立に、水素原子又はメチル基を表し、ｍは２～６の整数を表す。
＜８＞ 光ラジカル重合開始剤を更に含む、＜１＞～＜７＞のいずれか１つに記載の硬化性樹脂組成物。
＜９＞ オニウム塩を更に含む、＜１＞～＜８＞のいずれか１つに記載の硬化性樹脂組成物。
＜１０＞ 再配線層用層間絶縁膜の形成に用いられる、＜１＞～＜９＞のいずれか１つに記載の硬化性樹脂組成物。
＜１１＞ ＜１＞～＜１０＞のいずれか１つに記載の硬化性樹脂組成物を硬化してなる硬化膜。
＜１２＞ ＜１１＞に記載の硬化膜を２層以上含み、上記硬化膜同士のいずれかの間に金属層を含む積層体。
＜１３＞ ＜１＞～＜１０＞のいずれか１つに記載の硬化性樹脂組成物を基材に適用して膜を形成する膜形成工程を含む、硬化膜の製造方法。
＜１４＞ 上記膜を露光する露光工程及び上記膜を現像する現像工程を含む、＜１３＞に記載の硬化膜の製造方法。
＜１５＞ 上記膜を５０～４５０℃で加熱する加熱工程を含む、＜１３＞又は＜１４＞に記載の硬化膜の製造方法。
＜１６＞ ＜１１＞に記載の硬化膜又は＜１２＞に記載の積層体を含む、半導体デバイス。Examples of representative embodiments of the present invention are provided below.
<1> containing at least one polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors,
A curable resin composition, wherein the polymer precursor contains an aromatic ring to which an optionally substituted vinyl group is directly bonded.
<2> The polymer precursor is a polyimide precursor having a repeating unit represented by the following formula (1) or a polybenzoxazole precursor having a repeating unit represented by the following formula (2). 1> the curable resin composition;

In formula (1) or (2), A ¹ and A ² each independently represent an oxygen atom or —NH—, R ¹¹¹ represents a divalent organic group, and R ¹¹⁵ represents a tetravalent organic group, R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, and at least one of R ¹¹³ and R ¹¹⁴ is an aromatic ring directly bonded to an optionally substituted vinyl group wherein R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group, and R At least one of ¹²³ and R ¹²⁴ contains an aromatic ring to which an optionally substituted vinyl group is directly bonded.
<3> Curability according to <1> or <2>, including a group represented by the following formula (S-1) as the group having an aromatic ring to which the optionally substituted vinyl group is directly bonded resin composition;

In formula (S-1), R ^S1 represents a hydrogen atom or a methyl group, R ^S2 represents a substituent, L ^S1 represents a single bond or a divalent linking group, and n represents an integer of 0 to 4. , * represent binding sites with other structures.
<4> Any one of <1> to <3>, wherein the amount of the aromatic ring to which the optionally substituted vinyl group is directly bonded is 1 to 8 mol/g with respect to the total mass of the polymer precursor. The curable resin composition according to 1.
<5> The curable resin composition according to any one of <1> to <4>, further comprising a compound having two or more ethylenically unsaturated groups in the molecule.
<6><5>, wherein the compound having two or more ethylenically unsaturated groups in the molecule is a compound having two or more aromatic rings to which optionally substituted vinyl groups are directly bonded in the molecule; A curable resin composition as described.
<7> The compound according to <6>, wherein the compound having two or more aromatic rings to which the optionally substituted vinyl groups are directly bonded is a compound represented by the following formula (1-1). curable resin composition;

In formula (1-1), Z is a divalent or higher saturated aliphatic hydrocarbon group, a divalent or higher unsaturated aliphatic hydrocarbon group, a divalent or higher hydrocarbon ring group, -O-, -S-, -N(R ^A )-, -C(=O)-O-, -C(R ^A )=N-, -C(=O)-, -S(=O) ₂ -, 2 or higher complex an m-valent linking group selected from the group consisting of a cyclic group and a group ⁱⁿ which two or more of these are bonded, ^RA represents a hydrogen atom, an alkyl group or an aryl group; R ¹ may be the same or different, each R ¹ independently represents a hydrogen atom or a methyl group, and m represents an integer of 2-6.
<8> The curable resin composition according to any one of <1> to <7>, further comprising a photoradical polymerization initiator.
<9> The curable resin composition according to any one of <1> to <8>, further comprising an onium salt.
<10> The curable resin composition according to any one of <1> to <9>, which is used for forming an interlayer insulating film for rewiring layers.
<11> A cured film obtained by curing the curable resin composition according to any one of <1> to <10>.
<12> A laminate comprising two or more layers of the cured film according to <11> and a metal layer between any of the cured films.
<13> A method for producing a cured film, comprising a film forming step of applying the curable resin composition according to any one of <1> to <10> to a substrate to form a film.
<14> The method for producing a cured film according to <13>, comprising an exposure step of exposing the film and a development step of developing the film.
<15> The method for producing a cured film according to <13> or <14>, comprising a heating step of heating the film at 50 to 450°C.
<16> A semiconductor device comprising the cured film according to <11> or the laminate according to <12>.

According to the present invention, a curable resin composition in which a cured film obtained has excellent chemical resistance, a cured film obtained by curing the curable resin composition, a laminate including the cured film, and a method for producing the cured film. and a semiconductor device comprising the cured film 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 the present specification, weight average molecular weight (Mw) and number average molecular weight (Mn) are defined as polystyrene equivalent values according to gel permeation chromatography (GPC measurement), unless otherwise specified. 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 using Super HZ4000, TSKgel Super HZ3000, TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise stated, their molecular weights were determined using THF (tetrahydrofuran) as an eluent. In addition, unless otherwise specified, detection in GPC measurement uses a UV ray (ultraviolet) wavelength detector of 254 nm.
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. Further, unless otherwise specified, the direction in which the layers are stacked with respect to the substrate is referred to as "upper", or when there is a photosensitive layer, the direction from the substrate toward the photosensitive layer is referred to as "upper". 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 vertical 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. and the pressure is 101,325 Pa (1 atm) unless otherwise specified.
Combinations of preferred aspects are more preferred aspects herein.

(Curable resin composition)
The curable resin composition of the present invention contains at least one polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors, and the polymer precursor contains an optionally substituted vinyl group. contains an aromatic ring to which is directly attached.
The curable resin composition of the present invention preferably further contains a compound having two or more ethylenically unsaturated groups in the molecule, which will be described later.
Moreover, it is preferable that the curable resin composition of the present invention further contains a photoradical polymerization initiator, which will be described later.

A cured film obtained from the curable resin composition of the present invention is excellent in chemical resistance.
Although the mechanism by which the above effects are obtained is unknown, it is presumed as follows.

Conventionally, in a curable resin composition containing a heterocyclic ring-containing polymer precursor, a heterocyclic ring-containing polymer precursor having a radically polymerizable group is used, and the radically polymerizable group is radically polymerized by exposure, heating, or the like to obtain a cured film. It is done to obtain
Here, the above radical polymerization is known to be inhibited in the presence of oxygen, and when the above exposure, heating, etc. are performed in the presence of oxygen, unreacted radically polymerizable groups are removed. It is thought that the compound having such a compound remains in the cured film.
However, the heterocyclic ring-containing polymer precursor in the curable resin composition of the present invention contains an aromatic ring to which an optionally substituted vinyl group is directly bonded. Hereinafter, a heterocyclic ring-containing polymer precursor containing an aromatic ring to which an optionally substituted vinyl group is directly bonded is also referred to as a "specific heterocyclic ring-containing polymer precursor".
Since the vinyl group in the aromatic ring to which the optionally substituted vinyl group in the specific heterocyclic ring-containing polymer precursor is directly bonded is less susceptible to polymerization inhibition in the presence of oxygen, even in the presence of oxygen, during exposure, heating, etc. It is thought that the radical polymerization in is rapidly progressed.
As a result, the amount of unreacted radically polymerizable groups in the cured film is reduced. Therefore, according to the curable resin composition of the present invention, a cured film having low organic solvent permeability, low solubility in organic solvents, etc. can be obtained. It is considered to be obtained.
In addition, as described above, the vinyl group is unlikely to be inhibited by polymerization in the presence of oxygen, so the curable resin composition of the present invention is likely to be excellent in exposure sensitivity.

Here, Patent Document 1 or 2 does not describe or suggest a heterocyclic ring-containing polymer precursor (specific heterocyclic ring-containing polymer precursor) containing an aromatic ring to which an optionally substituted vinyl group is directly bonded.
Components contained in the curable resin composition of the present invention are described in detail below.

<Specific heterocycle-containing polymer precursor>
The curable resin composition of the present invention contains a specific heterocycle-containing polymer precursor.
The curable resin composition of the present invention contains, as a specific heterocycle-containing polymer precursor, at least one precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors, and contains a polyimide precursor. is preferred.
The specific heterocyclic ring-containing polymer precursor contains an aromatic ring to which an optionally substituted vinyl group is directly bonded.
In the present specification, an aromatic ring to which an optionally substituted vinyl group is directly bonded means that one carbon atom in the double bond of the optionally substituted vinyl group is directly bonded to the aromatic ring structure. structure. The aromatic ring may have a known substituent such as an alkyl group or a halogeno group.
The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and the aromatic hydrocarbon ring or aromatic heterocyclic ring includes an aromatic hydrocarbon ring or an aliphatic hydrocarbon ring or An aromatic heterocycle or an aliphatic heterocycle may be condensed. Moreover, these aromatic hydrocarbon rings, aliphatic hydrocarbon rings, aromatic heterocycles or aliphatic heterocycles may each have a known substituent such as an alkyl group or a halogeno group.
The aromatic ring in the aromatic ring to which the optionally substituted vinyl group is directly bonded is preferably an aromatic hydrocarbon ring, more preferably a benzene ring.
That is, the specific heterocycle-containing polymer precursor preferably contains a vinylphenyl group as a group containing an aromatic ring to which a vinyl group is directly bonded.

式（Ｓ－１）中、Ｒ^Ｓ１は水素原子又はメチル基を表し、Ｒ^Ｓ２は置換基を表し、Ｌ^Ｓ１は単結合又は２価の連結基を表し、ｎは０～４の整数を表し、＊は他の構造との結合部位を表す。[Group Represented by Formula (S-1)]
The specific heterocyclic ring-containing polymer precursor preferably contains a group represented by the following formula (S-1) as a group having an aromatic ring to which an optionally substituted vinyl group is directly bonded.

In formula (S-1), R ^S1 represents a hydrogen atom or a methyl group, R ^S2 represents a substituent, L ^S1 represents a single bond or a divalent linking group, and n represents an integer of 0 to 4. , * represent binding sites with other structures.

In formula (S-1), R ^{1 S1} represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

In formula (S-1), R ^{2 S2} is preferably a halogen atom, an alkyl group or an aryl group, more preferably a halogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group.

In formula (S-1), L ^S1 is a single bond, an alkylene group, an alkenylene group, a divalent hydrocarbon ring group, -O-, -S-, -N(R ^A )-, -C(= O) -O-, -C(R ^A )=N-, -C(=O)-, -S(=O) ₂ -, -CH ₂ CH(OH)CH ₂ -divalent heterocyclic group, And, preferably a linking group selected from the group consisting of groups in which two or more of these are bonded, a single bond, or an alkylene group, a divalent aromatic hydrocarbon ring group, -O-, -S-, -N ( R ^A )-, -C(=O)-O-, -C(=O)-, and a linking group selected from the group consisting of two or more of these linked groups are more preferred. Further, the linking group preferably includes a (poly)oxyalkylene group having 1 to 30 carbon atoms as a linking group combining an alkylene group and —O—. A (poly)oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group. The alkylene group in the (poly)oxyalkylene group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms. In particular, when the (poly)oxyalkylene group is a polyoxyalkylene group, the alkylene group is preferably an ethylene group or a propylene group. The number of repeating oxyalkylene structures in the (poly)oxyalkylene group is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3.
The alkylene group for L ^S1 is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms.
The alkenylene group in L ^S1 is preferably an alkenylene group having 2 to 8 carbon atoms, more preferably an alkenylene group having 2 to 6 carbon atoms.
The hydrocarbon ring group for L ^S1 is preferably a divalent to tetravalent group obtained by removing 2 to 4 hydrogen atoms from a hydrocarbon ring.
The number of ring members of the hydrocarbon ring in the hydrocarbon ring group in L ^S1 is preferably 6 to 20, more preferably 6 to 12, even more preferably 6.
The divalent hydrocarbon ring group in L ^S1 is preferably an aromatic hydrocarbon ring, more preferably a benzene ring.
The heterocyclic ring in the divalent heterocyclic group in L ^S1 is preferably an aromatic heterocyclic ring, preferably an aromatic heterocyclic ring having 5 to 20 ring members, more preferably an aromatic heterocyclic ring having 5 to 20 ring members. The heterocyclic ring may be a condensed ring of multiple heterocyclic rings, or a condensed ring of a heterocyclic ring and an aromatic hydrocarbon ring. When the heterocyclic ring is a condensed ring, the monocyclic heterocyclic ring contained in the condensed ring preferably has 5 to 6 ring members.
In addition, the heterocyclic ring in the divalent heterocyclic group in L ^S1 includes a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an isoxazole ring, an oxazole ring, an oxadiazole ring, an isothiazole ring, and a thiazole ring. , thiadiazole ring, thiatriazole ring, indole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring, benzoselenazole ring, benzothiadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring , a triazine ring, a quinoline ring, a quinoxaline ring, a furan ring, or a thiophene ring.

In formula (S-1), n represents an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0.

From the viewpoint of the chemical resistance and storage stability of the resulting cured film, the amount of the aromatic ring to which the vinyl group, which may be substituted, is directly bonded to the total weight of the specific heterocyclic ring-containing polymer precursor is 0. It is preferably 1 to 12 mol/g, more preferably 0.5 to 10 mol/g, even more preferably 1 to 8 mol/g.

