JPWO2020189481A1 - Curable resin composition, cured film, laminate, method for manufacturing cured film, and semiconductor device - Google Patents

Abstract

It has at least one branched structure selected from the group consisting of the branched structure represented by the following formula (A-1) and the branched structure represented by the following formula (A-2), and has. As the branched chain bonded to the branched structure, a curable resin composition containing a polyimide precursor having a branched chain having a repeating unit, a cured film obtained by curing the curable resin composition, and the cured film are included. In the laminate, the method for producing the cured film, and the cured film or the semiconductor device containing the laminate; in the formula (A-1) or the formula (A-2), R115 represents a tetravalent organic group, and RA21. Represents a hydrogen atom or a monovalent organic group, and * independently represents a bonding site with another structure.

Description

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.

A resin obtained by cyclizing and curing a polymer precursor such as a polyimide resin or a polybenzoxazole resin (hereinafter, a polyimide resin precursor and a polybenzoxazole resin precursor are collectively referred to as a "heterocycle-containing polymer precursor"). Is applied to various applications because of its excellent heat resistance and insulation. The application is not particularly limited, and examples thereof include a semiconductor device for mounting as a material for an insulating film or a sealing material, or a protective film. It is also used as a base film and coverlay for flexible substrates.

For example, in the above-mentioned applications, the heterocycle-containing polymer precursor is used as 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 heterocyclic-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 or the like, for example, there is a high degree of freedom in designing the shape, size, application position, etc. of the curable resin composition to be applied. It can be said that it has excellent adaptability. In addition to the high performance of polyimide resins and the like, from the viewpoint of excellent manufacturing adaptability, industrial application development of curable resin compositions containing heterocyclic-containing polymer precursors is expected more and more.

For example, Patent Document 1 contains (A) a polyimide precursor and (B) a photosensitive agent, and the (A) polyimide precursor is an amic acid represented by (a-1) the general formula (1). A photosensitive resin composition, which is a resin having a structural unit of an ester, is described.
Patent Document 2 describes a tetracarboxylic dianester compound characterized by having a specific structure.
Patent Document 3 describes a polyamic acid characterized by containing a specific repeating unit.

Japanese Unexamined Patent Publication No. 2018-165819 Japanese Unexamined Patent Publication No. 2017-193500 Special Table 2014-511909 Gazette

In a curable resin composition containing a heterocyclic-containing polymer precursor such as a polyimide precursor, it is desired to provide a curable resin composition having an excellent breaking elongation rate of the obtained cured product.

The present invention relates to a curable resin composition having an excellent breaking elongation rate of the obtained cured film, a cured film obtained by curing the curable resin composition, a laminate containing the cured film, a method for producing the cured film, and a method for producing the cured film. , It is an object of the present invention to provide a semiconductor device including the cured film or the laminated body.

式（Ａ−１）又は式（Ａ−２）中、Ｒ^１１５は４価の有機基を表し、Ｒ^Ａ２１は水素原子又は１価の有機基を表し、＊はそれぞれ独立に、他の構造との結合部位を表す。
＜２＞ 上記ポリイミド前駆体に含まれる上記分岐型構造の含有量が、組成物の全固形分に対し、０．０１〜１０μｍｏｌ／ｇである、＜１＞に記載の硬化性樹脂組成物。
＜３＞ 上記ポリイミド前駆体が下記式（１）で表される繰返し単位を有する、＜１＞又は＜２＞のいずれか１つに記載の硬化性樹脂組成物；

式（１）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、＊^１及び＊^２はそれぞれ独立に、他の構造との結合部位を表す。
＜４＞ 上記式（１）におけるＲ^１１３及びＲ^１１４の少なくとも一方がラジカル重合性基を含む、＜３＞に記載の硬化性樹脂組成物。
＜５＞ 上記式（１）におけるＲ^１１５が芳香環を含む基である、＜３＞又は＜４＞に記載の硬化性樹脂組成物。
＜６＞ 上記式（１）におけるＲ^１１１が−Ａｒ^０−Ｌ^０−Ａｒ^０−で表される、＜３＞〜＜５＞のいずれか１つに記載の硬化性樹脂組成物；
Ａｒ^０はそれぞれ独立に芳香族基を表し、Ｌ^０は、単結合、フッ素原子で置換されていてもよい炭素数１〜１０の脂肪族炭化水素基、−Ｏ−、−Ｃ（＝Ｏ）−、−Ｓ−、−Ｓ（＝Ｏ）_２−、−ＮＨＣ（＝Ｏ）−及び、これらを２以上組み合わせた基を表す。
＜７＞ 上記式（１）におけるＲ^１１１が、下記式（５１）又は式（６１）で表される、＜３＞〜＜６＞のいずれか１つに記載の硬化性樹脂組成物；

式（５１）又は式（６１）中、Ｒ^５０〜Ｒ^５７は、それぞれ独立に水素原子、フッ素原子又は１価の有機基を表し、Ｒ^５０〜Ｒ^５７の少なくとも１つはフッ素原子、メチル基、フルオロメチル基、ジフルオロメチル基又はトリフルオロメチル基を表し、Ｒ^５８及びＲ^５９は、それぞれ独立にフッ素原子、フルオロメチル基、ジフルオロメチル基又はトリフルオロメチル基を表し、＊はそれぞれ独立に、他の構造との結合部位を表す。
＜８＞ 上記分岐鎖に含まれる繰返し単位のうち少なくとも１種が、上記ポリイミド前駆体の主鎖に含まれる繰返し単位のうち少なくとも１種と同一である、＜１＞〜＜７＞のいずれか１つに記載の硬化性樹脂組成物。
＜９＞ ラジカル重合開始剤、ラジカル重合性化合物、シランカップリング剤及び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＞ 上記ポリイミド前駆体とは異なる他の複素環含有ポリマー前駆体を更に含む、＜１＞〜＜９＞のいずれか１つに記載の硬化性樹脂組成物。
＜１１＞ 再配線層用層間絶縁膜の形成に用いられる、＜１＞〜＜１０＞のいずれか１つに記載の硬化性樹脂組成物。
＜１２＞ ＜１＞〜＜１１＞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。
＜１３＞ ＜１２＞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。
＜１４＞ ＜１＞〜＜１１＞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。
＜１５＞ 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、＜１４＞に記載の硬化膜の製造方法。
＜１６＞ 上記膜を８０〜４５０℃で加熱する加熱工程を含む、＜１４＞又は＜１５＞に記載の硬化膜の製造方法。
＜１７＞ ＜１２＞に記載の硬化膜又は＜１３＞に記載の積層体を含む、半導体デバイス。Hereinafter, examples of typical embodiments of the present invention will be described.
<1> Has at least one branched structure selected from the group consisting of the branched structure represented by the following formula (A-1) and the branched structure represented by the following formula (A-2). A curable resin composition containing a polyimide precursor having a branched chain having a repeating unit as a branched chain bonded to the above-mentioned branched structure;

In formula (A-1) or formula (A-2), R ¹¹⁵ represents a tetravalent organic group ^{, RA 21} represents a hydrogen atom or a monovalent organic group, and * is an independent structure with another structure. Represents the binding site of.
<2> The curable resin composition according to <1>, wherein the content of the branched structure contained in the polyimide precursor is 0.01 to 10 μmol / g with respect to the total solid content of the composition.
<3> The curable resin composition according to any one of <1> and <2>, wherein the polyimide precursor has a repeating unit represented by the following formula (1);

In formula (1), A ¹ and A ² independently represent an oxygen atom or -NH-, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, and * ¹ and * ² each independently represent a bonding site with another structure.
<4> The curable resin composition according to <3>, wherein at least one ^{of R 113} and R ¹¹⁴ in the above formula (1) contains a radically polymerizable group.
<5> The curable resin composition according to <3> or <4>, wherein ^{R 115} in the above formula (1) is a group containing an aromatic ring.
<6> The curable resin composition according to any one of <3> to <5>, wherein ^{R 111} in the above formula (1) is represented by −Ar ⁰ −L ⁰ −Ar ^{0 −;}
Ar ⁰ represents an aromatic group independently, and L ⁰ is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, −O−, −C (= O). -, -S-, -S (= O) _2- , -NHC (= O)-, and a group in which two or more of these are combined are represented.
<7> The curable resin composition according to any one of <3> to <6>, wherein ^{R 111} in the above formula (1) is represented by the following formula (51) or formula (61);

In the formula (51) or the formula (61), R ^{50 to} R ⁵⁷ independently represent 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 and a methyl group. , Fluoromethyl group, difluoromethyl group or trifluoromethyl group, R ⁵⁸ and R ⁵⁹ independently represent a fluorine atom, fluoromethyl group, difluoromethyl group or trifluoromethyl group, and * independently represent each. Represents a site of binding to other structures.
<8> Any of <1> to <7>, wherein at least one of the repeating units contained in the branched chain is the same as at least one of the repeating units contained in the main chain of the polyimide precursor. The curable resin composition according to one.
<9> The curable resin composition according to any one of <1> to <8>, further comprising a radical polymerization initiator, a radically polymerizable compound, a silane coupling agent, and an onium salt.
<10> The curable resin composition according to any one of <1> to <9>, further comprising another heterocyclic-containing polymer precursor different from the polyimide precursor.
<11> The curable resin composition according to any one of <1> to <10>, which is used for forming an interlayer insulating film for a rewiring layer.
<12> A cured film obtained by curing the curable resin composition according to any one of <1> to <11>.
<13> A laminate containing two or more layers of the cured film according to <12> and containing a metal layer between any of the cured films.
<14> A method for producing a cured film, which comprises a film forming step of applying the curable resin composition according to any one of <1> to <11> to a substrate to form a film.
<15> The method for producing a cured film according to <14>, which comprises an exposure step for exposing the film and a developing step for developing the film.
<16> The method for producing a cured film according to <14> or <15>, which comprises a heating step of heating the film at 80 to 450 ° C.
<17> A semiconductor device comprising the cured film according to <12> or the laminate according to <13>.