式（１）又は式（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価の有機基を表し、Ｒ^１１３及びＲ^１１４の少なくとも一方は、置換されていてもよいビニル基が直接結合した芳香環を含み、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価の有機基を表し、Ｒ^１２３及びＲ^１２４の少なくとも一方は、置換されていてもよいビニル基が直接結合した芳香環を含む。[Repeating unit represented by formula (1) or repeating unit represented by formula (2)]
The specific heterocyclic ring-containing polymer precursor is a polyimide precursor having a repeating unit represented by the following formula (1), or a polybenzoxazole precursor having a repeating unit represented by the following formula (2). preferable.

In formula (1) or (2), A ¹ and A ² each independently represent an oxygen atom or —NH—, R ¹¹¹ represents a divalent organic group, and R ¹¹⁵ represents a tetravalent organic group, R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, and at least one of R ¹¹³ and R ¹¹⁴ is an aromatic ring directly bonded to an optionally substituted vinyl group wherein R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group, and R At least one of ¹²³ and R ¹²⁴ contains an aromatic ring to which an optionally substituted vinyl group is directly bonded.

[Polyimide precursor]
The polyimide precursor preferably contains a repeating unit represented by formula (1) above.

- A ¹ and A ² -
A ¹ and A ² in formula (1) each independently represent an oxygen atom or —NH—, preferably an oxygen atom.

-R ¹¹¹ -
R ¹¹¹ in formula (1) represents a divalent organic group. Examples of divalent organic groups include linear or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or groups in which two or more of these are combined. 2 to 20 linear aliphatic groups, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, aromatic groups having 6 to 20 carbon atoms, or two of these Groups in which the above are combined are preferred, and aromatic groups having 6 to 20 carbon atoms are more preferred.

R ¹¹¹ in formula (1) 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, the diamine is a linear aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or these A diamine containing a combination of two or more groups is preferable, and a diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable. Examples of aromatic groups include:

In the formula, A is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms optionally substituted with a fluorine atom, -O-, -C (= O) -, -S-, -S (=O) ₂ -, -NHC(=O)-, or a group in which two or more of these are combined, preferably a single bond, an alkylene group having 1 to 3 carbon atoms optionally substituted with a fluorine atom , -O-, -C(=O)-, -S- and S(=O) ₂ -, more preferably a group selected from -CH ₂ -, -O-, -S-, - It is more preferably a divalent group selected from the group consisting of S(=O) ₂ -, -C(CF ₃ ) ₂ - and -C(CH ₃ ) ₂ -.

Specific diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane; 1,2- or 1 ,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4- aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4′-diamino-3,3′-dimethylcyclohexylmethane or isophoronediamine; meta- or para-phenylenediamine, diaminotoluene, 4,4′- or 3 ,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone , 4,4′- or 3,3′-diaminodiphenyl sulfide, 4,4′- or 3,3′-diaminobenzophenone, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′- Dimethyl-4,4'-diaminobiphenyl (4,4'-diamino-2,2'-dimethylbiphenyl), 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-amino phenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl ) hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxy phenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoparaterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy ) phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10- Bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene , 1,3-bis(4-aminophenyl)benzene, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 4,4′-diamino Octafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4- aminophenyl)-10-hydroanthracene, 3,3′,4,4′-tetraaminobiphenyl, 3,3′,4,4′-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone , 3,3-dihydroxy-4,4′-diaminobiphenyl, 9,9′-bis(4-aminophenyl)fluorene, 4,4′-dimethyl-3,3′-diaminodiphenylsulfone, 3,3′, 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2-(3',5'-diaminobenzoyloxy)ethyl methacrylate, 2,4- or 2,5-diaminocumene, 2,5-dimethyl- paraphenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-paraphenylenediamine, 2,4,6-trimethyl-metaphenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7- Diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, 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]hexa Fluoropropane, parabis(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 at least one selected from '-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolyzine and 4,4'-diaminoquaterphenyl species of diamines.

Diamines (DA-1) to (DA-18) shown below are also preferred.

Diamines having at least two alkylene glycol units in the main chain are also preferred examples. Diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule are preferred, and diamines containing no aromatic ring are more preferred. Specific examples include Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, Jeffamine (registered trademark) ED-900, Jeffamine (registered trademark) ED-2003, Jeffamine (registered trademark) ) EDR-148, Jeffamine (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (trade names, manufactured by HUNTSMAN), 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. not.

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

In the above, x, y and z are arithmetic mean values.

R ¹¹¹ in formula (1) is preferably represented by -Ar ⁰ -L ⁰ -Ar ⁰ - from the viewpoint of the flexibility of the resulting cured film. Each Ar ⁰ is independently an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), preferably a phenylene group. L ⁰ is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms optionally substituted with a fluorine atom, -O-, -C(=O)-, -S-, -S(= O) ₂ —, —NHCO—, or a group in which two or more of these are combined. The preferred range of L ⁰ is synonymous with A above.

From the viewpoint of i-line transmittance, R ¹¹¹ in Formula (1) is preferably a divalent organic group represented by Formula (51) or Formula (61) below. In particular, from the viewpoint of i-line transmittance and availability, a divalent organic group represented by Formula (61) is more preferable.

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, a fluoromethyl group, It is a difluoromethyl group or a trifluoromethyl group, and each * independently represents a binding site to another structure.

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 fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group.

Diamine compounds that give the structure of formula (51) or (61) include dimethyl-4,4′-diaminobiphenyl, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 2,2 '-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like. One of these may be used, or two or more may be used in combination.

-R ¹¹⁵ -
R ¹¹⁵ in formula (1) 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.

R ¹¹² has the same definition as A, and the preferred range is also the same. Each * independently represents a binding site with another structure.

Specific examples of the tetravalent organic group represented by R ¹¹⁵ in formula (1) include a tetracarboxylic acid residue remaining after removal of the acid dianhydride group from the tetracarboxylic dianhydride. Only one kind of tetracarboxylic dianhydride may be used, or two or more kinds thereof may be used. Tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).

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

Specific examples of tetracarboxylic dianhydrides include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 3,3′,4 ,4′-diphenylsulfidetetracarboxylic 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 acid 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 di anhydride, 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 at least one selected from alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

In addition, the following tetracarboxylic dianhydrides (DAA-1) to (DAA-5) are also preferred examples.

-R ¹¹³ and R ¹¹⁴ -
R ¹¹³ and R ¹¹⁴ in formula (1) each independently represent a hydrogen atom or a monovalent organic group, and at least one of R ¹²³ and R ¹²⁴ is an aromatic ring to which an optionally substituted vinyl group is directly bonded. including.
As the group having an aromatic ring to which an optionally substituted vinyl group is directly bonded, a group represented by the above formula (S-1) is preferable.
When at least one of R ¹²³ and R ¹²⁴ is a group represented by the above formula (S-1), * in formula (S-1) is a binding site to A ¹ or A ² in formula (1) represents

One of R ¹¹³ and R ¹¹⁴ may not contain an aromatic ring to which an optionally substituted vinyl group is directly bonded.
When R ¹¹³ and R ¹¹⁴ do not contain an aromatic ring to which an optionally substituted vinyl group is directly bonded, one of R ¹¹³ and R ¹¹⁴ is directly bonded to an optionally substituted vinyl group. Although it may be a group having an ethylenically unsaturated bond other than an aromatic ring, it is preferably a group having no ethylenically unsaturated bond.

The group having an ethylenically unsaturated bond other than the aromatic ring to which the optionally substituted vinyl group in R ¹¹³ and R ¹¹⁴ is directly bonded includes a vinyl group, an allyl group, a (meth)acryloyl group, and the following formula (III). A group represented by and the like can be mentioned.

In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, preferably a methyl group.

In formula (III), R ²⁰¹ is an alkylene group having 2 to 12 carbon atoms, —CH ₂ CH(OH)CH ₂ —, or a (poly)oxyalkylene group having 4 to 30 carbon atoms (the alkylene group having 1 carbon 1 to 12 are preferred, 1 to 6 are more preferred, and 1 to 3 are particularly preferred; the repeating number is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3). In addition, a (poly)oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.
Examples of suitable R ²⁰¹ are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butanediyl group, 1,3-butanediyl group, pentamethylene group, hexamethylene group, octamethylene group and dodecamethylene group. , -CH ₂ CH(OH)CH ₂ -, and more preferably ethylene group, propylene group, trimethylene group and -CH ₂ CH(OH)CH ₂ -.
Particularly preferably, R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethylene group.
In formula (III), * represents a binding site with another structure.

Groups having no ethylenically unsaturated bond for R ¹¹³ and R ¹¹⁴ include aliphatic groups, aromatic groups and arylalkyl groups having 1, 2 or 3, preferably 1 acid group. Specific examples include an aromatic group having 6 to 20 carbon atoms having an acid group and an arylalkyl group having 7 to 25 carbon atoms having an acid group. More specific examples include a phenyl group having an acid group and a benzyl group having an acid group. The acid group is preferably a hydroxy group. That is, R ¹¹³ or R ¹¹⁴ is preferably a group having a hydroxy group.
As the group having no ethylenically unsaturated bond for R ¹¹³ and R ¹¹⁴ , a substituent that improves solubility in a developer is preferably used.

More preferably, R ¹¹³ or R ¹¹⁴ is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl or 4-hydroxybenzyl from the viewpoint of solubility in an aqueous developer.

From the viewpoint of solubility in organic solvents, the group having no ethylenically unsaturated bond in R ¹¹³ and R ¹¹⁴ is preferably a monovalent organic group. The monovalent organic group is preferably a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, more preferably an alkyl group substituted with an aromatic group.

The number of carbon atoms in the alkyl group is preferably 1 to 30 (3 or more in the case of cyclic). Alkyl groups may be linear, branched or cyclic. Linear or branched alkyl groups include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group and octadecyl group. , isopropyl, isobutyl, sec-butyl, t-butyl, 1-ethylpentyl, and 2-ethylhexyl groups. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of monocyclic cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups. Examples of polycyclic cyclic alkyl groups include adamantyl group, norbornyl group, bornyl group, camphenyl group, decahydronaphthyl group, tricyclodecanyl group, tetracyclodecanyl group, camphoroyl group, dicyclohexyl group and pinenyl group. is mentioned. Moreover, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described below is preferable.

Specific examples of aromatic groups include substituted or unsubstituted aromatic hydrocarbon groups (cyclic structures constituting the group include benzene ring, naphthalene ring, biphenyl ring, fluorene ring, pentalene ring, indene ring, azulene ring, ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene ring, triphenylene ring, etc.), or a substituted or unsubstituted aromatic heterocyclic group ( The cyclic structure constituting the group includes a fluorene ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an indolizine ring, an indole ring, and a benzofuran. ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring , xanthene ring, phenoxathiin ring, phenothiazine ring or phenazine ring).

Also, the polyimide precursor preferably has a fluorine atom in the repeating unit. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, more preferably 20% by mass or more. Although there is no particular upper limit, 50% by mass or less is practical.

For the purpose of improving adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with the repeating unit represented by formula (1). Specific examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(para-aminophenyl)octamethylpentasiloxane.

The repeating unit represented by formula (1) is preferably a repeating unit represented by formula (1-A) or (1-B).

A ¹¹ and A ¹² each independently represent an oxygen atom or —NH—, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or 1 represents a valent organic group, and at least one of R ¹¹³ and R ¹¹⁴ contains an aromatic ring to which an optionally substituted vinyl group is directly bonded.

The preferred ranges of A ¹¹ , A ¹² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ are the same as the preferred ranges of A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in Formula (1).

The preferred range of R ¹¹² has the same meaning as R ¹¹² in formula (5), and more preferably an oxygen atom.

The bonding positions of the carbonyl group in the formula to the benzene ring are preferably 4, 5, 3' and 4' in formula (1-A). In formula (1-B), 1, 2, 4 and 5 are preferred.

In the polyimide precursor, the number of repeating units represented by formula (1) may be one, or two or more. It may also contain structural isomers of the repeating unit represented by formula (1). The polyimide precursor may also contain other types of repeating units in addition to the repeating units of formula (1) above.

式（１－２）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^１１３ａ及びＲ^１１４ａは、それぞれ独立に、水素原子又は１価の有機基を表し、Ｒ^１１３ａ及びＲ^１１４ａは、置換されていてもよいビニル基が直接結合した芳香環を含まない。Examples of other types of repeating units include repeating units represented by the following formula (1-2).

In formula (1-2), A ¹ and A ² each independently represent an oxygen atom or —NH—, R ¹¹¹ represents a divalent organic group, and R ¹¹⁵ represents a tetravalent organic group. , R ^113a and R ^114a each independently represent a hydrogen atom or a monovalent organic group, and R ^113a and R ^114a do not contain an aromatic ring to which an optionally substituted vinyl group is directly bonded.

In formula (1-2), A ¹ , A ² , R ¹¹¹ and R ¹¹⁵ are respectively synonymous with A ¹ , A ² , R ¹¹¹ and R ¹¹⁵ in formula (1), and a preferred embodiment The same is true for
In formula (1-2), R ^113a and R ^114a are each the optionally substituted vinyl group in R ¹¹³ and R ¹¹⁴ described in the description of R ¹¹³ and R ¹¹⁴ in formula (1). A group having an ethylenically unsaturated bond other than a directly bonded aromatic ring, or a group similar to the group having no ethylenically unsaturated bond in R ¹¹³ and R ¹¹⁴ is preferable, and ethylene in R ¹¹³ and R ¹¹⁴ It is more preferably the same group as the group having no sexually unsaturated bond.
A group having an ethylenically unsaturated bond other than an aromatic ring directly bonded to an optionally substituted vinyl group for R ¹¹³ and R ¹¹⁴ , and a group having no ethylenically unsaturated bond for R ¹¹³ and R ¹¹⁴ Preferred embodiments of groups similar to are as described above.
The polyimide precursor may contain one repeating unit represented by formula (1-2), or may contain two or more repeating units.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, still more preferably 10,000 to 50,000. Further, 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, particularly preferably is between 4,000 and 24,000.