Hereinafter, the main embodiments of the present invention will be described. However, the present invention is not limited to the specified embodiments.
The numerical range represented by the symbol "~" in the present specification means a range including the numerical values before and after "~" as the lower limit value and the upper limit value, respectively.
As used herein, the term "process" means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended action of the process can be achieved.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substituent also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
As used herein, the term "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of the light used for exposure include emission line spectra of mercury lamps, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
As used herein, "(meth) acrylate" means both "acrylate" and "methacrylate", or either, and "(meth) acrylic" means both "acrylic" and "methacrylic", or. , Any, and "(meth) acryloyl" means both "acryloyl" and "methacrylic", or either.
In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
As used herein, the total solid content means the total mass of all the components of the composition excluding the solvent. Further, in the present 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, the weight average molecular weight (Mw) and the 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, for the weight average molecular weight (Mw) and the number average molecular weight (Mn), for example, HLC-8220GPC (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be obtained by using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise specified, their molecular weights shall be measured using THF (tetrahydrofuran) as an eluent. Further, unless otherwise specified, the detection in the GPC measurement shall be performed by using a detector having a wavelength of 254 nm of UV rays (ultraviolet rays).
In the present specification, when the positional relationship of each layer constituting the laminated body is described as "upper" or "lower", the other layer is on the upper side or the lower side of the reference layer among the plurality of layers of interest. All you need is. That is, a third layer or element may be further 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. Unless otherwise specified, the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a photosensitive layer, the direction from the base material to the photosensitive layer is referred to as "upper". The opposite direction is referred to as "down". It should be noted that such a vertical setting is for convenience in the present specification, and in an actual embodiment, the "up" direction in the present specification may be different from the vertical upward direction.
Unless otherwise specified in the present specification, the composition may contain, as each component contained in the composition, two or more compounds corresponding to the component. Unless otherwise specified, the content of each component in the composition means the total content of all the compounds corresponding to the component.
In the present specification, the physical property values are values under the conditions of a temperature of 23 ° C. and an atmospheric pressure of 101,325 Pa (1 atm) unless otherwise specified.
As used herein, a combination of preferred embodiments is a more preferred embodiment.

(Curable resin composition)
The curable resin composition of the present invention (hereinafter, also simply referred to as “the composition of the present invention”) is represented by a branched structure represented by the formula (A-1) and a formula (A-2). A polyimide precursor having at least one branched structure selected from the group consisting of the branched structures and having a branched chain having a repeating unit as a branched chain to be bonded to the branched structure (hereinafter referred to as “branched chain”). Also referred to as "specific polymer precursor").
Further, the curable resin composition of the present invention preferably further contains a radical polymerization initiator described later, a radical polymerizable compound described later, a silane coupling agent described later, and an onium salt described later.

The curable resin composition of the present invention is excellent in the elongation at break of the obtained cured film.
The mechanism by which the above effect is obtained is unknown, but it is presumed as follows.
By using a polyimide precursor having a branched chain having a repeating unit as a specific branched structure and a molecular chain bonded to the branched structure, the entanglement of the polymer chains in the polymer formed after curing is increased. Therefore, it is presumed that the elongation at break is improved.
In addition, it is considered that storage stability is likely to be improved because cyclization during storage is suppressed due to the steric hindrance effect of having the branched chain.
Further, the entanglement of the polymer chains in the cured portion due to exposure increases, and the difference in solubility in the developing solution increases between the exposed portion and the unexposed portion, so that the resolution when patterning by exposure is performed becomes large. Is considered to be easy to improve.

Here, Patent Documents 1 to 3 do not describe or suggest a composition containing a specific polymer precursor. Further, the cured film obtained by curing the curable resin composition in Patent Documents 1 to 3 has a problem that the elongation at break is low.
Hereinafter, the components contained in the curable resin composition of the present invention will be described in detail.

<Specific polymer precursor>
The curable resin composition of the present invention contains a specific polymer precursor.
The specific polymer precursor has at least one branched structure selected from the group consisting of the branched structure represented by the formula (A-1) and the branched structure represented by the formula (A-2). As the branched chain having and bonded to the above-mentioned branched structure, a polyimide precursor having a branched chain having a repeating unit is included.
The * in the formula (A-1) and the formula (A-2) is preferably bonded to a molecular chain having a repeating unit.
In the present specification, a molecular chain having a repeating unit and having the longest molecular chain is referred to as a main chain, and a molecular chain having a repeating unit and different from the main chain is referred to as a branched chain.
The main chain may have a branched structure, and the branched chain may further have a branched structure and a branched chain.
The branched chain is bound to the main chain or the branched chain via the above-mentioned branched structure.
Here, for example, the curable resin composition of the present invention is diluted with tetrahydrofuran, a mixed solvent of water: acetone = 30% by mass: 70% by mass is added, the precipitate is removed by filtration, and the filtrate is dried. By performing acetone extraction on the dried filtrate, the specific polymer precursor can be selectively obtained from the curable resin composition.

式（Ａ−１）〜（Ａ−２）中、Ｒ^１１５は４価の有機基を表し、Ｒ^Ａ２１は水素原子又は１価の有機基を表し、＊はそれぞれ独立に、他の構造との結合部位を表す。[Branch type structure]
The specific polymer precursor has a branched structure represented by the following formula (A-1), a branched structure represented by the formula (A-2), and a branched structure represented by the formula (A-3). Includes a structure represented by at least one equation selected from the group consisting of branched structures.

In formulas (A-1) to (A-2), R ¹¹⁵ represents a tetravalent organic group ^{, RA 21} represents a hydrogen atom or a monovalent organic group, and * represents an independent structure with another structure. Represents a binding site.

-R ¹¹⁵ (Equation (A-1))-
In formula (A-1), R ¹¹⁵ 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 formula (6) is more preferable.

R ¹¹² is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be single-bonded or 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 is preferable, and a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom,- More preferably, it is a group selected from O-, -C (= O)-, -S- and S (= O) _{2- , and -CH 2-} , -O-, -S-, -S ( _{= O) 2 -, - C} (CF 3) 2 -, and, -C _{(CH 3) 2} - and more preferably a divalent radical selected from the group consisting of. * Each independently represents a binding site with another structure.

^{Specifically, the tetravalent organic group represented by R 115} in the formula (A-1) is a tetracarboxylic acid residue (tetracarboxylic acid) remaining after removing the acid dianhydride group from the tetracarboxylic acid dianhydride. A structure in which all four of the four carboxy groups in the above are amidated) and the like. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).

R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ has the same meaning as ^{R 115} in formula (A-1).

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

-R ¹¹⁵ (Equation (A-2))-
In formula (A-2), R ¹¹⁵ represents a tetravalent organic group. ^{R 115} in formula (A-2) has the same meaning as ^{R 115} in formula (A-1), a preferable embodiment thereof is also the same.

^-RA21-
Wherein ^{(A-2), R A21} represents a hydrogen atom or a monovalent organic group, the group represented by hydrogen or ^-X A21 ^{-R A22} is preferable.
The X ^A21 represents an oxygen atom or −NH−, and an oxygen atom is preferable.
The ^RA22 represents a monovalent organic group, and a monovalent organic group containing a radically polymerizable group is preferable.
The radically polymerizable group may be any group that can undergo a cross-linking reaction by the action of a radical, and a preferable example thereof is a group having an ethylenically unsaturated bond.

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

In formula (III), ^R200 represents a hydrogen atom or a methyl group, and a methyl group is preferable.

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 (as an alkylene group having 1 carbon atom). ~ 12 is preferable, 1 to 6 is more preferable, 1 to 3 is particularly preferable; the number of repetitions is preferably 1 to 12, 1 to 6 is more preferable, and 1 to 3 is particularly preferable). The (poly) oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.
Examples of suitable R ²⁰¹ are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butandyl group, 1,3-butanjiyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group. , -CH ₂ CH (OH) CH _{2-, and} more preferably an ethylene group, a propylene group, a trimethylene group, and -CH ₂ CH (OH) CH _2-.
Particularly preferably, ^R200 is a methyl group and ^R201 is an ethylene group.
In formula (III), * represents a binding site with another structure.
As a preferred embodiment of the polyimide precursor in the present invention, as the ^{monovalent organic group in RA22} , an aliphatic group, an aromatic group, an arylalkyl group or the like having one, two or three, preferably one acid group, etc. Can be mentioned. Specific examples thereof include an aromatic group having an acid group having 6 to 20 carbon atoms and an arylalkyl group having an acid group having 7 to 25 carbon atoms. More specifically, a phenyl group having an acid group and a benzyl group having an acid group can be mentioned. The acid group is preferably a hydroxy group. That is, ^RA22 is preferably a group having a hydroxy group.
As the ^{monovalent organic group represented by RA22,} a substituent that improves the solubility of the developing solution is preferably used.

It is more preferable that ^RA22 is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl from the viewpoint of solubility in an aqueous developer.

From the viewpoint of solubility in an organic solvent, ^RA22 is preferably a monovalent organic group. As the monovalent organic group, a linear or branched alkyl group, a cyclic alkyl group and an aromatic group are preferable, and an alkyl group substituted with an aromatic group is more preferable.

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

Specific examples of the aromatic group include a substituted or unsubstituted aromatic hydrocarbon group (the cyclic structure constituting the group includes a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an inden ring, and azulene. Rings, heptalene rings, indacene rings, perylene rings, pentacene rings, acenaphthene rings, phenanthrene rings, anthracene rings, naphthacene rings, chrysen rings, triphenylene rings, etc.), or substituted or unsubstituted aromatic heterocyclic groups (including substituted or unsubstituted aromatic heterocyclic groups). 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 indolidine ring, an indole ring, and a benzofuran. Ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthylidine ring, quinoxalin ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, aclysine ring, phenanthrene ring, thianthrene ring, chromene ring. , Xanthene ring, phenoxatiin ring, phenothiazine ring or phenazine ring).