The polyimide precursor preferably has a molecular weight distribution of 1.5 to 3.5, more preferably 2 to 3.
In the present specification, the molecular weight dispersity refers to the value obtained by dividing the weight average molecular weight by the number average molecular weight (weight average molecular weight/number average molecular weight).

A polyimide precursor is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative using a halogenating agent and then reacting it with a diamine.
Methods for obtaining a polyimide precursor having an aromatic ring to which an optionally substituted vinyl group is directly bonded include the following methods.
(1) A method of reacting a tetracarboxylic acid derivative having an aromatic ring to which an optionally substituted vinyl group is directly bonded with a diamine (2) A tetracarboxylic acid derivative and an optionally substituted vinyl group are directly bonded. (3) After reacting a tetracarboxylic acid derivative with a diamine, reacting the obtained reactant with a styrene derivative having a hydroxyl group, an epoxy group, an isocyanato group, or the like. Method The tetracarboxylic acid derivative having an aromatic ring to which an optionally substituted vinyl group is directly bonded and the diamine can be obtained, for example, by reacting a tetracarboxylic acid derivative with a styrene derivative having an amino group or a hydroxyl group.
The diamine having an aromatic ring to which the optionally substituted vinyl group is directly bonded can be obtained, for example, by reacting a diamine having a hydroxyl group with a styrene derivative having an isocyanato group, an epoxy group, or the like.

In the method for producing a polyimide precursor, 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.

Examples of the organic solvent include pyridine, diethylene glycol dimethyl ether (diglyme), N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone.

The production of the polyimide precursor preferably includes a step of depositing a solid. Specifically, the polyimide precursor in the reaction solution is precipitated in water, and dissolved in a solvent such as tetrahydrofuran in which the polyimide precursor is soluble, whereby solid deposition can be performed.

[Polybenzoxazole precursor]
The polybenzoxazole precursor preferably contains repeating units represented by formula (2) above.

-R ¹²¹ -
In formula (2), R ¹²¹ represents a divalent organic group. The divalent organic group includes an aliphatic group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms) and an aromatic group (preferably 6 to 22 carbon atoms, 6 to 14 is more preferred, and 6 to 12 are particularly preferred). Examples of the aromatic group constituting R ¹²¹ include the examples of R ¹¹¹ in the above formula (1). As the aliphatic group, a linear aliphatic group is preferable. R ¹²¹ is preferably derived from 4,4'-oxydibenzoyl chloride.

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

-R ¹²³ and R ¹²⁴ -
R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group, have the same meanings as R ¹¹³ and R ¹¹⁴ in formula (1) above, and the preferred ranges are also the same.

The polybenzoxazole precursor may contain repeating units of formula (2) above, as well as other types of repeating units.

式（２－２）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^１２３ａ及びＲ^１２４ａは、それぞれ独立に、水素原子又は１価の有機基を表し、Ｒ^１２３ａ及びＲ^１２４ａは、置換されていてもよいビニル基が直接結合した芳香環を含まない。Other types of repeating units include repeating units represented by the following formula (2-2).

In formula (2-2), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, R ^123a and R ^124a each independently represent a hydrogen atom or a monovalent organic R ^123a and R ^124a do not contain an aromatic ring to which an optionally substituted vinyl group is directly bonded.

In formula (2-2), R ¹²¹ and R ¹²² have the same meanings as R ¹²¹ and R ¹²² in formula (2), respectively, and preferred embodiments are also the same.
In formula (2-2), R ^123a and R ^124a are directly bonded to optionally substituted vinyl groups in R ¹¹³ and R ¹¹⁴ described in the description of R ¹¹³ and R ¹¹⁴ in formula (1), respectively. or a group similar to the group having no ethylenically unsaturated bond for R ¹¹³ and R ¹¹⁴ , and the ethylenically unsaturated bond for R ¹¹³ and R ¹¹⁴ is preferred. It is more preferably the same group as the group having no saturated bond.
A group having an ethylenically unsaturated bond other than an aromatic ring directly bonded to an optionally substituted vinyl group for R ¹¹³ and R ¹¹⁴ , and a group having no ethylenically unsaturated bond for R ¹¹³ and R ¹¹⁴ Preferred embodiments of groups similar to are as described above.
The polybenzoxazole precursor may contain one repeating unit represented by formula (2-2), or may contain two or more repeating units.

In addition, the polybenzoxazole precursor preferably further contains a diamine residue represented by the following formula (SL) as another type of repeating unit in order to suppress the occurrence of warping of the cured film due to ring closure.

Z has an a structure and a b structure, R ^1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and R ^2s is a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and at least one of R ^3s , R ^4s , R ^5s and R ^6s is aromatic A group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), the remainder being hydrogen atoms or 1 to 30 carbon atoms (preferably 1 to 18 carbon atoms, more It is preferably an organic group having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and may be the same or different. Polymerization of a structure and b structure may be block polymerization or random polymerization. In the Z portion, preferably the a structure is 5-95 mol %, the b structure is 95-5 mol %, and a+b is 100 mol %.

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. Molecular weights can be determined by commonly used gel permeation chromatography. By setting the molecular weight in the above range, it is possible to reduce the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure, thereby achieving both the effect of suppressing warpage and the effect of improving solubility.

When the polybenzoxazole precursor contains a diamine residue represented by the formula (SL) as another type of repeating unit, in terms of improving the alkali solubility of the curable resin composition, further, tetracarboxylic dianhydride It preferably contains, as a repeating unit, a tetracarboxylic acid residue remaining after removal of the acid dianhydride group from the compound. Examples of such tetracarboxylic acid residues include those of R ¹¹⁵ in formula (1).

The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, still more preferably 10,000 to 50,000. be. 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 molecular weight dispersity of the polybenzoxazole precursor is preferably 1.5-3.5, more preferably 2-3.

The content of the specific heterocycle-containing polymer precursor in the curable resin composition of the present invention is preferably 20% by mass or more, and 30% by mass or more, relative to the total solid content of the curable resin composition. is more preferably 40% by mass or more, still more preferably 50% by mass or more, even more preferably 60% by mass or more, and even more preferably 70% by mass or more. Further, the content of the specific heterocycle-containing polymer precursor in the curable resin composition of the present invention is preferably 99.5% by mass or less with respect to the total solid content of the curable resin composition, and 99 mass % or less, more preferably 98 mass % or less, even more preferably 97 mass % or less, and even more preferably 95 mass % or less.

The curable resin composition of the present invention may contain only one type of specific heterocycle-containing polymer precursor, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<Other heterocycle-containing polymer precursors>
The curable resin composition of the present invention may further contain other heterocyclic ring-containing polymer precursors other than the specific heterocyclic ring-containing polymer precursor.
Other heterocyclic ring-containing polymer precursors include a polyimide precursor that does not contain an aromatic ring to which an optionally substituted vinyl group is directly bonded, or an aromatic ring to which an optionally substituted vinyl group is directly bonded. A polybenzoxazole precursor that does not contain any aromatic ring is preferred, and a polyimide precursor that does not contain an aromatic ring to which an optionally substituted vinyl group is directly bonded is more preferred.

[Polyimide Precursor Not Containing Aromatic Ring Directly Bonded with Optionally Substituted Vinyl Group]
The polyimide precursor that does not contain an aromatic ring directly bonded to an optionally substituted vinyl group preferably has a repeating unit represented by the above formula (1-2).

In the polyimide precursor that does not contain an aromatic ring to which an optionally substituted vinyl group is directly bonded, the repeating unit represented by formula (1-2) may be one type, but two or more types good too. Further, it may contain a structural isomer of the repeating unit represented by formula (1-2). The polyimide precursor may also contain other types of repeating units in addition to the repeating units represented by formula (1-2) above.

As one embodiment of the polyimide precursor that does not contain an aromatic ring to which an optionally substituted vinyl group is directly bonded in the present invention, 50 mol% or more, further 70 mol% or more, particularly 90 mol% of the total repeating units The polyimide precursor which is the repeating unit represented by the formula (1-2) above is exemplified. A practical upper limit is 100 mol % or less.

The weight average molecular weight (Mw) of the polyimide precursor which does not contain an aromatic ring to which an optionally substituted vinyl group is directly bonded is preferably 2,000 to 500,000, more preferably 5,000 to 100, 000, 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 polyimide precursor containing no aromatic ring to which an optionally substituted vinyl group is directly bonded preferably has a molecular weight dispersity of 1.5 to 3.5, more preferably 2 to 3.

A polyimide precursor containing no aromatic ring to which an optionally substituted vinyl group is directly bonded is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative using a halogenating agent and then reacting it with a diamine.

In the method for producing a polyimide precursor that does not contain an aromatic ring to which an optionally substituted vinyl group is directly bonded, 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 according to the raw material, and examples thereof include the same organic solvents as those used in the synthesis of the polyimide precursor, which is the precursor of the specific heterocyclic ring-containing polymer.

When producing a polyimide precursor that does not contain an aromatic ring to which an optionally substituted vinyl group is directly bonded, it is preferable to include a step of precipitating a solid. Specifically, the polyimide precursor in the reaction solution is precipitated in water, and dissolved in a solvent such as tetrahydrofuran in which the polyimide precursor is soluble, whereby solid deposition can be performed.

[Polybenzoxazole Precursor Not Containing Aromatic Ring Directly Bonded with Optionally Substituted Vinyl Group]
The polybenzoxazole precursor that does not contain an aromatic ring directly bonded to an optionally substituted vinyl group preferably has a repeating unit represented by the above formula (2-2).
In addition, the polybenzoxazole precursor that does not contain an aromatic ring to which an optionally substituted vinyl group is directly bonded further contains a diamine residue represented by the above formula (SL) as another type of repeating unit. is preferred.
When the polybenzoxazole precursor that does not contain an aromatic ring to which an optionally substituted vinyl group is directly bonded contains a diamine residue represented by the formula (SL) as another type of repeating unit, the curable resin composition In order to improve the alkali solubility of the compound, it is preferable that the tetracarboxylic acid residue remaining after removal of the acid dianhydride group from the tetracarboxylic acid dianhydride is further included as a repeating unit. Examples of such tetracarboxylic acid residues include those of R ¹¹⁵ in formula (1).

The weight average molecular weight (Mw) of the polybenzoxazole precursor which does not contain an aromatic ring to which an optionally substituted vinyl group is directly bonded is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, 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 molecular weight dispersity of the polybenzoxazole precursor that does not contain an aromatic ring to which an optionally substituted vinyl group is directly bonded is preferably 1.5 to 3.5, more preferably 2 to 3.

〔Content〕
When the curable resin composition of the present invention contains another heterocycle-containing polymer precursor, the content of the other heterocycle-containing polymer precursor is 20% by mass or more relative to the total solid content of the curable resin composition. It is preferably 30% by mass or more, and even more preferably 40% by mass or more. Further, the content of the other heterocycle-containing polymer precursor in the curable resin composition of the present invention is preferably 99.5% by mass or less with respect to the total solid content of the curable resin composition. It is more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less.
The curable resin composition of the present invention may contain only one other heterocyclic ring-containing polymer precursor, or may contain two or more thereof. When two or more types are included, the total amount is preferably within the above range.

<Compound having two or more ethylenically unsaturated groups in the molecule>
The curable resin composition of the present invention preferably contains a compound having two or more ethylenically unsaturated groups in its molecule.
The compound having two or more ethylenically unsaturated groups in the molecule is preferably a compound having two or more aromatic rings to which optionally substituted vinyl groups are directly bonded.

<Compound having two or more aromatic rings to which optionally substituted vinyl groups are directly bonded in the molecule>
From the viewpoint of further improving chemical resistance, the curable resin composition of the present invention is a compound having two or more aromatic rings to which optionally substituted vinyl groups are directly bonded in the molecule (hereinafter referred to as "specific polymerization It is also referred to as "chemical compound".) is preferably included.

[Aromatic ring to which an optionally substituted vinyl group is directly bonded]
In the present specification, an aromatic ring to which an optionally substituted vinyl group is directly bonded means that one carbon atom in the double bond of the optionally substituted vinyl group is directly bonded to the aromatic ring structure. structure. The aromatic ring may have a known substituent such as an alkyl group or a halogeno group.
The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and the aromatic hydrocarbon ring or aromatic heterocyclic ring includes an aromatic hydrocarbon ring or an aliphatic hydrocarbon ring or An aromatic heterocycle or an aliphatic heterocycle may be condensed. Moreover, these aromatic hydrocarbon rings, aliphatic hydrocarbon rings, aromatic heterocycles or aliphatic heterocycles may each have a known substituent such as an alkyl group or a halogeno group.
The aromatic ring in the aromatic ring to which the optionally substituted vinyl group is directly bonded is preferably an aromatic hydrocarbon ring, more preferably a benzene ring.
That is, the specific polymerizable compound preferably contains a vinylphenyl group as the group containing the aromatic ring to which the vinyl group is directly bonded.
The number of aromatic rings to which a vinyl group is directly bonded in the specific polymerizable compound is preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 4, and 2 or 3. Especially preferred.
Further, the specific polymerizable compound may have an ethylenically unsaturated group other than the vinyl group in the aromatic ring to which the vinyl group is directly bonded. An embodiment having no ethylenically unsaturated groups other than the vinyl group is mentioned.
In addition, the vinyl group in the aromatic ring in the aromatic ring to which the vinyl group in the specific polymerizable compound is directly bonded preferably has radical polymerizability.
Further, examples of substituents in the vinyl group which may be substituted include an alkyl group and the like, and examples thereof include a mode in which α hydrogen in the vinyl group is substituted with a methyl group or the like.

The amount (molar amount) of the vinyl group in 1 g of the specific polymerizable compound is preferably 2 to 8 mol/g, more preferably 3 to 7 mol/g.