The content of the branched structure contained in the specific polymer precursor is preferably 0.01 to 10 μmol / g with respect to the total solid content of the composition from the viewpoint of improving the elongation at break of the cured product. It is preferably 0.01 to 8 μmol / g, and more preferably 0.02 to 5 μmol / g.
The specific polymer precursor may have only one type of branched structure represented by the formula (A-1) or the formula (A-2) as the branched structure, or the formula (A-1) or. The branched structure represented by the formula (A-2) may be provided as two or more types of branched structures having different structures. When the specific polymer precursor has two or more kinds of branched structures, the content of the branched structure is the branch represented by all the formulas (A-1) or (A-2) in the specific polymer precursor. The total content of the mold structure.

式（Ａ−３）中、Ｒ^Ａ３１はｎ価の連結基を表し、ｎは３以上の整数を表し、＊はそれぞれ独立に、他の構造との結合部位を表す。[Other branched structures]
The specific polymer precursor may further have a branched structure represented by the following formula (A-3) as another branched structure.

In formula (A-3), ^RA31 represents an n-valent linking group, n represents an integer of 3 or more, and * represents a binding site with another structure independently.

^-RA31-
In formula (A-3), ^RA31 represents an n-valent linking group, which is a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, a heteroarophatic group, or a group thereof. Examples of a group in which two or more are combined are a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and a cyclic aliphatic group having 6 to 20 carbon atoms. An aromatic group of 20 or a group in which two or more of these are combined is preferable, and an aromatic group having 6 to 20 carbon atoms is more preferable.

^RA31 in the formula (A-3) is preferably derived from an n-valent amine compound. Examples of the n-valent amine compound used for producing the polyimide precursor include linear or branched-chain aliphatic, cyclic aliphatic or aromatic n-valent amine compounds. Only one kind of n-valent amine compound may be used, or two or more kinds may be used.

上記式中、ｎは３以上の整数を表し、ａは１以上の整数を表し、ｂは１以上の整数を表し、ａ＋ｂは３以上であり、Ａはフッ素原子で置換されていてもよい炭素数１〜１０の脂肪族炭化水素基、−Ｏ−、−Ｃ（＝Ｏ）−、−Ｓ−、−Ｓ（＝Ｏ）_２−、−ＮＨＣ（＝Ｏ）−、又は、これらを２以上組み合わせた基であり、＊はそれぞれ独立に、他の構造との結合部位を表す。
ｎは３〜１０の整数が好ましく、３〜６の整数がより好ましい。
ａは１〜１０の整数が好ましく、１〜４の整数がより好ましく、１又は２がより好ましい。
ｂは１〜１０の整数が好ましく、１〜４の整数がより好ましく、１又は２がより好ましい。
ａ＋ｂは３〜１０の整数が好ましく、３〜６の整数がより好ましい。
Ａは単結合、フッ素原子で置換されていてもよい炭素数１〜３のアルキレン基、−Ｏ−、−Ｃ（＝Ｏ）−、−Ｓ−及びＳ（＝Ｏ）_２−よりなる群から選択される基であることが好ましく、−ＣＨ_２−、−Ｏ−、−Ｓ−、−Ｓ（＝Ｏ）_２−、−Ｃ（ＣＦ_３）_２−、及び、−Ｃ（ＣＨ_３）_２−よりなる群から選択される２価の基であることがより好ましい。
ｎ個の＊はそれぞれ、式中の同一の炭素原子に結合していてもよいが、異なる炭素原子に結合していることが好ましい。
ａ個の＊はそれぞれ、式中の同一の炭素原子に結合していてもよいが、異なる炭素原子に結合していることが好ましい。
ｂ個の＊はそれぞれ、式中の同一の炭素原子に結合していてもよいが、異なる炭素原子に結合していることが好ましい。Specifically, the n-valent amine compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, and an aromatic group having 6 to 20 carbon atoms. Alternatively, it is preferably an n-valent amine compound containing a group in which two or more of these are combined, and more preferably an n-valent amine compound containing an aromatic group having 6 to 20 carbon atoms. Examples of aromatic groups include:

In the above equation, n represents an integer of 3 or more, a represents an integer of 1 or more, b represents an integer of 1 or more, a + b is 3 or more, and A is a carbon which may be substituted with a fluorine atom. Aliphatic hydrocarbon groups of number 1-10, -O-, -C (= O)-, -S-, -S (= O) _2- , -NHC (= O)-, or 2 or more of these It is a combined group, and each independently represents a binding site with another structure.
n is preferably an integer of 3 to 10, and more preferably an integer of 3 to 6.
For a, an integer of 1 to 10 is preferable, an integer of 1 to 4 is more preferable, and 1 or 2 is more preferable.
b is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and more preferably 1 or 2.
a + b is preferably an integer of 3 to 10, and more preferably an integer of 3 to 6.
A consists of a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, −O−, −C (= O) −, −S− and S (= O) _2−. It is preferably the group of choice, −CH ₂ −, −O−, −S−, −S (= O) ₂ −, −C (CF ₃ ) ₂ −, and −C (CH ₃ ) _2. More preferably, it is a divalent group selected from the group consisting of −.
Each of the n * may be bonded to the same carbon atom in the formula, but it is preferably bonded to different carbon atoms.
Each of a * may be bonded to the same carbon atom in the formula, but it is preferably bonded to different carbon atoms.
Each of the b * may be bonded to the same carbon atom in the formula, but it is preferably bonded to different carbon atoms.

Examples of the n-valent amine compound include compounds having the following structures.

−N−
In the formula (A-3), n represents an integer of 3 or more, an integer of 3 to 10 is preferable, and an integer of 3 to 6 is more preferable.

式（Ｂ−１）〜式（Ｂ−３）中、Ｒ^１１５は４価の有機基を表し、Ｒ^Ａ２１は水素原子又は１価の有機基を表し、Ｒ^Ｂ１１、Ｒ^Ｂ１２、Ｒ^Ｂ１３、Ｒ^Ｂ１４、Ｒ^Ｂ２１、Ｒ^Ｂ２２及びＲ^Ｂ２３はそれぞれ独立に、２価の連結基を表し、Ｒ^Ａ３１はｎ価の連結基を表し、ｎは３以上の整数を表し、ａは１〜３の整数を表し、ｂは０〜２の整数を表し、ａ＋ｂは３であり、＊はそれぞれ独立に、他の構造との結合部位を表す。[Repeat unit with branched structure]
The specific polymer precursor is selected from the group consisting of a repeating unit represented by the following formula (B-1) and a repeating unit represented by the following formula (B-2) as a repeating unit having a branched structure. It is preferable to contain at least one kind.
Further, the specific polymer precursor may further have a repeating unit represented by the following formula (B-3).

In formulas (B-1) to (B-3), R ¹¹⁵ represents a tetravalent organic group, ^{RA 21} represents a hydrogen atom or a monovalent organic group, and R ^B11 , ^RB12 , ^RB13 , R. ^B14 , ^RB21 , ^RB22 and ^RB23 each independently represent a divalent linking group, ^RA31 represents an n-valent linking group, n represents an integer of 3 or more, and a represents an integer of 1-3. , B represents an integer of 0 to 2, a + b is 3, and * represents a binding site with another structure independently.

-R ¹¹⁵ (Equation (B-1))-
Wherein ^{(B-1), R 115} has the same meaning as ^{R 115} in the above formula (A-1), a preferable embodiment thereof is also the same.

^-RB11 , ^RB12 , ^RB13 and ^RB14-
In formula (B-1), ^RB11 , ^RB12 , ^RB13 and ^RB14 each independently represent a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group in which two or more of these are combined, and the number of carbon atoms is exemplified. A linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or 2 of these. The above combined groups are preferable, and aromatic groups having 6 to 20 carbon atoms are more preferable.

Each ^{R B11, R B12, R B13} and ^{R B14} are independently of formula (B-1), is preferably derived from a diamine. Examples of the diamine used for producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one kind of diamine may be used, or two or more kinds of diamines may be used.

Specifically, the diamine is 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 two or more combined 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 an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be single-bonded or 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 is preferable, and it is a single bond or an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom. , -O-, -C (= O)-, -S- and S (= O) _2- , more preferably -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 examples of the diamine 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 paraphenylenediamine, 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'-diaminodiphenylsulfide, 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'-diaminoparatelphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) ) Phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (2-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 9,10- Bis (4-aminophenyl) anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl sulfone, 1,3-bis (4-aminophenoxy) 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'-Diaminooctafluorobiphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9,9 -Bis (4-aminophenyl) -10-hydroanthracene, 3,3', 4,4'-tetraaminobiphenyl, 3,3', 4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1 , 5-Diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis (4-aminophenyl) fluorene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2- (3', 5'-diaminobenzoyloxy) ethyl methacrylate, 2,4- or 2,5-diaminocumen, 2 , 5-Dimethyl-paraphenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-paraphenylenediamine, 2,4,6-trimethyl-metaphenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane , 2,7-Diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-aminophenyl) ethane, diaminobenzanilide, diaminobenzoic acid ester, 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 (trifluoro) Methyl) Phenyl] Hexafluoropropane, 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) diphenyl sulfone, 4,4'-bis (3-amino-5-trifluoromethylphenoxy) diphenyl sulfone, 2,2-bis [4- (4-amino-3-trifluoromethylphenoxy) ) Phenyl] Hexafluoropropane, 3,3', 5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2, Included are at least one diamine selected from 2', 5,5', 6,6'-hexafluorotridin and 4,4'-diaminoquaterphenyl.

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

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

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

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

Each ^{R B11, R B12, R B13} and ^{R B14} in Formula (1) independently from the viewpoint of the flexibility of the cured film ^obtained, -Ar ⁰ -L ⁰ -Ar ⁰ - is preferably represented by. Ar ⁰ is independently an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), and a phenylene group is preferable. L ⁰ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be single-bonded or substituted with a fluorine atom, −O−, −C (= O) −, −S−, −S (=). _O) 2 -, - NHCO-, or represent these two or more combined groups. The preferred range of L ⁰ is synonymous with A above.