式（１－１）中、Ｚは２価以上の飽和脂肪族炭化水素基、２価以上の不飽和脂肪族炭化水素基、２価以上の炭化水素環基、－Ｏ－、－Ｓ－、－Ｎ（Ｒ^Ａ）－、－Ｃ（＝Ｏ）－Ｏ－、－Ｃ（Ｒ^Ａ）＝Ｎ－、－Ｃ（＝Ｏ）－、－Ｓ（＝Ｏ）_２－、２価以上の複素環基、及び、これらが２以上結合した基よりなる群から選ばれたｍ価の連結基であり、Ｒ^Ａは水素原子、アルキル基又はアリール基を表し、Ｒ^Ａが複数存在する場合、複数のＲ^Ａは同一であっても異なっていてもよく、Ｒ^１はそれぞれ独立に、水素原子又はメチル基を表し、ｍは２～６の整数を表す。
式（１－１）におけるベンゼン環における水素原子は、置換基により置換されていてもよい。置換基としては、本発明の目的が達成される限りにおいて特に限定されず、公知の置換基を用いることができる。また、これらの置換基を有しない態様も、本発明において好ましい態様である。[Compound Represented by Formula (1-1)]
The specific polymerizable compound is preferably a compound represented by the following formula (1-1).

In formula (1-1), Z is a divalent or higher saturated aliphatic hydrocarbon group, a divalent or higher unsaturated aliphatic hydrocarbon group, a divalent or higher hydrocarbon ring group, -O-, -S-, -N(R ^A )-, -C(=O)-O-, -C(R ^A )=N-, -C(=O)-, -S(=O) ₂ -, 2 or higher complex an m-valent linking group selected from the group consisting of a cyclic group and a group ⁱⁿ which two or more of these are bonded, ^RA represents a hydrogen atom, an alkyl group or an aryl group; R ¹ may be the same or different, each R ¹ independently represents a hydrogen atom or a methyl group, and m represents an integer of 2-6.
A hydrogen atom in the benzene ring in formula (1-1) may be substituted with a substituent. The substituent is not particularly limited as long as the object of the present invention is achieved, and known substituents can be used. Moreover, the aspect which does not have these substituents is also a preferable aspect in this invention.

-Z-
The bivalent or higher saturated aliphatic hydrocarbon group for Z is preferably a saturated aliphatic hydrocarbon group having 1 to 100 carbon atoms, more preferably a saturated aliphatic hydrocarbon group having 2 to 30 carbon atoms.
The above bivalent or higher aliphatic saturated hydrocarbon group is preferably a 2- to 20-valent aliphatic saturated hydrocarbon group, preferably a 2- to 10-valent aliphatic saturated hydrocarbon group. It is more preferably a saturated aliphatic hydrocarbon group.
In addition, the above bivalent or higher aliphatic saturated hydrocarbon group may have a known substituent as long as the effects of the present invention can be obtained.
The divalent or higher aliphatic unsaturated hydrocarbon group for Z is preferably an aliphatic unsaturated hydrocarbon group having 2 to 100 carbon atoms, more preferably an unsaturated aliphatic hydrocarbon group having 2 to 30 carbon atoms. preferable.
The above bivalent or higher aliphatic unsaturated hydrocarbon group is preferably a divalent to 20 valent aliphatic unsaturated hydrocarbon group, preferably a divalent to 10 valent aliphatic unsaturated hydrocarbon group, A divalent to hexavalent aliphatic unsaturated hydrocarbon group is more preferred.
In addition, the above divalent or higher aliphatic unsaturated hydrocarbon group may have a known substituent as long as the effects of the present invention can be obtained.
In formula (1-1), Z is preferably a group containing at least one selected from the group consisting of a divalent or higher valent hydrocarbon ring group and a divalent or higher heterocyclic group.

The divalent or higher valent hydrocarbon ring group for Z is preferably a divalent to tetravalent group obtained by removing 2 to 4 hydrogen atoms from a hydrocarbon ring.
The number of ring members of the hydrocarbon ring in the divalent or higher hydrocarbon ring group for Z is preferably 6 to 20, more preferably 6 to 12, even more preferably 6.
As the hydrocarbon ring in the divalent or higher hydrocarbon ring group for Z, an aromatic hydrocarbon ring is preferable, and a benzene ring is more preferable.

The divalent or higher heterocyclic group for Z is preferably a divalent to tetravalent group obtained by removing 2 to 4 hydrogen atoms from a heterocyclic ring.
The heteroatom (heteroatom) in the heterocyclic ring is preferably an oxygen atom, a nitrogen atom, a sulfur atom, or a selenium atom. Moreover, the number of heteroatoms contained as ring members in the heterocyclic ring is preferably 1 to 4.
The heterocyclic ring in the divalent or higher heterocyclic group represented by Z is preferably an aromatic heterocyclic ring, preferably an aromatic heterocyclic ring having 5 to 20 ring members, more preferably an aromatic heterocyclic ring having 5 to 20 ring members. The heterocyclic ring may be a condensed ring of multiple heterocyclic rings, or a condensed ring of a heterocyclic ring and an aromatic hydrocarbon ring. When the heterocyclic ring is a condensed ring, the monocyclic heterocyclic ring contained in the condensed ring preferably has 5 to 6 ring members.

From the viewpoint of improving intermolecular interaction and further improving chemical resistance, Z is a heterocyclic ring in the divalent or higher heterocyclic group, such as pyrrole ring, pyrazole ring, imidazole ring, triazole ring, tetrazole ring, iso oxazole ring, oxazole ring, oxadiazole ring, isothiazole ring, thiazole ring, thiadiazole ring, thiatriazole ring, indole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring, benzoselenazole ring, benzothiadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, quinoline ring, quinoxaline ring, furan ring, and at least one heterocyclic ring selected from the group consisting of a thiophene ring Pyrazole ring, imidazole ring, triazole ring, isoxazole ring, oxazole ring, oxadiazole ring, isothiazole ring, thiazole ring, thiadiazole ring, thiatriazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, More preferably, it contains at least one heterocyclic ring selected from the group consisting of a triazine ring, a quinoline ring, a quinoxaline ring, a furan ring, and a thiophene ring.

式（Ｚ－１）又は式（Ｚ－２）中、Ａ１及びＡ２はそれぞれ独立に、炭化水素環基又は複素環基を表し、Ｌ^Ｚ１～Ｌ^Ｚ５はそれぞれ独立に、アルキレン基、アルケニレン基、炭化水素環基、－Ｏ－、－Ｓ－、－Ｎ（Ｒ^Ａ）－、－Ｃ（＝Ｏ）－Ｏ－、－Ｃ（Ｒ^Ａ）＝Ｎ－、－Ｃ（＝Ｏ）－、－Ｓ（＝Ｏ）_２－、複素環基、及び、これらが２以上結合した基よりなる群から選ばれた２価の連結基を表し、Ｒ^Ａは水素原子、アルキル基又はアリール基を表し、Ｒ^Ａが複数存在する場合、複数のＲ^Ａは同一であっても異なっていてもよく、＊はそれぞれ独立に、式（１－１）におけるベンゼン環との結合部位を表す。Moreover, Z is preferably a group represented by the following formula (Z-1) or formula (Z-2).

In formula (Z-1) or formula (Z-2), A1 and A2 each independently represent a hydrocarbon ring group or a heterocyclic group, and L ^Z1 to L ^Z5 each independently represent an alkylene group, an alkenylene group, hydrocarbon ring group, -O-, -S-, -N(R ^A )-, -C(=O)-O-, -C(R ^A )=N-, -C(=O)-, - S(=O) ₂ —, a heterocyclic group, and a divalent linking group selected from the group consisting of groups in which two or more of these are bonded, R ^A represents a hydrogen atom, an alkyl group or an aryl group; When a plurality of ^RAs are present, the plurality of ^RAs may be the same or different, and each * independently represents a binding site to the benzene ring in formula (1-1).

<<A1 and A2>>
In formula (Z-1) or formula (Z-2), A1 and A2 are each independently preferably an aromatic hydrocarbon ring group or an aromatic heterocyclic group.
A benzene ring is preferable as the aromatic hydrocarbon ring in the aromatic hydrocarbon ring group.
Examples of the aromatic heterocyclic ring in the aromatic heterocyclic group include pyrrole ring, pyrazole ring, imidazole ring, triazole ring, tetrazole ring, isoxazole ring, oxazole ring, oxadiazole ring, isothiazole ring, thiazole ring, and thiadiazole ring. , thiatriazole ring, indole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring, benzoselenazole ring, benzothiadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring , quinoline ring, quinoxaline ring, furan ring, or thiophene ring are preferred, pyrazole ring, imidazole ring, triazole ring, isoxazole ring, oxazole ring, oxadiazole ring, isothiazole ring, thiazole ring, thiadiazole ring, thiatriazole A ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, quinoline ring, quinoxaline ring, furan ring, or thiophene ring is more preferable.

In formula (Z-1) or formula (Z-2), L ^Z1 to L ^Z5 are each independently an alkylene group, a divalent aromatic hydrocarbon ring group, —O—, —S—, —N(R ^A )-, -C(=O)-O-, -C(R ^A )=N-, -C(=O)-, -S(=O) ₂ -, divalent aromatic heterocyclic group, And, it is preferably a divalent linking group selected from the group consisting of two or more bonded groups, an alkylene group, a divalent aromatic hydrocarbon ring group, -O-, -S-, -N More preferably, (R ^A )— is a divalent linking group in which two or more are bonded.
R 1 ^A in formula (Z-1) or formula (Z-2) has the same meaning as R ¹ in formula (1-1) above, and preferred embodiments are also the same.
A phenyl group is preferable as the divalent aromatic hydrocarbon ring group.
Examples of the divalent aromatic heterocyclic group include pyrrole ring, pyrazole ring, imidazole ring, triazole ring, tetrazole ring, isoxazole ring, oxazole ring, oxadiazole ring, isothiazole ring, thiazole ring, thiadiazole ring, thia triazole ring, indole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring, benzoselenazole ring, benzothiadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, quinoline A divalent aromatic heterocyclic group obtained by removing two hydrogen atoms from a ring, a quinoxaline ring, a furan ring, or a thiophene ring is preferable, such as a pyrazole ring, an imidazole ring, a triazole ring, an isoxazole ring, an oxazole ring, and an oxadiazole ring. removing two hydrogen atoms from a ring, isothiazole ring, thiazole ring, thiadiazole ring, thiatriazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, quinoline ring, quinoxaline ring, furan ring, or thiophene ring A divalent aromatic heterocyclic group is more preferred.

^-RA-
In formula (1-1), R 1 ^A represents a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, more preferably a hydrogen atom.

-R ¹ -
In formula (1-1), R ¹ represents a hydrogen atom or a methyl group, more preferably a hydrogen atom.

-m-
In formula (1-1), m represents an integer of 2 to 6, preferably an integer of 2 to 4, more preferably 2 or 3.

The specific polymerizable compound preferably has a ratio of sp ³ carbon to the total number of atoms in Z excluding hydrogen atoms of 0.2 to 0.4.
Here, the ratio of sp ³ carbon to the total number of atoms excluding hydrogen atoms in Z is a value calculated by "the number of sp ³ carbon atoms contained in Z / the total number of atoms excluding hydrogen atoms in Z" .

[Molecular weight]
The molecular weight of the specific polymerizable compound may be determined in consideration of the cyclization temperature, volatility, etc., but is preferably 200 or more, more preferably 250 or more, and more preferably 300 or more. It is preferably 400 or more, and more preferably 400 or more. Although the upper limit is not particularly limited, it is preferably 2,000 or less.

〔Concrete example〕
Specific polymerizable compounds include, but are not limited to, the following compounds.

[Synthesis method]
A specific polymerizable compound is synthesized, for example, by the following method.
For example, compounds such as (B-1) to (B-5), (B-8) or (B-12) are known thioetherification reactions such as reacting polyhydric mercapto compounds with halogenomethylstyrene. obtained by
Compounds such as (B-6), (B-7), (B-9) or (B-11) are known ethers such as reacting polyhydric alcohol compounds with halogenomethylstyrene or halogenated styrene. obtained by chemical reaction.
A compound such as (B-10) can be obtained by a known esterification reaction such as reacting a polyhydric alcohol compound with a vinyl benzoic acid halide.

〔Content〕
When the curable resin composition of the present invention contains a specific polymerizable compound, the content of the specific polymerizable compound is from the viewpoint of improving the storage stability of the curable resin composition and the elongation at break of the resulting cured film. is preferably 0.005 to 50% by mass based on the total solid content of the curable resin composition. The lower limit is more preferably 0.05% by mass or more, still more preferably 0.5% by mass or more, particularly preferably 1% by mass or more, and most preferably 3% by mass or more.
From the viewpoint of the mechanical properties of the cured film, the upper limit of the content is more preferably 40% by mass or less, still more preferably 30% by mass or less, and particularly preferably 20% by mass or less.
The curable resin composition of the present invention may contain only one type of specific polymerizable compound, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<Other polyfunctional polymerizable compounds>
A compound having two or more ethylenically unsaturated groups in the molecule is a compound having two or more ethylenically unsaturated groups other than an aromatic ring to which an optionally substituted vinyl group is directly bonded ("Other polyfunctional polymerization (also referred to as "chemical compound").
The other polyfunctional polymerizable compound may have one aromatic ring to which an optionally substituted vinyl group is directly bonded, or has an aromatic ring to which an optionally substituted vinyl group is directly bonded. It doesn't have to be.
A compound having two or more aromatic rings to which optionally substituted vinyl groups are directly bonded and having two or more ethylenically unsaturated groups other than the aromatic rings to which optionally substituted vinyl groups are directly bonded corresponds to the specific polymerizable compound described above and does not correspond to other polyfunctional polymerizable compounds.

Examples of groups having an ethylenically unsaturated group in other polyfunctional polymerizable compounds include vinyl groups, allyl groups, vinylphenyl groups, (meth)acryloyl groups, etc. Among these, (meth)acryloyl groups are preferred. A (meth)acryloxy group is more preferred from the viewpoint of reactivity.

The number of groups having an ethylenically unsaturated group in the other polyfunctional polymerizable compound may be 1 or 2 or more, and preferably 3 or more. The upper limit is preferably 15 or less, more preferably 10 or less, even more preferably 8 or less.