Each ^{R B11, R B12, R B13} and ^{R B14} is independently in Formula (1), from the viewpoint of i-line transmittance is a divalent organic group represented by the following formula (51) or (61) Is preferable. In particular, a divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-ray transmittance and availability.

In formula (51), R ^{50 to} R ⁵⁷ are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and ^{at least one of R 50 to} R ⁵⁷ is a fluorine atom, a methyl group, a fluoromethyl group, and the like. It is a difluoromethyl group or a trifluoromethyl group, and * independently represents a binding site with another structure.

The ^{monovalent organic group of R 50 to} R ⁵⁷ includes an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkyl fluoride group.

In formula (61), R ⁵⁸ and R ⁵⁹ are independently fluorine atoms, fluoromethyl groups, difluoromethyl groups, or trifluoromethyl groups, respectively.

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

-R ¹¹⁵ (Equation (B-2))-
Wherein ^{(B-2), R 115} has the same meaning as ^{R 115} in the above formula (A-2), preferable embodiments thereof are also the same.

^-RA21-
Wherein ^{(B-2), R A21} has the same meaning as ^{R A21} in the above formula (A-2), preferable embodiments thereof are also the same.

^-RB21 , ^RB22 and ^RB23-
In formula ^(B-2), the R ^{B21, R B22} and ^{R B23} are each independently has the same meaning as ^{R B11, R B12, R B13} and ^{R B14} in the above formula (B-1), preferred embodiments are also same Is.

-R ¹¹⁵ (Equation (B-3))-
Wherein ^{(B-3), R 115} has the same meaning as ^{R 115} in the above formula (A-1), a preferable embodiment thereof is also the same.

^-RA31-
Wherein ^{(B-3), R A31} has the same meaning as ^{R A31} in the above formula (A-3), preferable embodiments thereof are also the same.

−N−
In the formula (B-3), n has the same meaning as n in the above formula (A-3), and the preferred embodiment is also the same.

−A−
In formula (B-3), a is preferably 1.

−B−
In formula (B-3), b is preferably 2.

When the specific polymer precursor contains a repeating unit represented by the formula (B-1), the repeating unit represented by the formula (B-1) may be one kind, but may be two or more kinds. good. Further, it may contain a structural isomer of a repeating unit represented by the formula (B-1). Similarly, when the repeating unit represented by the formula (B-2) is included and when the repeating unit represented by the formula (B-3) is included, these repeating units may be one kind. However, it may be two or more kinds and may contain structural isomers.

[Other repeating units]
The specific polymer precursor preferably contains a repeating unit other than the repeating unit having the above-mentioned branched structure.
The specific polymer precursor preferably has a repeating unit represented by the following formula (1) as the other repeating unit.

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

The specific polymer precursor is selected from the group consisting of a repeating unit represented by the formula (1), a repeating unit represented by the formula (B-1), and a repeating unit represented by the formula (B-2). ^{When including at least one repeating unit, * 1} in the repeating unit represented by the formula (1), the repeating unit represented by the formula (B-1), or the table using the formula (B-2). It is preferable that * in the repeating unit to be combined is combined. Further, in this case, * ² in the repeating unit represented by the equation (1) is preferably combined with ^{* 1} in the repeating unit represented by the other equation (1).
When the specific polymer precursor contains a repeating unit represented by the formula (1) and a repeating unit represented by the formula (B-3), * ^{2 in the repeating unit represented by the formula (1).} And * in the repeating unit represented by the formula (B-3) are preferably combined. Further, in this case, it is preferable that ^{* 1 in the repeating unit represented by the equation (1) is combined with * 2} in the repeating unit represented by the other equation (1).

Further, as one embodiment of the specific polymer precursor in the present invention, the repeating unit represented by the formula (B-1), the repeating unit represented by the formula (B-2), and the formula (B-) for all the repeating units. The specific polymer precursor having a total content of the repeating unit represented by 3) and the repeating unit represented by the formula (1) of 50 mol% or more, further 70 mol% or more, particularly 90 mol% or more. Is exemplified. As an upper limit, 100 mol% or less is practical.
However, even when the specific polymer precursor contains the repeating unit represented by the formula (1), the above-mentioned branched structure and the repeating unit represented by the formula (1) are bonded by any structure. May be good. That is, even when the specific polymer precursor contains the repeating unit represented by the formula (1), the structure of the specific polymer precursor is not particularly limited as long as it has the above-mentioned branched structure.

-A ¹ and A ^{2-
A 1} and A ² in the formula (1) independently represent an oxygen atom or −NH−, and an oxygen atom is preferable.

−R ¹¹¹ −
In the formula (1), R ^{111 has the same meaning as RB 11} in the above formula (B-1), and the preferred embodiment is also the same.

-R ^115-
Wherein ^{(1), R 115} has the same meaning as ^{R 115} in the above formula (A-1), a preferable embodiment thereof is also the same.

-R ¹¹³ and R ^114-
In the formula (1), R ¹¹³ and R ^{114 are independently synonymous with RA 22} included in the preferred embodiment ^{of RA 21} in the above formula (A-1), and the preferred embodiments are also the same.

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

A ¹¹ and A ¹² represent an oxygen atom or -NH-, R ¹¹¹ and R ¹¹² each independently represent a divalent organic radical, and R ¹¹³ and R ¹¹⁴ independently represent a hydrogen atom or 1 It represents a valent organic group, * ¹ and * ² each independently represent a binding site with another structure, and ^{at least one of R 113} and R ¹¹⁴ is preferably a group containing a radically polymerizable group. It is more preferably a radically polymerizable group.

The preferred ranges of A ¹¹ , A ¹² , R ¹¹¹ , R ^113, R ¹¹⁴ , * ¹ and * ^{2 , respectively, are A 1} , A ² , R ¹¹¹ , R ¹¹³ , R ¹¹⁴ , * ¹ and * 1 in equation (1), respectively. It is synonymous with the preferable range of * ^2.

A preferred range of R ¹¹² has the same meaning as ^{R 112} in formula (5), and more preferably among others oxygen atoms.

The bonding position of the carbonyl group to the benzene ring in the formula is preferably 4, 5, 3', 4'in the formula (1-A). In formula (1-B), it is preferably 1, 2, 4, 5.

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

[Relationship between main chain and branched chain]
It is preferable that at least one of the repeating units contained in the branched chain of the specific polymer precursor is the same as at least one of the repeating units contained in the main chain of the specific polymer precursor.
Of the repeating units contained in the main chain, only one branched chain containing the same repeating unit as at least one repeating unit may be contained in the specific polymer precursor, or two or more may be contained. .. Further, the specific polymer precursor may further have a branched chain that does not contain the same repeating unit as at least one of the repeating units contained in the main chain, but an embodiment that does not have the repeating unit is also preferable.
The branched chain preferably contains a repeating unit represented by the above formula (1).
The main chain is represented by the formula (1) and at least one selected from the group consisting of the repeating unit represented by (B-1) and the repeating unit represented by the formula (B-2). It is preferable to include a repeating unit.
The main chain may further contain a repeating unit represented by the formula (B-3).
Further, it is preferable that both the main chain and the branched chain contain a repeating unit represented by the formula (1), and both the main chain and the branched chain are the repeating units represented by the formula (1). It is more preferable to include the same repeating unit.

[Molecular weight]
The weight average molecular weight of the specific polymer precursor is preferably 1,000 to 100,000, more preferably 3,000 to 90,000, and even more preferably 5,000 to 75,000. ..
The degree of dispersion of the molecular weight of the polyimide precursor is preferably 1.2 to 3.5, more preferably 1.5 to 3.
In the present specification, the degree of molecular weight dispersion means a value obtained by dividing the weight average molecular weight by the number average molecular weight (weight average molecular weight / number average molecular weight).

〔Concrete example〕
Specific examples of the specific polymer precursor include PA-1 to PA-4 used in Examples described later, and compounds represented by the following structural formulas.
In the following structure, two or three repeating units contained in parentheses are combined to form a resin. In addition, * and the wavy line portion are combined in each repetition unit. Furthermore, in the present invention, these resins may have still other repeating units as long as the effects of the present invention can be obtained.

[Synthesis method]
The specific polymer precursor is synthesized, for example, by the synthetic method shown in the synthetic examples in Examples described later.
Specifically, for example, it is obtained by reacting a polyvalent carboxylic acid or a polyvalent carboxylic acid derivative with a diamine. As the polyvalent carboxylic acid or the polyvalent carboxylic acid derivative, at least a trivalent or higher polyvalent carboxylic acid or a trivalent or higher polyvalent carboxylic acid derivative is used, and a trivalent or tetravalent polyvalent carboxylic acid (tricarboxylic acid) is used. Alternatively, it is preferable to use at least a trivalent or tetravalent polyvalent carboxylic acid derivative (tricarboxylic acid derivative or tetracarboxylic acid derivative).
Further, in addition to the above trivalent or higher polyvalent carboxylic acid or trivalent or higher polyvalent carboxylic acid derivative, a divalent carboxylic acid (dicarboxylic acid) or a divalent carboxylic acid derivative (dicarboxylic acid derivative) is further used. May be good.
Preferably, the polyvalent carboxylic acid or the polyvalent carboxylic acid derivative is obtained by halogenating it with a halogenating agent and then reacting it with a diamine.
As another synthetic method, a method of reacting a dicarboxylic acid or a dicarboxylic acid derivative with a trivalent or higher polyvalent amine can be mentioned. In this case, it is preferable that the dicarboxylic acid or the dicarboxylic acid derivative is halogenated with a halogenating agent and then reacted with a trivalent or higher polyvalent amine.