The molecular weight of the other polyfunctional polymerizable compound 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 other polyfunctional polymerizable compounds is preferably 100 or more.

From the viewpoint of developability, the other polyfunctional polymerizable compound preferably contains at least one difunctional or higher polyfunctional polymerizable compound, and more preferably contains at least one trifunctional or higher polyfunctional polymerizable compound. . It may also be a mixture of a bifunctional polyfunctional polymerizable compound and a trifunctional or higher polyfunctional polymerizable compound.
A bifunctional polyfunctional polymerizable compound refers to a polyfunctional polymerizable compound having two groups having the above ethylenically unsaturated groups.

Specific examples of other polyfunctional polymerizable compounds include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides. Esters of unsaturated carboxylic acids and polyhydric alcohol compounds and amides of unsaturated carboxylic acids and polyhydric amine compounds are preferred. 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.

Further, the other polyfunctional polymerizable compound is 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 (meth)acrylate, trimethylolpropane tri(acryloyloxypropyl)ether, tri(acryloyloxyethyl)isocyanurate, glycerin and trimethylolethane. Compounds obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth)acrylated are 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)acryl Polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products with acids, 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 other preferred polyfunctional polymerizable compounds other than those described above, JP-A-2010-160418, JP-A-2010-129825, JP-A-4364216, etc., having a fluorene ring and ethylenic Compounds having two or more groups having unsaturated bonds and cardo resins can also be used.

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, pages 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 another polyfunctional polymerizable compound.

Furthermore, compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as other polyfunctional polymerizable compounds, the contents of which are incorporated herein.

Other polyfunctional polymerizable compounds include dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; Japan Kayaku Co., Ltd., A-TMMT: Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; Nippon Kayaku Co., Ltd.), dipenta Erythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.), and these (meth) acryloyl groups are ethylene glycol residues or propylene glycol Structures that are linked via residues are preferred. These oligomeric types can also be used.

Other commercially available polyfunctional polymerizable compounds include, for example, SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, and a bifunctional methacrylate having four ethyleneoxy chains, manufactured by Sartomer. SR-209, 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 (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blenmer PME400 (NOF Corporation) made), etc.

Other polyfunctional polymerizable compounds include urethanes as described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, and JP-B-02-016765. Acrylates and 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. be. Furthermore, as the radically polymerizable compound, compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238 are used. can also be used.

Other polyfunctional polymerizable compounds may be radically polymerizable compounds having acid groups such as carboxy groups and phosphoric acid groups. The radically polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. A radically polymerizable compound having a group is more preferred. Particularly preferably, in a radically polymerizable compound 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 dipenta A compound that is erythritol. Examples of commercially available products include polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd. such as M-510 and M-520.

The other polyfunctional polymerizable compound having an acid group preferably has an acid value of 0.1 to 40 mgKOH/g, particularly preferably 5 to 30 mgKOH/g. If the acid value of the other polyfunctional polymerizable compound is within the above range, the handleability in production is excellent, and further, the developability is excellent. Moreover, the polymerizability is good. The acid value is measured according to JIS K 0070:1992.

When other polyfunctional polymerizable compounds are contained, the content thereof is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the curable 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.
Other polyfunctional polymerizable compounds may be used singly or in combination of two or more. When two or more are used in combination, the total amount is preferably within the above range.

<Other polymerizable compounds>
The curable resin composition of the present invention may further contain polymerizable compounds other than the specific polymerizable compound and other polyfunctional polymerizable compounds described above.
Other polymerizable compounds include monofunctional radically polymerizable compounds; compounds having a hydroxymethyl group, alkoxymethyl group or acyloxymethyl group; epoxy compounds; oxetane compounds; and benzoxazine compounds.

[Monofunctional Radical Polymerizable Compound]
The curable resin composition of the present invention may further contain a monofunctional radically polymerizable compound from the viewpoint of suppressing warpage associated with elastic modulus control of the cured film. Monofunctional radically polymerizable compounds include n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl ( (Meta) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc. ) Acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allyl glycidyl ether, diallyl phthalate and triallyl trimellitate are preferably used. As the monofunctional radically polymerizable compound, a compound having a boiling point of 100° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.

[Compound having hydroxymethyl group, alkoxymethyl group or acyloxymethyl group]
Compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group are preferably compounds represented by the following formulas (AM1), (AM4) or (AM5).

（式中、ｔは、１～２０の整数を示し、Ｒ^１０４は炭素数１～２００のｔ価の有機基を示し、Ｒ^１０５は、－ＯＲ^１０６又は、－ＯＣＯ－Ｒ^１０７で示される基を示し、Ｒ^１０６は、水素原子又は炭素数１～１０の有機基を示し、Ｒ^１０７は、炭素数１～１０の有機基を示す。）

（式中、Ｒ^４０４は炭素数１～２００の２価の有機基を示し、Ｒ^４０５は、－ＯＲ^４０６又は、－ＯＣＯ－Ｒ^４０７で示される基を示し、Ｒ^４０６は、水素原子又は炭素数１～１０の有機基を示し、Ｒ^４０７は、炭素数１～１０の有機基を示す。）

（式中ｕは３～８の整数を示し、Ｒ^５０４は炭素数１～２００のｕ価の有機基を示し、Ｒ^５０５は、－ＯＲ^５０６又は、－ＯＣＯ－Ｒ^５０７で示される基を示し、Ｒ^５０６は、水素原子又は炭素数１～１０の有機基を示し、Ｒ^５０７は、炭素数１～１０の有機基を示す。）

(Wherein, t represents an integer of 1 to 20, R ¹⁰⁴ represents a t-valent organic group having 1 to 200 carbon atoms, and R ¹⁰⁵ represents a group represented by —OR ¹⁰⁶ or —OCO—R ¹⁰⁷ , R ¹⁰⁶ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R ¹⁰⁷ represents an organic group having 1 to 10 carbon atoms.)

(Wherein, R ⁴⁰⁴ represents a divalent organic group having 1 to 200 carbon atoms, R ⁴⁰⁵ represents a group represented by -OR ⁴⁰⁶ or -OCO-R ⁴⁰⁷ , and R ⁴⁰⁶ represents a hydrogen atom or carbon represents an organic group having 1 to 10 carbon atoms, and R ⁴⁰⁷ represents an organic group having 1 to 10 carbon atoms.)

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

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

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

[Epoxy compound (compound having an epoxy group)]
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a cross-linking reaction at 200° C. or 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 curable resin composition.

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 resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; Epoxy group-containing silicones such as (oxypropyl)siloxane, etc., but not limited to these. 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) EXA-4710, Epiclon (registered trademark) HP-4770, Epiclon (registered trademark) EXA-859CRP, Epiclon (registered trademark) EXA-1514, Epiclon (registered trademark) EXA-4880, Epiclon (registered trademark) EXA-4850-150, Epiclon EXA-4850-1000, Epiclon (registered trademark) EXA-4816, Epiclon (registered trademark) EXA-4822 (trade names, manufactured by DIC Corporation), Ricaresin (registered trademark) BEO-60E (trade name, Shin Nippon Rika Co., Ltd.), EP-4003S, EP-4000S (trade names, manufactured by ADEKA Corporation), and the like. Among these, an epoxy resin containing a polyethylene oxide group is preferable from the viewpoint of suppressing warpage and being excellent in heat resistance. For example, Epiclon (registered trademark) EXA-4880, Epiclon (registered trademark) EXA-4822, and Ricaresin (registered trademark) BEO-60E are preferable because they contain polyethylene oxide groups.

[Oxetane compound (compound having an oxetanyl group)]
The 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. (e.g., OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used. Or you may mix 2 or more types.

[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 Ba-type benzoxazine, Bm-type benzoxazine (these are trade names, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resins, phenol novolac dihydrobenzoxazine oxazine compounds. These may be used alone or in combination of two or more.

When other polymerizable compounds are contained, the content is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the curable 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.
Moreover, the curable resin composition of the present invention can also be in an aspect in which it does not substantially contain other polymerizable compounds. In such an aspect, for example, the content of the other polymerizable compound is preferably 0 to 5% by mass, based on the total solid content of the curable resin composition of the present invention, and 0 to 1 mass %, more preferably 0 to 0.1% by mass. Moreover, 0 mass % may be sufficient as the said content.
Other polymerizable compounds may be used singly or in combination of two or more. When two or more are used in combination, the total amount is preferably within the above range.

<Onium salt>
The curable resin composition of the present invention preferably contains an onium salt.
Although the type of onium salt is not particularly limited, ammonium salts, iminium salts, sulfonium salts, iodonium salts and phosphonium salts are preferred.
Among these, ammonium salts or iminium salts are preferred from the viewpoint of high thermal stability, and sulfonium salts, iodonium salts or phosphonium salts are preferred from the viewpoint of compatibility with polymers.

In addition, an onium salt is a salt of a cation having an onium structure and an anion, and the cation and anion may be bonded via a covalent bond or may not be bonded via a covalent bond. .
That is, the onium salt may be an intramolecular salt having a cation part and an anion part in the same molecular structure, or a cation molecule and an anion molecule, which are different molecules, are ionically bonded. It may be an intermolecular salt, but an intermolecular salt is preferred. Moreover, in the curable resin composition of the present invention, the cationic moiety or cationic molecule and the anionic moiety or anionic molecule may be bonded or dissociated by an ionic bond.
The cations in the onium salt are preferably ammonium cations, pyridinium cations, sulfonium cations, iodonium cations or phosphonium cations, and more preferably at least one cation selected from the group consisting of tetraalkylammonium cations, sulfonium cations and iodonium cations.

The onium salt used in the present invention may be a thermal base generator, which will be described later.
A thermal base generator is a compound that generates a base upon heating, and includes, for example, a compound that generates a base when heated to 40° C. or higher.

[Ammonium salt]
In the present invention, an ammonium salt means a salt of an ammonium cation and an anion.

式（１０１）中、Ｒ^１～Ｒ^４はそれぞれ独立に、水素原子又は炭化水素基を表し、Ｒ^１～Ｒ^４の少なくとも２つはそれぞれ結合して環を形成してもよい。-Ammonium cation-
Preferred ammonium cations are quaternary ammonium cations.
Moreover, as the ammonium cation, a cation represented by the following formula (101) is preferable.

In formula (101), R ¹ to R ⁴ each independently represent a hydrogen atom or a hydrocarbon group, and at least two of R ¹ to R ⁴ may combine to form a ring.

In formula (101), R ¹ to R ⁴ are each independently preferably a hydrocarbon group, more preferably an alkyl group or an aryl group, and an alkyl group having 1 to 10 carbon atoms or 6 to 6 carbon atoms. 12 aryl groups are more preferred. R ¹ to R ⁴ may have substituents, and examples of substituents include hydroxy group, aryl group, alkoxy group, aryloxy group, arylcarbonyl group, alkylcarbonyl group, alkoxycarbonyl group, aryloxy A carbonyl group, an acyloxy group, and the like can be mentioned.
When at least two of R ¹ to R ⁴ each combine to form a ring, the ring may contain a heteroatom. A nitrogen atom is mentioned as said hetero atom.

The ammonium cation is preferably represented by either formula (Y1-1) or (Y1-2) below.

In formulas (Y1-1) and (Y1-2), R ¹⁰¹ represents an n-valent organic group, R ¹ has the same definition as R ¹ in formula (101), and Ar ¹⁰¹ and Ar ¹⁰² are each independently , represents an aryl group, and n represents an integer of 1 or more.
In formula (Y1-1), R ¹⁰¹ is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from a structure in which these are bonded, and has 2 to 30 carbon atoms. is more preferably a group obtained by removing n hydrogen atoms from saturated aliphatic hydrocarbon, benzene or naphthalene.
In formula (Y1-1), n is preferably 1 to 4, more preferably 1 or 2, even more preferably 1.
In formula (Y1-2), Ar ¹⁰¹ and Ar ¹⁰² are each independently preferably a phenyl group or a naphthyl group, more preferably a phenyl group.

－Anion－
The anion in the ammonium salt is preferably one selected from carboxylate anions, phenol anions, phosphate anions and sulfate anions, and carboxylate anions are more preferable because both salt stability and thermal decomposition can be achieved. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion.
The carboxylate anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxy groups, more preferably an anion of a divalent carboxylic acid. According to this aspect, the stability, curability and developability of the curable resin composition can be further improved. In particular, by using a divalent carboxylic acid anion, the stability, curability and developability of the curable resin composition can be further improved.

式（Ｘ１）において、ＥＷＧは、電子求引性基を表す。The carboxylate anion is preferably represented by the following formula (X1).

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

In the present embodiment, the electron-withdrawing group means a group having a positive Hammett's substituent constant σm. Here, σm is described in Yuho Tsuno Review, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965) p. 631-642. In addition, the electron-withdrawing group in the present embodiment is not limited to the substituents described in the above documents.
Examples of substituents in which σm shows a positive value include a CF ₃ group (σm=0.43), a CF ₃ C(=O) group (σm=0.63), and an HC≡C group (σm=0. 21), CH ₂ =CH group (σm = 0.06), Ac group (σm = 0.38), MeOC(=O) group (σm = 0.37), MeC(=O)CH=CH group ( σm=0.21), PhC(=O) group (σm=0.34), H ₂ NC(=O)CH ₂ group (σm=0.06), and the like. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (hereinafter the same).

式（ＥＷＧ－１）～（ＥＷＧ－６）中、Ｒ^ｘ１～Ｒ^ｘ３は、それぞれ独立に、水素原子、アルキル基、アルケニル基、アリール基、ヒドロキシ基又はカルボキシ基を表し、Ａｒは芳香族基を表す。EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).

In formulas (EWG-1) to (EWG-6), R ^x1 to R ^x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxy group or a carboxy group, and Ar is an aromatic group. represents

式（ＸＡ）において、Ｌ^１０は、単結合、又は、アルキレン基、アルケニレン基、芳香族基、－ＮＲ^Ｘ－及びこれらの組み合わせよりなる群から選ばれる２価の連結基を表し、Ｒ^Ｘは、水素原子、アルキル基、アルケニル基又はアリール基を表す。In the present invention, the carboxylate anion is preferably represented by the following formula (XA).

In formula (XA), L ¹⁰ represents a single bond or a divalent linking group selected from the group consisting of an alkylene group, an alkenylene group, an aromatic group, —NR ^X — and combinations thereof, and R ^X is , represents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group.

Specific examples of carboxylate anions include maleate, phthalate, N-phenyliminodiacetate and oxalate anions.

The onium salt in the present invention contains an ammonium cation as a cation, and the onium salt is an anion, because the cyclization of the specific precursor is easily performed at a low temperature and the storage stability of the curable resin composition is easily improved. As, it preferably contains an anion having a conjugate acid pKa (pKaH) of 2.5 or less, more preferably 1.8 or less.
The lower limit of the pKa is not particularly limited, but it is preferably -3 or more, and -2 or more from the viewpoint that the generated base is hardly neutralized and the cyclization efficiency of the specific precursor is improved. is more preferable.
The above pKa is determined according to Determination of Organic Structures by Physical Methods (authors: Brown, H.C., McDaniel, D.H., Hafliger, O., Nachod, F.C.; compilation: Braude, E.A. ， Nachod, F. C.; Academic Press, New York, 1955) and Data for Biochemical Research (authors: Dawson, RMC et al; Oxford, Clarendon Press, 1959). can be done. For compounds not described in these documents, values calculated from structural formulas using software ACD/pKa (manufactured by ACD/Labs) are used.

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

[Iminium salt]
In the present invention, an iminium salt means a salt of an iminium cation and an anion. Examples of the anion include the same anions as those in the ammonium salt described above, and preferred embodiments are also the same.

-iminium cation-
Preferred iminium cations are pyridinium cations.
As the iminium cation, a cation represented by the following formula (102) is also preferable.

In formula (102), R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, R ⁷ represents a hydrocarbon group, and at least two of R ⁵ to R ⁷ each combine to form a ring. may be formed.
In formula (102), R ⁵ and R ⁶ have the same definitions as R1 to R4 in formula (101) above, and preferred embodiments are also the same.
In formula (102), R ⁷ preferably combines with at least one of R ⁵ and R ⁶ to form a ring. The ring may contain heteroatoms. A nitrogen atom is mentioned as said hetero atom. Moreover, as said ring, a pyridine ring is preferable.

式（Ｙ１－３）～（Ｙ１－５）において、Ｒ^１０１は、ｎ価の有機基を表し、Ｒ^５は式（１０２）におけるＲ^５と同義であり、Ｒ^７は式（１０２）におけるＲ^７と同義であり、ｎ及びｍは、１以上の整数を表す。
式（Ｙ１－３）において、Ｒ^１０１は、脂肪族炭化水素、芳香族炭化水素、又は、これらが結合した構造からｎ個の水素原子を除いた基であることが好ましく、炭素数２～３０の飽和脂肪族炭化水素、ベンゼン又はナフタレンからｎ個の水素原子を除いた基であることがより好ましい。
式（Ｙ１－３）において、ｎは１～４であることが好ましく、１又は２であることがより好ましく、１であることが更に好ましい。
式（Ｙ１－５）において、ｍは０～４であることが好ましく、１又は２であることがより好ましく、１であることが更に好ましい。The iminium cation is preferably represented by any one of the following formulas (Y1-3) to (Y1-5).

In formulas (Y1-3) to (Y1-5), R ¹⁰¹ represents an n-valent organic group, R ⁵ has the same definition as R ⁵ in formula (102), and R ⁷ represents R in formula (102). is synonymous with ⁷ , and n and m represent an integer of 1 or more.
In formula (Y1-3), R ¹⁰¹ is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from a structure in which these are bonded, and has 2 to 30 carbon atoms. is more preferably a group obtained by removing n hydrogen atoms from saturated aliphatic hydrocarbon, benzene or naphthalene.
In formula (Y1-3), n is preferably 1 to 4, more preferably 1 or 2, even more preferably 1.
In formula (Y1-5), m is preferably 0 to 4, more preferably 1 or 2, even more preferably 1.

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

[Sulfonium salt]
In the present invention, a sulfonium salt means a salt of a sulfonium cation and an anion. Examples of the anion include the same anions as those in the ammonium salt described above, and preferred embodiments are also the same.

-Sulfonium cation-
As the sulfonium cation, a tertiary sulfonium cation is preferred, and a triarylsulfonium cation is more preferred.
Moreover, as the sulfonium cation, a cation represented by the following formula (103) is preferable.

In formula (103), R ⁸ to R ¹⁰ each independently represent a hydrocarbon group.
R ⁸ to R ¹⁰ are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. is more preferably an aryl group, more preferably a phenyl group.
R ⁸ to R ¹⁰ may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, and an aryloxy group. A carbonyl group, an acyloxy group, and the like can be mentioned. Among these, as a substituent, it is preferable to have an alkyl group or an alkoxy group, more preferably to have a branched alkyl group or an alkoxy group, a branched alkyl group having 3 to 10 carbon atoms, or a branched alkyl group having 1 to 1 carbon atoms More preferably it has 10 alkoxy groups.
R ⁸ to R ¹⁰ may be the same group or different groups, but from the viewpoint of synthesis suitability, they are preferably the same group.

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

[Iodonium salt]
In the present invention, an iodonium salt means a salt of an iodonium cation and an anion. Examples of the anion include the same anions as those in the ammonium salt described above, and preferred embodiments are also the same.

-Iodonium cation-
As the iodonium cation, a diaryliodonium cation is preferred.
Moreover, as the iodonium cation, a cation represented by the following formula (104) is preferable.

In formula (104), R ¹¹ and R ¹² each independently represent a hydrocarbon group.
R ¹¹ and R ¹² are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. is more preferably an aryl group, more preferably a phenyl group.
R ¹¹ and R ¹² may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxy A carbonyl group, an acyloxy group, and the like can be mentioned. Among these, as a substituent, it is preferable to have an alkyl group or an alkoxy group, more preferably to have a branched alkyl group or an alkoxy group, a branched alkyl group having 3 to 10 carbon atoms, or a branched alkyl group having 1 to 10 carbon atoms It is more preferable to have an alkoxy group of
R ¹¹ and R ¹² may be the same group or different groups, but from the viewpoint of synthesis suitability, they are preferably the same group.

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

[Phosphonium salt]
In the present invention, a phosphonium salt means a salt of a phosphonium cation and an anion. Examples of the anion include the same anions as those in the ammonium salt described above, and preferred embodiments are also the same.

-Phosphonium cation-
The phosphonium cation is preferably a quaternary phosphonium cation, and examples thereof include tetraalkylphosphonium cations and triarylmonoalkylphosphonium cations.
Moreover, as the phosphonium cation, a cation represented by the following formula (105) is preferable.

In formula (105), R ¹³ to R ¹⁶ each independently represent a hydrogen atom or a hydrocarbon group.
R ¹³ to R ¹⁶ are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. is more preferably an aryl group, more preferably a phenyl group.
R ¹³ to R ¹⁶ may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, and an aryloxy group. A carbonyl group, an acyloxy group, and the like can be mentioned. Among these, as a substituent, it is preferable to have an alkyl group or an alkoxy group, more preferably to have a branched alkyl group or an alkoxy group, a branched alkyl group having 3 to 10 carbon atoms, or a branched alkyl group having 1 to 10 carbon atoms It is more preferable to have an alkoxy group of
R ¹³ to R ¹⁶ may be the same group or different groups, but from the viewpoint of synthesis suitability, they are preferably the same group.

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

When the curable resin composition of the present invention contains an onium salt, the content of the onium salt is preferably 0.1 to 50% by mass based on the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, still more preferably 0.85% by mass or more, and even more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, still more preferably 20% by mass or less, even more preferably 10% by mass or less, and may be 5% by mass or less, or may be 4% by mass or less.
One or two or more onium salts can be used. When two or more kinds are used, the total amount is preferably within the above range.

<Thermal base generator>
The curable resin composition of the present invention may contain a thermal base generator.
The thermal base generator may be a compound corresponding to the onium salt described above, or may be a thermal base generator other than the onium salt described above.
Other thermal base generators include nonionic thermal base generators.
Nonionic thermal base generators include compounds represented by formula (B1) or formula (B2).

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, 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 (having preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, more preferably 3 to 12 carbon atoms, and still more preferably 3 to 12 carbon atoms) which may have a substituent, more preferably 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.

The molecular weight of the nonionic thermal 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.

Among the above-mentioned onium salts, specific examples of compounds that are thermal base generators or specific examples of other thermal base generators include the following compounds.

The content of the thermal base generator is preferably 0.1 to 50% by mass based on the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and even more preferably 20% by mass or less. One or two or more thermal base generators can be used. When two or more kinds are used, the total amount is preferably within the above range.

<Photoinitiator>
The curable resin composition of the present invention preferably contains a photopolymerization initiator.
The photopolymerization initiator may be a photocationic polymerization initiator, but 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 photo-radical polymerization initiator having curability with respect 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 range of about 300 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 preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.

As the radical photopolymerization initiator, 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, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. mentioned. 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.

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 (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

Hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used as photoradical polymerization initiators. 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 also be used.

As the hydroxyacetophenone initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.

As the aminoacetophenone-based initiator, commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.

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

Acylphosphine-based initiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and the like. In addition, commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) can be used.

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

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, and compounds described in JP-A-2006-342166.

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 curable resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as a radical photopolymerization initiator. An oxime-based photopolymerization initiator has a linking group represented by >C=N--O--C(=O)- 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 2012-014052 A radical polymerization initiator 2) is also preferably used. In addition, TR-PBG-304 (manufactured by Changzhou Yuan Electronics New Materials Co., Ltd.), Adeka Arkles NCI-831 and Adeka Arkles NCI-930 (manufactured by ADEKA Co., Ltd.) can also be used. Also, DFI-091 (manufactured by Daito Chemix Co., Ltd.) can be used.

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. Examples thereof include compound (C-3) described in paragraph 0101 of JP-A-164471.

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

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. More preferably, at least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds, more preferably metallocene compounds or oxime compounds, and oxime compounds. is 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, 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, and 2 to 2 carbon atoms interrupted by one or more oxygen atoms; a phenyl group substituted with at least one of an alkyl group of 18 and an alkyl group having 1 to 4 carbon atoms, or biphenyl, and R ^I01 is a group represented by formula (II) or is the same as R ^I00 and each of R ¹⁰² to R ¹⁰⁴ is independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or halogen.

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

Further, as the radical photopolymerization initiator, compounds described in paragraphs 0048 to 0055 of WO 2015/125469 can also be used.

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 curable 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 is preferably within the above range.

<Thermal polymerization initiator>
The curable resin composition of the present invention may contain a thermal polymerization initiator, particularly a thermal radical polymerization initiator, as a polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals by heat energy and initiates or promotes a polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction of the specific heterocycle-containing polymer precursor can be progressed together with the cyclization of the specific heterocycle-containing polymer precursor, so that a higher degree of heat resistance can be achieved. Become.

Specific examples of thermal radical polymerization initiators include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.

When a thermal radical 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 curable resin composition of the present invention. %, more preferably 5 to 15% by mass. One type of thermal radical polymerization initiator may be contained, or two or more types may be contained. When two or more thermal radical polymerization initiators are contained, the total is preferably within the above range.

<Solvent>
The curable 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, aromatic hydrocarbons, sulfoxides, and amides.

Esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone , δ-valerolactone, 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., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- methyl ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionate alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate) etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyloxy-2-methylpropion methyl acid and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, pyruvate Suitable examples include propyl acid, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like.

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Preferred examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like.

Preferred examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone.

Suitable examples of aromatic hydrocarbons include toluene, xylene, anisole, limonene, and the like.

Suitable sulfoxides include, for example, dimethyl sulfoxide.

Suitable amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide 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- 1 solvent selected from butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, or composed of two or more solvents A mixed solvent is preferred. A combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

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

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

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

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), compounds having thioureas and sulfanyl groups, hindered phenolic compounds , salicylic acid derivative-based compounds, and hydrazide derivative-based compounds. In particular, triazole compounds such as 1,2,4-triazole and benzotriazole, and tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole are 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. Compounds described in paragraph 0052, compounds described in paragraphs 0114, 0116 and 0118 of JP-A-2012-194520, compounds described in paragraph 0166 of WO 2015/199219, and the like can be used.

Specific examples of migration inhibitors include the following compounds.

When the curable resin composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the curable resin composition, and 0 It is more preferably from 0.05 to 2.0% by mass, and even more preferably from 0.1 to 1.0% by mass.

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

Polymerization inhibitors include, for example, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4' -thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine , N-phenylnaphthylamine, 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 and the like 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.

For example, the following compounds can be used (Me is a methyl group).

When the curable resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is 0.01 to 5% by mass with respect to the total solid content of the curable resin composition of the present invention. is preferred, 0.02 to 3 mass % is more preferred, and 0.05 to 2.5 mass % is even more preferred.

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.

<Metal adhesion improver>
The curable 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. A silane coupling agent etc. are mentioned as a metal adhesion improving agent.

Examples of silane coupling agents 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 are included. 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 formulas below, Et represents an ethyl group.

Further, as the metal adhesion improver, 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 also be used. .

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass when the total amount of the specific heterocycle-containing polymer precursor and the other heterocycle-containing polymer precursor is 100 parts by mass. , more preferably in the range of 0.5 to 15 parts by mass, more preferably in the range of 0.5 to 5 parts by mass. When it is at least the above lower limit value, the adhesiveness between the cured film and the metal layer after the curing step is improved, and when it is at most the above upper limit value, the heat resistance and mechanical properties of the cured film after the curing step 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.