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

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

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

〔Content〕
The content of the specific polymer precursor in the curable resin composition of the present invention is 0.001% by mass with respect to the total solid content of the curable resin composition from the viewpoint of improving the breaking elongation of the obtained cured film. The above is preferable, 0.01% by mass or more is more preferable, and 0.5% by mass or more is further preferable.
The upper limit of the content is preferably 30% by mass or less, more preferably 20% by mass or less, and 15% by mass or less from the viewpoint of improving the resolution of the curable resin composition. It is more preferably 10% by mass or less, and even more preferably 5% by mass or less.
When the curable resin composition of the present invention contains another heterocyclic-containing polymer precursor described later, the content of the specific polymer precursor is specified from the viewpoint of improving the breaking elongation of the obtained cured film. It is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and 0.05% by mass or more with respect to the total amount of the polymer precursor and other heterocyclic-containing polymer precursors. It is more preferable to have.
The upper limit of the content is preferably 50% by mass or less, more preferably 40% by mass or less, and 30% by mass or less from the viewpoint of improving the resolution of the curable resin composition. It is more preferably 25% by mass or less, and even more preferably 10% by mass or less.

The curable resin composition of the present invention may contain only one type of specific polymer precursor, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.

<Other heterocyclic-containing polymer precursors>
The curable resin composition of the present invention preferably contains other heterocyclic-containing polymer precursors (hereinafter, also simply referred to as “other polymer precursors”) other than the above-mentioned specific polymer precursors.
The curable resin composition of the present invention preferably contains, as the other polymer precursor, at least one precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, and the polyimide precursor is preferably used. It is more preferable to include it.

[Polyimide precursor]
From the viewpoint of the film strength of the obtained cured film, the polyimide precursor preferably has the repeating unit represented by the formula (1) in the above-mentioned specific polymer precursor.

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

As one embodiment of the polyimide precursor in the present invention, 50 mol% or more, more 70 mol% or more, particularly 90 mol% or more of all the repeating units are the repeating units represented by the formula (1). Is exemplified. As an upper limit, 100 mol% or less is practical.

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. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.

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

The polyimide precursor 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 with a halogenating agent and then reacting with a diamine.

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

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

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

[Polybenzoxazole precursor]
The polybenzoxazole precursor preferably contains a repeating unit represented by the following formula (2).

In formula (2), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group. show.

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

−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 preferable range is also the same. R ¹²² is preferably derived from 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.

-R ¹²³ and R ^124-
R ¹²³ and R ¹²⁴ independently represent a hydrogen atom or a monovalent organic group, ^{and have the same meaning as R 113} and R ¹¹⁴ in the above formula (1), and the preferred range is also the same.

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

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

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.} It is a group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), and the rest is a hydrogen atom or 1 to 30 carbon atoms (preferably 1 to 18 carbon atoms). It is preferably an organic group having 1 to 12 carbon atoms, particularly preferably 1 to 6) carbon atoms, and may be the same or different from each other. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. In the Z moiety, preferably a structure is 5 to 95 mol%, b structure is 95 to 5 mol%, and a + b is 100 mol%.

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

When the polybenzoxazole precursor contains a diamine residue represented by the formula (SL) as another kind of repeating unit, the tetracarboxylic dianhydride is further provided in that it improves the alkali solubility of the curable resin composition. It is preferable to include the tetracarboxylic dian residue remaining after the removal of the acid dianhydride group from the substance as a repeating unit. Examples of such a tetracarboxylic acid residue include the example of R ¹¹⁵ in the formula (1).

The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, still more preferably 10,000 to 50,000. be. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.

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

The content of the other polymer precursor in the curable resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total solid content of the curable resin composition. It is more preferably 40% by mass or more, further preferably 50% by mass or more, further preferably 60% by mass or more, and further preferably 70% by mass or more. Further, the content of other polymer precursors in the curable resin composition of the present invention is preferably 99.5% by mass or less, preferably 99% by mass or less, based on the total solid content of the curable resin composition. It is more preferably 98% by mass or less, further 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 kind of other polymer precursors, or may contain two or more kinds. When two or more kinds are contained, it is preferable that the total amount is within the above range.

[Other resins]
The curable resin composition of the present invention may further contain other resins.
As another resin, for example, it has a branched structure represented by the above formula (A-1), and as a branched chain bonded to the branched structure, it has a branched chain having a repeating unit and has a branched chain. Examples thereof include compounds that do not form an imide structure by heating.
Other resins are not polyimide precursors because they do not form an imide structure when heated.
Specific examples thereof include a resin having a branched structure represented by the above formula (A-1) and not having a repeating unit represented by the above formula (1).

Specific examples of other resins include, but are not limited to, PA-5 used in the examples, resins having the following structures, and the like. In the following structure, two repeating units contained in parentheses are combined to form a resin. In addition, * and the wavy line portion are combined in each repetition unit. Furthermore, in the present invention, these resins may have still other repeating units as long as the effects of the present invention can be obtained.

When the curable resin composition of the present invention contains another resin, the content of the other resin may be more than 0% by mass and 50% by mass or less with respect to the total solid content of the curable resin composition. It is more preferably more than 0% by mass and 30% by mass or less.

<Onium salt>
The curable resin composition of the present invention preferably contains an onium salt.
The type of onium salt and the like are not particularly specified, but ammonium salt, iminium salt, sulfonium salt, iodonium salt or phosphonium salt are preferably mentioned.
Among these, an ammonium salt or an iminium salt is preferable from the viewpoint of high thermal stability, and a sulfonium salt, an iodonium salt or a phosphonium salt is preferable from the viewpoint of compatibility with a polymer.

Further, the onium salt is a salt of a cation and an anion having an onium structure, and the cation and the anion may 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 it is preferably an intermolecular salt. Further, in the curable resin composition of the present invention, the cation portion or the cation molecule and the anion portion or the anion molecule may be bonded or dissociated by an ionic bond.
As the cation in the onium salt, an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation is preferable, and at least one cation selected from the group consisting of a tetraalkylammonium cation, a sulfonium cation and an iodonium cation is more preferable.

The onium salt used in the present invention may be a thermal base generator.
The thermal base generator refers to a compound that generates a base by heating, and examples thereof include an acidic compound that generates a base when heated to 40 ° C. or higher.

[Ammonium salt]
In the present invention, the 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-
As the ammonium cation, a quaternary ammonium cation is preferable.
The ammonium cation is preferably a cation represented by the following formula (101).

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 be bonded to each other to form a ring.

In the 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. It is more preferably 12 aryl groups. R ^{1 to} R ⁴ 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. Examples thereof include a carbonyl group and an acyloxy group.
When ^{at least two of R 1 to} R ⁴ are bonded to each other to form a ring, the ring may contain a heteroatom. Examples of the heteroatom include a nitrogen atom.

The ammonium cation is preferably represented by any of the following formulas (Y1-1) and (Y1-2).

In the formula (Y1-1) and ^{(Y1-2), R 101} represents an n-valent organic group, ^{R 1} has the same meaning as ^{R 1} in the formula ^{(101), Ar 101} and ^{Ar 102} are each independently , Represents an aryl group, and n represents an integer of 1 or more.
In the 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. More preferably, it is a group obtained by removing n hydrogen atoms from the saturated aliphatic hydrocarbon, benzene or naphthalene.
In the formula (Y1-1), n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
In the formula (Y1-2), Ar ¹⁰¹ and Ar ¹⁰² are preferably phenyl groups or naphthyl groups, respectively, and more preferably phenyl groups.

− Anion −
As the anion in the ammonium salt, one selected from a carboxylic acid anion, a phenol anion, a phosphoric acid anion and a sulfate anion is preferable, and a carboxylic acid anion is more preferable because both salt stability and thermal decomposability can be achieved. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylic acid anion.
The carboxylic acid anion is preferably a divalent or higher carboxylic acid anion having two or more carboxy groups, and more preferably a divalent carboxylic acid anion. 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 carboxylic acid 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 that Hammett's substituent constant σm shows a positive value. Here, σm is a review article by Yusuke Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965) p. It is described in detail in 631-642. The electron-withdrawing group in the present embodiment is not limited to the substituent described in the above document.
Examples of substituents in which σm shows a positive value are CF ₃ groups (σm = 0.43), CF ₃ C (= O) groups (σm = 0.63), and HC≡C groups (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。The EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).

In the formulas (EWG-1) to (EWG-6), R ^{x1 to} R ^x3 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 carboxylic acid anion is preferably represented by the following formula (XA).

In the formula ^{(XA), L 10} represents a single bond or an alkylene group, an alkenylene group, an aromatic group, -NR ^X - represents and divalent connecting group selected from the group consisting a combination thereof, ^{R X} is , Hydrogen atom, alkyl group, alkenyl group or aryl group.

Specific examples of the carboxylic acid anion include maleic acid anion, phthalate anion, N-phenyliminodiacetic acid anion and oxalic acid anion.

From the viewpoint that 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, the onium salt in the present invention contains an ammonium cation as a cation, and the onium salt is an anion. As a result, it is preferable to contain an anion having a pKa (pKaH) of 2.5 or less, and more preferably to contain an anion having a pKa (pKaH) of 1.8 or less.
The lower limit of pKa is not particularly limited, but it is preferably -3 or more, preferably -2 or more, from the viewpoint that the generated base is difficult to neutralize and the cyclization efficiency of the specific precursor or the like is improved. Is more preferable.
The above pKa includes Determination of Organic Structures by Physical Methods (authors: Brown, HC, McDaniel, D.H., Hafliger, O., Nachod, F. C.; Nachod, F.C .; Academic Press, New York, 1955) and Data for Biotechical Research (Author: Dawson, RMC et al; Oxford, Clarendon, see Value 59). Can be done. For compounds not described in these documents, the values calculated from the structural formulas using software of ACD / pKa (manufactured by ACD / Labs) shall be used.

Specific examples of the ammonium salt include, but are not limited to, the following compounds.

[Iminium salt]
In the present invention, the iminium salt means a salt of an iminium cation and an anion. As the anion, the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.

-Iminium cation-
As the iminium cation, a pyridinium cation is preferable.
Further, 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 are bonded to each other to form a ring. It may be formed.
Wherein (102), ^{R 5} and ^{R 6} have the same meanings as R1~R4 in the above formula (101), preferable embodiments thereof 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 a heteroatom. Examples of the heteroatom include a nitrogen atom. Further, as the 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。The iminium cation is preferably represented by any of the following formulas (Y1-3) to (Y1-5).

In Formula ^{(Y1-3) ~ (Y1-5),} R 101 represents an n-valent organic group, ^{R 5} has the same meaning as ^{R 5} in the formula (102), ^{R 7} is R in the formula (102) ^{Synonymous with 7} , n and m represent integers of 1 or more.
In the formula (Y1-3), R ¹⁰¹ is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from the structure to which these are bonded, and has 2 to 30 carbon atoms. More preferably, it is a group obtained by removing n hydrogen atoms from the saturated aliphatic hydrocarbon, benzene or naphthalene.
In the formula (Y1-3), n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
In the formula (Y1-5), m is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.

Specific examples of the iminium salt include, but are not limited to, the following compounds.

[Sulfonium salt]
In the present invention, the sulfonium salt means a salt of a sulfonium cation and an anion. As the anion, the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.

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

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. It is more preferably an aryl group, and even 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. Examples thereof include a carbonyl group and an acyloxy group. Among these, it is preferable to have an alkyl group or an alkoxy group as the substituent, more preferably to have a branched alkyl group or an alkoxy group, and a branched alkyl group having 3 to 10 carbon atoms or a branched alkyl group having 1 to 1 carbon atoms. It is more preferable to have 10 alkoxy groups.
R ^{8 to} R ¹⁰ may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.

Specific examples of the sulfonium salt include, but are not limited to, the following compounds.

[Iodonium salt]
In the present invention, the iodonium salt means a salt of an iodonium cation and an anion. As the anion, the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.

-Iodonium cation-
The iodonium cation is preferably a diallyl iodonium cation.
Further, 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. It is more preferably an aryl group, and even 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 and an aryloxy group. Examples thereof include a carbonyl group and an acyloxy group. Among these, it is preferable to have an alkyl group or an alkoxy group as the substituent, more preferably to have a branched alkyl group or an alkoxy group, and 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 synthetic suitability, they are preferably the same group.

Specific examples of the iodonium salt include, but are not limited to, the following compounds.

[Phoenium salt]
In the present invention, the phosphonium salt means a salt of a phosphonium cation and an anion. As the anion, the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.

-Phoenium cation-
As the phosphonium cation, a quaternary phosphonium cation is preferable, and examples thereof include a tetraalkylphosphonium cation and a triarylmonoalkylphosphonium cation.
Further, 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. It is more preferably an aryl group, and even 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. Examples thereof include a carbonyl group and an acyloxy group. Among these, it is preferable to have an alkyl group or an alkoxy group as the substituent, more preferably to have a branched alkyl group or an alkoxy group, and 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 synthetic suitability, they are preferably the same group.

Specific examples of the phosphonium salt include, but are not limited to, the following compounds.

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 with respect to 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, further 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, further preferably 20% by mass or less, further preferably 10% by mass or less, 5% by mass or less, or 4% by mass or less.
As the onium salt, one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.

<Thermal base generator>
The curable resin composition of the present invention may contain a thermosetting agent.
The thermobase generator may be a compound corresponding to the above-mentioned onium salt, or may be a thermobase generator other than the above-mentioned onium salt.
It is assumed that the other thermobase generator does not contain the compound corresponding to the above-mentioned onium salt.
Examples of other thermobase generators include nonionic thermobase generators.
Examples of the nonionic thermal base generator include compounds represented by the formula (B1) or the formula (B2).

In the formula (B1) and the formula (B2), Rb ¹ , Rb ² and Rb ³ are independently organic groups, halogen atoms or hydrogen atoms having no tertiary amine structure. However, Rb ¹ and Rb ² do not become hydrogen atoms at the same time. Further, ^{none of Rb 1} , Rb ² and Rb ³ has a carboxy group. In the present 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, this does not apply when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when an amide group is formed together with a nitrogen atom.

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

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, still more preferably 3 to 12 carbon atoms), and an alkenyl group (preferably 2 to 24 carbon atoms). , 2-18 are more preferred, 3-12 are more preferred), aryl groups (6-22 carbons are preferred, 6-18 are more preferred, 6-10 are even more preferred), or arylalkyl groups (7 carbons). ~ 25 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable). These groups may have a substituent as long as the effect of the present invention is exhibited. Rb ¹ and Rb ² may be coupled to each other to form a ring. As the ring to be formed, a 4- to 7-membered nitrogen-containing heterocycle is preferable. Rb ¹ and Rb ² are particularly linear, branched or cyclic alkyl groups which may have substituents (preferably 1 to 24 carbon atoms, more preferably 2 to 18 and even more preferably 3 to 12). It is more preferably a cycloalkyl group which may have a substituent (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms) and having a substituent. Maybe cyclohexyl groups are more preferred.

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

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

In the formula, Rb ¹¹ and Rb ¹² , and Rb ³¹ and Rb ³² are the same as ^{Rb 1} and Rb ² in the formula (B1), respectively.
Rb ¹³ has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms) and an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms) and 3 to 12 carbon atoms. Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and a substituent may be provided as long as the effect of the present invention is exhibited. Among them, Rb ¹³ is preferably an arylalkyl group.

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

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

As the compound represented by the formula (B1-1), the compound represented by the formula (B1-1a) is also preferable.

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

The molecular weight of the nonionic thermal base generator is preferably 800 or less, more preferably 600 or less, and 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, the following compounds can be mentioned as specific examples of the compound which is a thermal base generator or other specific examples of the thermal base generator.

The content of the thermosetting agent is preferably 0.1 to 50% by mass with respect to 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, further preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less. As the thermal base generator, one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.

<Photopolymerization initiator>
The curable resin composition of the present invention preferably contains a photopolymerization initiator.
The photopolymerization initiator is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited and may be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. Further, it may be an active agent that causes some action with a photoexcited sensitizer and generates an active radical.

The photoradical polymerization 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 preferable. The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

As the photoradical polymerization initiator, a known compound can be arbitrarily used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime derivatives and the like. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azido compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. Can be mentioned. For details thereof, the description in paragraphs 0165 to 0182 of JP2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219 can be referred to, and the contents thereof are incorporated in the present specification.

As the ketone compound, for example, the compound described in paragraph 0087 of JP-A-2015-087611 is exemplified, and the content thereof is incorporated in the present specification. As a commercially available product, KayaCure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

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

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

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

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

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

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

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

As specific examples of the oxime compound, the compound described in JP-A-2001-233842, the compound described in JP-A-2000-080068, and the compound described in JP-A-2006-342166 can be used.

Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminovtan-2-one, and 2-acetoxy. Iminopentan-3-one, 2-acetoxyimimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one , And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like. In the curable resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as the photoradical polymerization initiator. The oxime-based photopolymerization initiator has a> C = N—O—C (= O) − linking group in the molecule.

Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), ADEKA PTOMER N-1919 (manufactured by ADEKA Corporation, JP-A-2012-014502). A radical polymerization initiator 2) is also preferably used. Further, TR-PBG-304 (manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.), ADEKA Arklus NCI-831 and ADEKA Arklus NCI-930 (manufactured by ADEKA Corporation) can also be used. Further, DFI-091 (manufactured by Daito Chemix Co., Ltd.) can be used.

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

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

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

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

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

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

In the formula, R ^{I05 to} R ^I07 are the same as ^{R I 02 to} R I ⁰⁴ of the above formula (I).

Further, as the photoradical polymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469 can also be used.

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

<Thermal polymerization initiator>
The curable resin composition of the present invention may contain a thermal polymerization initiator as the polymerization initiator, and may particularly contain a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the heterocyclic polymer precursor can be promoted together with the cyclization of the heterocyclic polymer precursor, so that higher heat resistance can be achieved.

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

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

<Polymerizable compound>
[Radical polymerizable compound]
The curable resin composition of the present invention preferably contains a polymerizable compound.
As the polymerizable compound, a radically polymerizable compound can be used. The radically polymerizable compound is a compound having a radically polymerizable group. Examples of the radically polymerizable group include groups having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group and a (meth) acryloyl group. The radically polymerizable group is preferably a (meth) acryloyl group, and more preferably a (meth) acryloyl group from the viewpoint of reactivity.

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

The molecular weight of the radically polymerizable compound is preferably 2,000 or less, more preferably 1,500 or less, still more preferably 900 or less. The lower limit of the molecular weight of the radically polymerizable compound is preferably 100 or more.

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

Specific examples of the radically polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides, and preferred examples thereof. Esters of unsaturated carboxylic acid and polyhydric alcohol compound, and amides of unsaturated carboxylic acid and polyhydric amine compound. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a sulfanyl group with a monofunctional or polyfunctional isocyanate group or an epoxy group, or a monofunctional or polymorphic acid group. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a polyelectron substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines and thiols, and a halogeno group. Substitution reaction products of unsaturated carboxylic acid esters or amides having a desorbing substituent such as tosyloxy group and monofunctional or polyfunctional alcohols, amines and thiols are also suitable. Further, as another example, it is also possible to use a compound group in which the above unsaturated carboxylic acid is replaced with a vinylbenzene derivative such as unsaturated phosphonic acid or styrene, vinyl ether, allyl ether or the like. As a specific example, the description in paragraphs 0113 to 0122 of JP-A-2016-0273557 can be referred to, and these contents are incorporated in the present specification.

Further, as the radically polymerizable compound, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable. Examples are polyethylene glycol di (meth) acrylate, trimethyl ethanetri (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, trimethylolpropanetri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin, trimethylolethane, etc. A compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, is described in JP-A-48-041708, JP-A-50-006034, and JP-A-51-0379193. Urethane (meth) acrylates as described above, polyester acrylates, epoxy resins and (meth) acrylics described in JP-A-48-064183, Japanese Patent Publication No. 49-043191, and Japanese Patent Publication No. 52-030490. Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acids, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Further, a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether group such as glycidyl (meth) acrylate and a compound having an ethylenically unsaturated bond can also be mentioned.