<Other additives>
The curable resin composition of the present invention may contain various additives, such as thermal acid generators, sensitizers such as N-phenyldiethanolamine, and chain transfer agents, as long as the effects of the present invention are not impaired. , surfactants, higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, anti-aggregation agents and the like can be added. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the curable resin composition.

[Sensitizer]
The curable resin composition of the present invention may contain a sensitizer. A sensitizer absorbs specific actinic radiation and enters an electronically excited state. The electronically excited sensitizer comes into contact with a thermal curing accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, and the like, and causes electron transfer, energy transfer, heat generation, and the like. As a result, the thermosetting accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo chemical changes and are decomposed to generate radicals, acids, or bases.
Sensitizers include N-phenyldiethanolamine and the like.
Moreover, you may use a sensitizing dye as a sensitizer.
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 curable resin composition of the present invention contains a sensitizer, the content of the sensitizer is 0.01 to 20% by mass with respect to the total solid content of the curable resin composition of the present invention. It is preferably from 0.1 to 15% by mass, and even more preferably from 0.5 to 10% by mass. The sensitizers may be used singly or in combination of two or more.

[Chain transfer agent]
The curable resin composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in Kobunshi Dictionary, 3rd edition (edited by Kobunshi Gakkai, 2005), pp. 683-684. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. They can 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.

When the curable resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the curable resin composition of the present invention. It is preferably 1 to 10 parts by mass, and even more preferably 1 to 5 parts by mass. 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.

また、界面活性剤は、国際公開第２０１５／１９９２１９号の段落０１５９～０１６５に記載の化合物を用いることもできる。[Surfactant]
Various types of surfactants may be added to the curable resin composition of the present invention from the viewpoint of further improving coatability. As the surfactant, various kinds of surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants and silicone surfactants can be used. The following surfactants are also preferred. In the following formula, the parenthesis indicating the repeating unit of the main chain indicates the content (mol %) of each repeating unit, and the parenthesis indicating the repeating unit of the side chain indicates the repeating number of each repeating unit.

In addition, surfactants can also be used compounds described in paragraphs 0159 to 0165 of WO 2015/199219.

When the curable resin composition of the present invention has a surfactant, the content of the surfactant is 0.001 to 2.0% by mass with respect to the total solid content of the curable resin composition of the present invention. preferably 0.005 to 1.0% by mass. One type of surfactant may be used, or two or more types may be used. When two or more surfactants are used, the total is preferably within the above range.

[Higher Fatty Acid Derivative]
In the curable 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. It may be unevenly distributed on the surface of the object.

Moreover, the higher fatty acid derivative can also use the compound of the paragraph 0155 of international publication 2015/199219.

When the curable resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is 0.1 to 10% by mass with respect to the total solid content of the curable resin composition of the present invention. is preferred. 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.

<Restrictions on other contained substances>
The water content of the curable resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass, from the viewpoint of coated surface properties.

From the viewpoint of insulation, the metal content of the curable resin composition of the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Metals include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. 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 curable resin composition of the present invention, a raw material having a low metal content is selected as a raw material constituting the curable resin composition of the present invention. Examples include methods such as performing filter filtration on the raw materials constituting the curable resin composition of the invention, and lining the inside of the apparatus with polytetrafluoroethylene or the like to perform distillation under conditions that suppress contamination as much as possible. be able to.

Considering the use as a semiconductor material, the curable resin composition of the present invention has a halogen atom content of preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, more preferably less than 300 ppm by mass, from the viewpoint of wiring corrosion resistance. Less than ppm 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.

Conventionally known containers can be used as the container for the curable resin composition of the present invention. In addition, for the storage container, for the purpose of suppressing the contamination of the raw material and the curable resin composition, a multi-layer bottle whose inner wall is made of 6 types and 6 layers of resin, and 7 types of 6 types of resin are used. It is also preferred to use a layered bottle. Examples of such a container include the container described in JP-A-2015-123351.

<Preparation of curable resin composition>
The curable 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.

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 curable resin composition. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. 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. Also, various materials may be filtered multiple times. When filtering multiple times, circulation filtration may be used. Moreover, you may filter by pressurizing. When pressurizing and filtering, the pressure to pressurize is preferably 0.05 MPa or more and 0.3 MPa or less.
In addition to filtration using a filter, impurities may be removed using an adsorbent. 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.

<Application of curable resin composition>
The curable resin composition of the present invention is preferably used for forming an interlayer insulating film for rewiring layers.
In addition, it can also be used for forming an insulating film of a semiconductor device, forming a stress buffer film, or the like.

(Cured film, laminate, semiconductor device, and manufacturing method thereof)
Next, cured films, laminates, semiconductor devices, and manufacturing methods thereof will be described.

The cured film of the present invention is obtained by curing the curable resin composition of the present invention. The film thickness of the cured film of the present invention can be, for example, 0.5 μm or more, and can be 1 μm or more. Moreover, as an upper limit, it can be set to 100 μm or less, and can also be set to 30 μm or less.

Two or more layers of the cured film of the present invention, or three to seven layers may be laminated to form a laminate. It is preferable that the laminate of the present invention contains two or more cured films and a metal layer between any of the cured films. For example, a laminate containing at least a layer structure in which three layers of a first cured film, a metal layer, and a second cured film are laminated in this order is preferred. Both the first cured film and the second cured film are cured films of the present invention, for example, both the first cured film and the second cured film have the curability of the present invention A preferred embodiment is a film obtained by curing a resin composition. The curable resin composition of the present invention used for forming the first cured film and the curable resin composition of the present invention used for forming the second cured film have the same composition. may be present, or may be compositions having different compositions. The metal layer in the laminate of the present invention is preferably used as a metal wiring such as a rewiring layer.

Fields to which the cured film of the present invention can be applied include insulating films for semiconductor devices, interlayer insulating films for rewiring layers, stress buffer films, and the like. 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 cured films according to the invention can also be used in the production of printing plates such as offset or screen printing plates, in the etching of molded parts, in the production of protective lacquers and dielectric layers in electronics, especially microelectronics.

The method for producing a cured film of the present invention (hereinafter also simply referred to as "the production method of the present invention") includes a film forming step of applying the curable resin composition of the present invention to a substrate to form a film. is preferred.
The method for producing a cured film of the present invention preferably includes the film forming step, an exposure step of exposing the film, and a developing step of developing the film.
Further, the method for producing a cured film of the present invention more preferably includes the film forming step and, if necessary, the developing step, and also includes a heating step of heating the film at 50 to 450°C.
Specifically, it is also preferable to include the following steps (a) to (d).
(a) a film forming step of applying a curable resin composition to a substrate to form a film (a curable resin composition layer); (b) an exposure step of exposing the film after the film forming step; (d) a heating step of heating the developed film at 50 to 450° C. The resin layer cured by exposure can be further cured by heating in the heating step. In this heating step, for example, the above-mentioned thermal base generator is decomposed to obtain sufficient curability.

A method for producing a laminate according to a preferred embodiment of the present invention includes the method for producing a cured film of the present invention. In the method for producing a laminate of the present embodiment, after forming a cured film according to the above method for producing a cured film, the step (a), or the steps (a) to (c), or (a ) to (d) are performed. In particular, it is preferable to perform each of the above steps in order multiple times, for example, 2 to 5 times (that is, 3 to 6 times in total). By laminating the cured films in this manner, a laminate can be obtained. In the present invention, it is particularly preferred to provide a metal layer on the portion where the cured film is provided, between the cured films, or both. In the production of the laminate, it is not necessary to repeat all the steps (a) to (d), and as described above, at least (a), preferably (a) to (c) or (a) to (d) ) can be performed a plurality of times to obtain a cured film laminate.
<Film forming step (layer forming step)>
A production method according to a preferred embodiment of the present invention includes a film forming step (layer forming step) of applying a curable resin composition to a substrate to form a film (layered).

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, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, plasma display panel (PDP) electrode plates, etc. are not particularly limited. In the present invention, a semiconductor production substrate is particularly preferable, and a silicon substrate is more preferable.
As the base material, for example, a plate-like base material (substrate) is used.

Moreover, when forming a curable resin composition layer on the surface of a resin layer or the surface of a metal layer, a resin layer or a metal layer serves as a base material.

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

Specifically, applicable means include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and ink jet method. From the viewpoint of uniformity of the thickness of the curable resin composition layer, the spin coating method, slit coating method, spray coating method, and inkjet method are more preferable. A resin layer having a desired thickness can be obtained by appropriately adjusting the solid content concentration and coating conditions according to the method. In addition, the coating method can be appropriately selected depending on the shape of the substrate. Spin coating, spray coating, inkjet 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 2,000 rpm for about 10 seconds to 1 minute.
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.

<Drying process>
The production method of the present invention may include a step of drying to remove the solvent after forming the film (curable resin composition layer) and after the film forming step (layer forming step). The drying temperature is preferably 50 to 150°C, more preferably 70 to 130°C, even more preferably 90 to 110°C. The drying time is exemplified from 30 seconds to 20 minutes, preferably from 1 minute to 10 minutes, more preferably from 3 minutes to 7 minutes.

<Exposure process>
The production method of the present invention may include an exposure step of exposing the film (curable resin composition layer). The amount of exposure is not particularly defined as long as the curable resin composition can be cured ^. It is more preferable to irradiate cm ² .

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 (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-line (wavelength 436 nm), h (4) excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength: 157 nm), (5) extreme ultraviolet; EUV (wavelength: 13.6 nm), (6) electron beam, and the like. For the curable 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.

<Development process>
The production method of the present invention may include a development step of developing the exposed film (curable resin composition layer) (developing the film). By developing, the unexposed portions (non-exposed portions) are removed. The developing method is not particularly limited as long as a desired pattern can be formed.

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

Organic solvents include esters 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. . 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 acid, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and , ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and aromatic hydrocarbons such as toluene, xylene, anisole, limonene etc., dimethyl sulfoxide is preferably exemplified as sulfoxides.

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

The developer preferably contains 50% by mass or more of the organic solvent, more preferably 70% by mass or more of the organic solvent, and even more preferably 90% by mass or more of the organic solvent. Further, the developer may contain 100% by mass of the organic solvent.

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

After processing with the developer, rinsing may be carried out. Rinsing is preferably done with a solvent different from the developer. For example, the solvent contained in the curable resin composition can be used for rinsing. Rinsing time is preferably 5 seconds to 1 minute.

<Heating process>
The production method of the present invention preferably includes a step of heating the developed film at 50 to 450° C. (heating step).
The heating step is preferably included after the film forming step (layer forming step), the drying step, and the developing step. In the heating step, for example, the thermal base generator decomposes to generate a base, and the cyclization reaction of the specific heterocycle-containing polymer precursor proceeds. In addition, the curable resin composition of the present invention contains a compound having two or more ethylenically unsaturated groups in the molecule other than the specific heterocyclic ring-containing polymer precursor, but an unreacted ethylenically unsaturated group is included in the molecule. Curing of compounds having two or more can also proceed in this step. The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50° C. or higher, more preferably 80° C. or higher, even more preferably 140° C. or higher, and 150° C. or higher. is more preferable, 160° C. or higher is even more preferable, and 170° C. or higher is even more preferable. The upper limit is preferably 500° C. or lower, more preferably 450° C. or lower, still more preferably 350° C. or lower, even more preferably 250° C. or lower, and 220° C. or lower. Even more preferable.

Heating is preferably carried out from the temperature at the start of heating to the maximum heating temperature at a temperature rising rate of 1 to 12°C/min, more preferably 2 to 10°C/min, and even 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 amine while ensuring productivity, and by setting the temperature increase rate to 12° C./min or less, the cured film can be cured. Residual stress can be relaxed.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, 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 curable resin composition is applied onto a substrate and then dried, the temperature of the film (layer) after drying is higher than the boiling point of the solvent contained in the curable resin composition. It is preferable to gradually raise the temperature from a low temperature of 30 to 200°C.

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

Particularly when forming a multi-layer laminate, the heating temperature is preferably 180° C. to 320° C., more preferably 180° C. to 260° C., from the viewpoint of adhesion between the layers of the cured film. Although the reason for this is not clear, at this temperature, the vinyl groups in the aromatic rings to which the optionally substituted vinyl groups of the specific heterocycle-containing polymer precursor between the layers are directly bonded undergo a cross-linking reaction. This is thought to be due to

Heating may be done in stages. As an example, the temperature is raised from 25° C. to 180° C. at 3° C./min, held at 180° C. for 60 minutes, heated from 180° C. to 200° C. at 2° C./min, and held at 200° C. for 120 minutes. , may be performed. The heating temperature in the pretreatment step is preferably 100 to 200°C, more preferably 110 to 190°C, even more preferably 120 to 185°C. In this pretreatment step, it is also preferable to carry out 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, pretreatment step 1 may be performed at 100 to 150°C, and then pretreatment step 2 may be performed at 150 to 200°C.

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, in order to prevent decomposition of the specific heterocycle-containing polymer precursor. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.

<Metal layer forming step>
The production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the developed film (curable resin composition layer).

The metal layer is not particularly limited, and existing metal species can be used. Copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified. More preferred.

The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used. For example, photolithography, lift-off, 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.

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

<Lamination process>
Preferably, the production method of the present invention further includes a lamination step.

The lamination step means that the surface of the cured film (resin layer) or metal layer is again subjected to (a) film formation step (layer formation step), (b) exposure step, (c) development step, and (d) heating step. , in that order. However, only the film forming step (a) may be repeated. Also, (d) the heating step may be performed collectively at the end or in the middle of lamination. That is, the steps (a) to (c) may be repeated a predetermined number of times, and then the laminated curable resin composition layers may be cured at once by heating (d). In addition, after the (c) development step, (e) a metal layer forming step may be included, and even if the heating of (d) is performed each time at this time, after stacking a predetermined number of times, (d) is collectively performed. Heating may be performed. Needless to say, the lamination step may further include the drying step, the heating step, and the like as appropriate.

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

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

For example, the resin layer structure is preferably 3 to 7 layers, such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, and more preferably 3 to 5 layers.

In the present invention, it is particularly preferable to form a cured film (resin layer) of the curable resin composition so as to cover the metal layer after providing the metal layer. Specifically, (a) film formation step, (b) exposure step, (c) development step, (e) metal layer formation step, and (d) heating step are repeated in this order, or (a) film formation (b) the exposure step, (c) the development step, and (e) the metal layer formation step, and the step (d) is collectively provided at the end or in the middle. By alternately performing the lamination step of laminating the curable resin composition layer (resin layer) and the metal layer forming step, the curable resin composition layer (resin layer) and the metal layer can be alternately laminated.

The invention also discloses a semiconductor device comprising the cured film or laminate of the invention. Specific examples of semiconductor devices using the curable resin composition of the present invention for forming an interlayer insulating film for rewiring layers are described in paragraphs 0213 to 0218 of JP-A-2016-027357 and the description in FIG. , the contents of which are incorporated herein.

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 polyimide precursor (A-1) from 4,4′-oxydiphthalic dianhydride, 4,4′-diaminodiphenyl ether and 4-aminostyrene]
20.0 g (64.5 mmol) of 4,4′-oxydiphthaldianhydride (dried at 140° C. for 12 hours), 15.4 g (129 mmol) of 4-aminostyrene and 0.05 g of hydroquinone , 20.4 g (258 mmol) of pyridine and 100 g of diglyme were mixed and stirred at 0° C. for 1 hour and then at 60° C. for 1 hour to give 4,4′-oxydiphthalic acid and 4-aminostyrene. was prepared. The reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) of pyridine and 90 mL of N-methylpyrrolidone were added.
The reaction mixture was then cooled to -10.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. 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 to the reaction mixture over 20 minutes while maintaining the temperature between -5 and 0°C. Dripped. 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 for 15 minutes. The polyimide precursor was filtered off, stirred again in 4 liters of water for 30 minutes and filtered again. The resulting polyimide precursor was then dried under reduced pressure at 45° C. for 3 days. The weight average molecular weight of this polyimide precursor was 18,000.

<Synthesis Example 2>
[Polybenzoxazole precursor (A-2) from 2,2′-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 4,4′-oxydibenzoyl chloride and 4-vinylbenzoyl chloride Synthesis]
13.92 g of 2,2′-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was added to 100 mL of N-methyl-2-pyrrolidone and dissolved with stirring. Subsequently, while maintaining the temperature at 0-5° C., 11.21 g of 4,4′-oxydibenzoyl chloride was added dropwise over 10 minutes and then stirring was continued for 60 minutes. 4-Vinylbenzoyl chloride (1.27 g) was then added and stirred for 60 minutes. The polybenzoxazole precursor was then precipitated in 6 liters of water and the water-polybenzoxazole precursor mixture was stirred at a speed of 5000 rpm for 15 minutes. The polybenzoxazole precursor was filtered off, stirred again in 6 liters of water for 30 minutes and filtered again. The resulting polybenzoxazole precursor was then dried under reduced pressure at 45° C. for 3 days. The weight average molecular weight of this polybenzoxazole precursor was 15,000.

<Synthesis Example 3>
[Synthesis of polyimide precursor (A-3: polyimide precursor having radically polymerizable group) from 4,4′-oxydiphthaldianhydride, 4,4′-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate]
155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) was placed in a 2-liter separable flask, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added. A reaction mixture was obtained by adding 79.1 g of pyridine while stirring at room temperature. After the end of heat generation due to the reaction, the mixture was allowed to cool to room temperature and allowed to stand still for 16 hours.
Next, under ice-cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Subsequently, a suspension of 93.0 g of 4,4'-diaminodiphenyl ether in 350 ml of γ-butyrolactone was added with stirring over 60 minutes. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and the mixture was stirred for 1 hour. Then 400 ml of γ-butyrolactone was added. A precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.
The resulting reaction solution was added to 3 liters of ethyl alcohol to produce a precipitate consisting of crude polymer. The resulting crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was dropped into 28 liters of water to precipitate the polymer, and the resulting precipitate was collected by filtration and vacuum dried to obtain a powdery polymer A-3. When the weight average molecular weight (Mw) of this polymer A-3 was measured, it was 20,000.

<Synthesis Example 4>
[3,3′,4,4′-biphenyltetracarboxylic dianhydride, 4,4′-diaminodiphenyl ether, and polyimide precursor from 2-hydroxyethyl methacrylate (A-4: polyimide having a radically polymerizable group Synthesis of precursor)]
Synthesis Example 3 except that 147.1 g of 3,3'4,4'-biphenyltetracarboxylic dianhydride was used in place of 155.1 g of 4,4'-oxydiphthalic dianhydride in Synthesis Example 3. Polymer A-4 was obtained by carrying out the reaction in the same manner as described in . When the weight average molecular weight (Mw) of this polymer A-4 was measured, it was 22,000.

<Synthesis Example 5>
[Synthesis of compound B-1]
450 g of methanol, 15 g of bismuthiol (manufactured by TCI), and 25.3 g of triethylamine were added to a three-necked flask and completely dissolved. Thereafter, 30.5 g of parachloromethylstyrene (manufactured by Seimi Chemical Co., Ltd.) dissolved in 50 g of methanol was added dropwise over 20 minutes while cooling with ice. After the dropwise addition was completed, the mixture was stirred for 4 hours while cooling with water (crystals precipitated in the reaction solution). The reaction solution was added to 1,000 g of pure water and stirred at room temperature for 30 minutes, after which crystals were separated by filtration. The resulting crude crystals were reslurried with 300 g of methanol and 100 g of ethyl acetate and dried under vacuum to obtain 11.5 g of B-1 (yield 30%).

[Synthesis of Compound B-5 and Compound B-12]
Compounds B-5 and B-12 were synthesized in the same manner as in the synthesis of compound B-1 above, except that the synthetic raw materials were appropriately changed. The structures of compounds B-1, B-5 and B-12 are respectively shown in the following formulas (B-1), (B-5) and (B-12).

<Examples and Comparative Examples>
In each example, the components shown in Table 1 below were mixed to obtain each curable resin composition. In addition, in each comparative example, the components shown in Table 1 below were mixed to obtain each comparative composition.
Specifically, the content of the components described in the columns other than "solvent" in Table 1 is the amount described in "parts by mass" in Table 1, and the content of the components described in the "solvent" column in Table 1. The amount was such that the solid content concentration of the composition was the value shown in Table 1.
Further, for example, the descriptions of "I-1/I-2" and "80/20" in "solvent" in Table 1 indicate that the ratio of the contents of I-1 and I-2 is I-1: It shows that I-2=80:20.
The resulting curable resin composition and comparative composition were filtered under pressure through a polytetrafluoroethylene filter having a pore width of 0.8 μm.
In addition, in Table 1, the description of "-" indicates that the composition does not contain the corresponding component.

Details of each component described in Table 1 are as follows.

[Polymer precursor]
· A-1 to A-4: A-1 to A-4 synthesized above

[Specific polymerizable compound]
· B-1, B-5 and B-12: B-1, B-5 and B-12 synthesized above

[Polymerizable compound]
- C-1 to C-3: compounds having the following structures

〔Additive〕
・ J-1: N-phenyldiethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Photopolymerization initiator]
- D-1 and D-2: compounds having the following structures

[Thermal base generator]
- E-1 to E-2: compounds having the following structures

[Polymerization inhibitor]
・F-1 to F-2: compounds having the following structures ・F-3: 2-nitroso-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.)

〔金属接着性改良剤〕
・Ｈ－１～Ｈ－３：下記構造の化合物

[Migration inhibitor]
- G-1 to G-2: compounds having the following structures

[Metal adhesion improver]
· H-1 to H-3: compounds having the following structures

〔solvent〕
・ I-1: γ-butyrolactone (manufactured by Sanwa Yuka Co., Ltd.)
・ I-2: dimethyl sulfoxide (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
· I-3: N-methyl-2-pyrrolidone (manufactured by Ashland)
・ I-4: Ethyl lactate (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Production of cured film>
In each example and comparative example, the curable resin composition or comparative composition was applied onto a silicon wafer by spin coating to form a resin layer. The silicon wafer having the resin layer formed thereon was dried on a hot plate at 100° C. for 4 minutes to form a resin composition layer having a uniform thickness of 20 μm on the silicon wafer.
The resin composition layer on the silicon wafer is exposed with an exposure energy of 400 mJ/cm ² using a broadband exposure machine (Ushio Inc.: UX-1000SN-EH01), and the exposed resin composition layer is exposed to Under a nitrogen atmosphere, the temperature was raised at a rate of temperature increase of 5° C./min, and after reaching 180° C., heating was continued at this temperature for 2 hours. The resin composition layer after heating and the silicon wafer were immersed in a 3 mass % hydrofluoric acid aqueous solution, and the resin composition layer after heating was peeled off from the silicon wafer. The resin composition layer after the peeling and heating was used as a cured film.

<Evaluation>
In each example and comparative example, chemical resistance was evaluated using the obtained cured film.
The details of the evaluation method in each evaluation are described below.

〔chemical resistance〕
The obtained cured film was immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated.
Chemical solution: 90:10 (mass ratio) mixture of dimethyl sulfoxide (DMSO) and 25% by mass of tetramethylammonium hydroxide (TMAH) aqueous solution Evaluation conditions: Before and after immersion of the cured film in the chemical solution at 75 ° C. for 15 minutes were compared, and the dissolution rate (nm/min) was calculated. The film thickness was measured at 10 points on the coated surface using an ellipsometer (KT-22 manufactured by Foothill), and the arithmetic mean value was obtained.
Evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in Table 1. It can be said that the smaller the dissolution rate, the better the chemical resistance of the cured film.

-Evaluation criteria-
A: The dissolution rate is less than 250 nm/min.
B: The dissolution rate is 250 nm/min or more and less than 500 nm/min.
C: The dissolution rate is 500 nm/min or more.

From the above results, it can be seen that the curable resin composition containing the specific heterocycle-containing polymer precursor according to the present invention has excellent chemical resistance of the cured film.
The curable resin composition according to Comparative Example 1 does not contain a specific heterocycle-containing polymer precursor. It can be seen that the curable resin composition according to Comparative Example 1 is inferior in chemical resistance of the cured film.

<Example 101>
The curable resin composition used in Example 1 was applied in a layered manner by a spin coating method to the surface of the resin substrate on which the thin copper layer was formed, and dried at 100 ° C. for 5 minutes to obtain a curable film thickness of 20 μm. After forming the resin composition layer, it was exposed using a stepper (manufactured by Nikon Corporation, NSR1505 i6). 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 exposure, the layer was patterned by developing with cyclopentanone for 30 seconds and rinsing with PGMEA for 20 seconds.
Then, it was heated at 230° C. for 3 hours to form an interlayer insulating film for rewiring layer. 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 (14)

At least one polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors,
The polymer precursor contains an aromatic ring to which an optionally substituted vinyl group is directly bonded,
The polymer precursor is a polyimide precursor having a repeating unit represented by the following formula (1), or a polybenzoxazole precursor having a repeating unit represented by the following formula (2),
The vinyl group has radical polymerizability
A curable resin composition.

In formula (1) or (2), A ¹ and A ² each independently represent an oxygen atom or —NH—, R ¹¹¹ represents a divalent organic group, and R ¹¹⁵ represents a tetravalent organic group, R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, and at least one of R ¹¹³ and R ¹¹⁴ is an aromatic ring directly bonded to an optionally substituted vinyl group wherein R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group, and R At least one of ¹²³ and R ¹²⁴ contains an aromatic ring to which an optionally substituted vinyl group is directly bonded. The curable resin composition according to claim 1 , comprising a group represented by the following formula (S-1) as the group having an aromatic ring to which the optionally substituted vinyl group is directly bonded;

In formula (S-1), R ^S1 represents a hydrogen atom , R ^S2 represents a substituent, L ^S1 represents a single bond or a divalent linking group, n represents an integer of 0 to 4, * represents a binding site with another structure. 3. The curable resin composition according to claim 1 , further comprising a compound having two or more ethylenically unsaturated groups in the molecule. Curing according to claim 3 , wherein the compound having two or more ethylenically unsaturated groups in the molecule is a compound having two or more aromatic rings to which optionally substituted vinyl groups are directly bonded in the molecule. elastic resin composition. The curable resin according to claim 4 , wherein the compound having two or more aromatic rings to which the optionally substituted vinyl group is directly bonded in the molecule is a compound represented by the following formula (1-1). Composition;

In formula (1-1), Z is a divalent or higher saturated aliphatic hydrocarbon group, a divalent or higher unsaturated aliphatic hydrocarbon group, a divalent or higher hydrocarbon ring group, -O-, -S-, -N(R ^A )-, -C(=O)-O-, -C(R ^A )=N-, -C(=O)-, -S(=O) ₂ -, 2 or higher complex an m-valent linking group selected from the group consisting of a cyclic group and a group ⁱⁿ which two or more of these are bonded, ^RA represents a hydrogen atom, an alkyl group or an aryl group; R ¹ may be the same or different, each R ¹ independently represents a hydrogen atom or a methyl group, and m represents an integer of 2-6. The curable resin composition according to any one of claims 1 to 5 , further comprising a photoradical polymerization initiator. The curable resin composition according to any one of claims 1 to 6 , further comprising an onium salt. The curable resin composition according to any one of claims 1 to 7 , which is used for forming an interlayer insulating film for rewiring layers. A cured film obtained by curing the curable resin composition according to any one of claims 1 to 8 . A laminate comprising two or more layers of the cured film according to claim 9 and a metal layer between any of the cured films. A method for producing a cured film, comprising a film forming step of applying the curable resin composition according to any one of claims 1 to 8 to a substrate to form a film. 12. The method for producing a cured film according to claim 11 , comprising an exposure step of exposing the film and a development step of developing the film. The method for producing a cured film according to claim 11 or 12 , comprising a heating step of heating the film at 50 to 450°C. A semiconductor device comprising the cured film according to claim 9 or the laminate according to claim 10 .