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

Further, as other examples, the specific unsaturated compound described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, Japanese Patent Publication No. 01-040336, and Japanese Patent Application Laid-Open No. 02-025493. Vinyl phosphonic acid compounds and the like can also be mentioned. Further, a compound containing a perfluoroalkyl group described in JP-A-61-022048 can also be used. Furthermore, the journal of the Japan Adhesive Association vol. 20, No. Those introduced as photopolymerizable monomers and oligomers on pages 7, 300-308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964 and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used, and the contents thereof are described in the present specification. Incorporated into the book.

Further, the compound described in JP-A No. 10-062986 together with specific examples as the formulas (1) and (2), which is obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated, is also available. It can be used as a radically polymerizable compound.

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

Examples of the radically polymerizable compound include dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nippon Kayaku). Made by A-TMMT Co., Ltd .: Shin-Nakamura Chemical Industry Co., Ltd.), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), Dipentaerythritol hexa ( Meta) Acrylate (Kayarad DPHA as a commercial product; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and these (meth) acryloyl groups contain ethylene glycol residues or propylene glycol residues. A structure that is bonded via a structure is preferable. These oligomer types can also be used.

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

Examples of the radically polymerizable compound include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Laid-Open No. 02-032293, and Japanese Patent Application Laid-Open No. 02-016765. , Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418. Urethane compounds having an ethylene oxide-based skeleton are also suitable. Further, as the radically polymerizable compound, compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238 are used. It can also be used.

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

The acid value of the radically polymerizable compound having an acid group is preferably 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When the acid value of the radically polymerizable compound is within the above range, it is excellent in manufacturable handling and further excellent in developability. Moreover, the polymerizability is good. The acid value is measured according to the description of JIS K 0070: 1992.

In the curable resin composition of the present invention, a monofunctional radically polymerizable compound can be preferably used as the radically polymerizable compound from the viewpoint of suppressing warpage associated with controlling the elastic modulus of the cured film. Examples of the monofunctional radically polymerizable compound include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl (meth). (Meta) acrylates, benzyl (meth) acrylates, phenoxyethyl (meth) acrylates, N-methylol (meth) acrylamides, glycidyl (meth) acrylates, polyethylene glycol mono (meth) acrylates, polypropylene glycol mono (meth) acrylates and the like (meth). ) N-vinyl compounds such as acrylic acid derivatives, N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allylglycidyl 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.

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

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

（式中、ｔは、１〜２０の整数を示し、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。）

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

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

(In the formula, u indicates an integer of 3 to 8, R ⁵⁰⁴ indicates an organic group having a u-valence of 1 to 200 carbon atoms, and R ⁵⁰⁵ indicates 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 indicates an organic group having 1 to 10 carbon atoms.)

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

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

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

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

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

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

-Benzoxazine compound (compound having a benzoxazolyl group)-
Since the benzoxazine compound is a cross-linking reaction derived from the cycloaddition reaction, degassing does not occur during curing, and heat shrinkage is further reduced to suppress the occurrence of warpage, which is preferable.

Preferred examples of the benzoxazine compound include B-a type benzoxazine, Bm type benzoxazine (hereinafter, trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, and phenol novolac type dihydrobenzo. Examples include oxazine compounds. These may be used alone or in combination of two or more.

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

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

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

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

Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol. Suitable examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.

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

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

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

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

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

In the present invention, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ- Consists of one solvent selected from butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, or two or more. The mixed solvent to be mixed is preferable. The combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

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

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

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

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

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

Examples of other migration inhibitors include the rust preventive agent described in paragraph 0094 of JP2013-015701, the compound described in paragraphs 0073 to 0076 of JP2009-283711, and JP-A-2011-059656. The compound described in paragraph 0052, the compound described in paragraphs 0114, 0116 and 0118 of JP2012-194520A, the compound described in paragraph 0166 of International Publication No. 2015/199219 and the like can be used.

Specific examples of the migration inhibitor 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 is 0. .05 to 2.0% by mass is more preferable, and 0.1 to 1.0% by mass is further preferable.

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

<Polymerization inhibitor>
The curable resin composition of the present invention preferably contains a polymerization inhibitor.

Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'. -Thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine , N-Phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1 -Nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5 (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, Bis (4-hydroxy-3,5-tert-butyl) phenylmethane and the like are preferably used. Further, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compound described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used.

In addition, 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 shall be 0.01 to 5% by mass with respect to the total solid content of the curable resin composition of the present invention. Is more preferable, 0.02 to 3% by mass is more preferable, and 0.05 to 2.5% by mass is further preferable.

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

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

Examples of the silane coupling agent include the compound described in paragraph 0167 of International Publication No. 2015/199219, the compound described in paragraphs 0062 to 0073 of JP-A-2014-191002, paragraph of International Publication No. 2011/080992. The compounds described in 0063 to 0071, the compounds described in paragraphs 0060 to 0061 of JP-A-2014-191252, the compounds described in paragraphs 0045-0052 of JP-A-2014-041264, International Publication No. 2014/097594. Examples include the compounds described in paragraph 0055. Further, 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. Further, it is also preferable to use the following compounds as the silane coupling agent. In the following formula, Et represents an ethyl group.

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

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

<Other additives>
The curable resin composition of the present invention comprises various additives, for example, a thermal acid generator, a sensitizer such as N-phenyldiethanolamine, and a chain transfer agent, as needed, 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, antiaggregating agents and the like can be blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the curable resin composition.

[Sensitizer]
The curable resin composition of the present invention may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in the electronically excited state comes into contact with the thermal curing accelerator, the thermal radical polymerization initiator, the photoradical polymerization initiator, and the like, and acts such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal curing accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo a chemical change and decompose to generate a radical, an acid, or a base.
Examples of the sensitizer include sensitizers such as N-phenyldiethanolamine.
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-2016-027355 can be referred to, and the contents thereof are incorporated in the present specification.

When the curable resin composition of the present invention contains a sensitizer, the content of the sensitizer may be 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 0.1 to 15% by mass, more preferably 0.5 to 10% by mass. The sensitizer may be used alone or in combination of two or more.

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

Further, as the chain transfer agent, the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219 can also be used.

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

また、界面活性剤は、国際公開第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]
Each kind of surfactant may be added to the curable resin composition of the present invention from the viewpoint of further improving the coatability. As the surfactant, various types of surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. The following surfactants are also preferable. In the following formula, the parentheses indicating the constituent units of the main chain represent the content (mol%) of each constituent unit, and the brackets indicating the constituent units of the side chain represent the number of repetitions of each constituent unit.

Further, as the surfactant, the compound described in paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used.

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 based on the total solid content of the curable resin composition of the present invention. It is preferably 0.005 to 1.0% by mass, more preferably 0.005 to 1.0% by mass. The surfactant may be only one kind or two or more kinds. When there are two or more types of surfactant, the total is preferably in the above range.

[Higher fatty acid derivative]
The curable resin composition of the present invention has a curable resin composition in the process of drying after application by adding a higher fatty acid derivative such as behenic acid or behenic acid amide in order to prevent polymerization inhibition due to oxygen. It may be unevenly distributed on the surface of an object.

Further, as the higher fatty acid derivative, the compound described in paragraph 0155 of International Publication No. 2015/199219 can also be used.

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

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

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

Further, 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 the raw material constituting the curable resin composition of the present invention. Methods such as filtering the raw materials constituting the curable resin composition of the present invention with a filter, lining the inside of the apparatus with polytetrafluoroethylene or the like, and performing distillation under conditions in which contamination is suppressed as much as possible are mentioned. be able to.

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

A conventionally known storage container can be used as the storage container for the curable resin composition of the present invention. In addition, as the storage container, for the purpose of suppressing contamination of raw materials and curable resin composition with impurities, a multi-layer bottle having the inner wall of the container composed of 6 types and 6 layers of resin and 6 types of resin are used. It is also preferable to use a bottle having a layered structure. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.

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

Further, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the curable resin composition. The filter hole diameter is preferably 1 μm or less, more preferably 0.5 μm or less, still more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel for use. When using a plurality of types of filters, filters having different pore diameters or materials may be used in combination. In addition, various materials may be filtered a plurality of times. When filtering multiple times, circulation filtration may be used. Moreover, you may pressurize and perform filtration. When pressurizing and filtering, the pressurizing pressure is preferably 0.05 MPa or more and 0.3 MPa or less.
In addition to filtration using a filter, impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

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

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

The cured film of the present invention is obtained by curing the 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. Further, the upper limit value can be 100 μm or less, and can be 30 μm or less.

Two or more layers of the cured film of the present invention may be laminated, and further, 3 to 7 layers may be laminated to form a laminated body. It is preferable that the laminated body of the present invention contains two or more cured films and includes 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 preferable. The first cured film and the second cured film are both cured films of the present invention. For example, both the first cured film and the second cured film are curable of the present invention. A preferred embodiment is a film obtained by curing the 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. The compositions may be present or may have different compositions, but from the viewpoint of production suitability, the compositions having the same composition are preferable. Such a metal layer is preferably used as a metal wiring such as a rewiring layer.

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

Further, the cured film in the present invention can also be used for manufacturing a plate surface such as an offset plate surface or a screen plate surface, using it for etching molded parts, and manufacturing a protective lacquer and a dielectric layer in electronics, particularly microelectronics.

The method for producing a cured film of the present invention (hereinafter, also simply referred to as "the method for producing 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 preferable.
Further, the method for producing a cured film of the present invention further includes the film forming step, and further includes an exposure step for exposing the film and a developing step for developing the film (developing the film). Is more preferable.
Further, the method for producing a cured film of the present invention includes the film forming step (and, if necessary, the developing step), and further includes a heating step of heating the film at 80 to 450 ° C. preferable.
Specifically, it is also preferable to include the following steps (a) to (d).
(A) Film forming step of applying the curable resin composition to a substrate to form a film (curable resin composition layer) (b) After the film forming step, an exposure step of exposing the film (c) is exposed. Development step of developing the developed film (d) Heating step of heating the developed film at 80 to 450 ° C. By heating in the heating step, the resin layer cured by exposure is further cured. Can be made to. Sufficient curability can be obtained by, for example, decomposing the above-mentioned onium salt or other thermobase generator in this heating step.

The 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 the laminated body of the present embodiment, after forming the cured film according to the above-mentioned method for producing the cured film, the steps (a), the steps (a) to (c), or (a) are further performed. )-(D). In particular, it is preferable to perform each of the above steps a plurality of times, for example, 2 to 5 times (that is, 3 to 6 times in total) in order. By laminating the cured film in this way, a laminated body can be obtained. In the present invention, it is particularly preferable to provide a metal layer on the portion provided with the cured film, between the cured films, or both. 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 laminated body of the cured film.

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

The type of substrate can be appropriately determined depending on the application, but semiconductor fabrication substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin film, There are no particular restrictions on magnetic film, reflective film, metal substrate such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, plasma display panel (PDP) electrode plate, and the like. In the present invention, a semiconductor-made base material is particularly preferable, and a silicon base material is more preferable.
Further, as the base material, for example, a plate-shaped base material (board) is used.

When the curable resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer serves as a base material.

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

Specifically, the means to be applied include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, and a slit coating method. And the inkjet method and the like are exemplified. From the viewpoint of the uniformity of the thickness of the curable resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an inkjet method are more preferable. A resin layer having a desired thickness can be obtained by adjusting an appropriate solid content concentration and coating conditions according to the method. Further, the coating method can be appropriately selected depending on the shape of the substrate. For a circular substrate such as a wafer, a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular substrate, a slit coating method or a spray coating method is preferable. The method, the inkjet method and the like are preferable. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute.
Further, it is also possible to apply a method of transferring a coating film previously applied onto a temporary support by the above-mentioned application method onto a substrate.
Regarding the transfer method, the production method described in paragraphs 0023 and 0036 to 0051 of JP-A-2006-023696 and paragraphs 0090 to 0108 of JP-A-2006-047592 can be suitably used in the present invention.

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

<Exposure process>
The production method of the present invention may include an exposure step of exposing the film (curable resin composition layer). The exposure amount is not particularly determined as long as the curable resin composition can be cured, but for example, ^{it is preferable to irradiate 100 to 10,000 mJ / cm 2 in} terms of exposure energy at a wavelength of 365 nm, and 200 to 8,000 mJ /. It is more preferable to irradiate with cm ^2.

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

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

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

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

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

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

The developer preferably has 50% by mass or more of an organic solvent, more preferably 70% by mass or more of an organic solvent, and further preferably 90% by mass or more of an organic solvent. Further, the developer may be 100% by mass of an organic solvent.

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

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

<Heating process>
The production method of the present invention preferably includes a step (heating step) of heating the developed film at 80 to 450 ° C.
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 above-mentioned onium salt or other thermal base generator is decomposed to generate a base, and the cyclization reaction of the heterocyclic-containing polymer precursor proceeds. Further, the curable resin composition of the present invention may contain a radically polymerizable compound other than the heterocyclic-containing polymer precursor, but may also cure a radically polymerizable compound other than the unreacted heterocyclic-containing polymer precursor. It can be advanced in this step. The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 80 ° C. or higher, more preferably 140 ° C. or higher, further preferably 150 ° C. or higher, and 160 ° C. or higher. Is particularly preferable, and it is most preferable that the temperature is 170 ° C. or higher. The upper limit is preferably 450 ° C. or lower, more preferably 350 ° C. or lower, further preferably 250 ° C. or lower, and particularly preferably 220 ° C. or lower.

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

The temperature at the start of heating is preferably 20 ° C. to 150 ° C., more preferably 20 ° C. to 130 ° C., and even more preferably 25 ° C. to 120 ° C. The temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature is started. For example, when the curable resin composition is applied onto a substrate and then dried, it is the temperature of the film (layer) after drying, and is, for example, higher than the boiling point of the solvent contained in the curable resin composition. It is preferable to gradually raise the temperature from a temperature as low as 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, and even more preferably 30 to 240 minutes.

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

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

Further, 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 performed in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon from the viewpoint of preventing decomposition of the heterocyclic-containing polymer precursor. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

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

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

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

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

<Laminating process>
The production method of the present invention preferably further includes a laminating step.

In the laminating step, (a) a film forming step (layer forming step), (b) an exposure step, (c) a developing step, and (d) a heating step are performed again on the surface of the cured film (resin layer) or the metal layer. , A series of steps including performing in this order. However, it may be an embodiment in which only the film forming step (a) is repeated. Further, (d) the heating step may be performed collectively at the end or the middle of the lamination. That is, the steps (a) to (c) may be repeated a predetermined number of times, and then the heating of (d) may be performed to cure the laminated curable resin composition layer all at once. Further, the (c) developing step may include (e) a metal layer forming step, and even if the heating is performed each time (d), the (d) is collectively performed after laminating a predetermined number of times. Heating may be performed. Needless to say, the laminating step may further include the above-mentioned drying step, heating step and the like as appropriate.

When the laminating step is further performed, the surface activation treatment step may be further performed after the heating step, the exposure step, or the metal layer forming step. Plasma treatment is exemplified as the surface activation treatment.

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

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

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 the metal layer is provided. Specifically, an embodiment in which (a) a film forming step, (b) an exposure step, (c) a developing step, (e) a metal layer forming step, and (d) a heating step are repeated in this order, or (a) film forming. Examples thereof include an embodiment in which (b) an exposure step, (c) a development step, and (e) a metal layer forming step are repeated in this order, and (d) a heating step is collectively provided at the end or in the middle. By alternately performing the laminating 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 present invention also discloses a semiconductor device having the cured film or laminate of the present invention. As specific examples of the semiconductor device in which the curable resin composition of the present invention is used to form the interlayer insulating film for the rewiring layer, the description in paragraphs 0213 to 0218 and FIG. 1 of JP-A-2016-0273557 are taken into consideration. Yes, these contents are incorporated herein.

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

(Synthesis of linear polyimide precursor (other polyimide precursor))
<Synthesis example 1>
[Synthesis of polyimide precursor (A-1: polyimide precursor having no radical polymerizable group) from pyromellitic acid dianhydride, 4,4'-diaminodiphenyl ether and benzyl alcohol]
14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C. for 12 hours) and 14.22 g (131.58 mmol) of benzyl alcohol were suspended in 50 mL of N-methylpyrrolidone. , Dryed in a molecular sieve. The suspension (moisture content 76 ppm) was heated at 100 ° C. for 3 hours. The reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) of pyridine and 90 mL of N-methylpyrrolidone were added. The reaction mixture was then cooled to −10 ° C. and 16.12 g (135.5 mmol) of SOCL ₂ was added over 10 minutes while keeping the temperature at −10 ± 4 ° C. Viscosity increased while SOCL _{2 was added.} After diluting 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 dissolved in 100 mL of N-methylpyrrolidone was then added dropwise to the reaction mixture at −5-0 ° C. over 20 minutes. Then, the reaction mixture was reacted at 0 ° C. for 1 hour, 70 g of ethanol was added, and the mixture was stirred 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 rate of 5,000 rpm (revolutions per minute) for 15 minutes. The polyimide precursor was filtered off, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor was 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>
[Synthesis of polyimide precursor (A-2: polyimide precursor having radical polymerizable group) from pyromellitic acid dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate]
14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, and 20 .4 g (258 mmol) of pyridine and 100 g of diglyme (diethylene glycol dimethyl ether) are mixed (water content 85 ppm) and stirred at a temperature of 60 ° C. for 18 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. did. Next, the obtained diester was _{chlorinated with SOCL 2} , converted to a polyimide precursor with 4,4'-diaminodiphenyl ether by the same method as in Synthesis Example 1, and the polyimide precursor was obtained by the same method as in Synthesis Example 1. Obtained. The weight average molecular weight of this polyimide precursor was 19,000.

<Synthesis example 3>
[Synthesis of polyimide precursor (A-3: polyimide precursor having radical polymerizable group) from 4,4'-oxydiphthalic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate]
20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140 ° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, and 0.05 g of hydroquinone. , 20.4 g (258 mmol) of pyridine and 100 g of diglime (water content 95 ppm), stirred at a temperature of 60 ° C. for 18 hours, 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Diester was produced. Next, the obtained diester was _{chlorinated with SOCL 2} , converted to a polyimide precursor with 4,4'-diaminodiphenyl ether by the same method as in Synthesis Example 1, and the polyimide precursor was obtained by the same method as in Synthesis Example 1. Obtained. The weight average molecular weight of this polyimide precursor was 18,000.

<Synthesis example 4>
[3,3', 4,4'-biphenyltetracarboxylic acid anhydride, 4,4'-diaminodiphenyl ether and polyimide precursor from 2-hydroxyethyl methacrylate (A-4: polyimide precursor having a radically polymerizable group) ) Synthesis]
20.0 g (64.5 mmol) of 3,3', 4,4'-biphenyltetracarboxylic acid anhydride (dried at 140 ° C. for 12 hours) and 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate. , 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine, and 100 g of diglyme (moisture content 88 ppm), stirred at a temperature of 60 ° C. for 18 hours, 3,3', 4 , 4'-Biphenyltetracarboxylic acid and 2-hydroxyethylmethacrylate diesters were prepared. Next, the obtained diester was _{chlorinated with SOCL 2} , converted to a polyimide precursor with 4,4'-diaminodiphenyl ether by the same method as in Synthesis Example 1, and the polyimide precursor was obtained by the same method as in Synthesis Example 1. Obtained. The weight average molecular weight of this polyimide precursor was 20,000.

<Synthesis Example 5>
[4,4'-oxydiphthalic anhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (orthotridin) and polyimide precursor from 2-hydroxyethyl methacrylate (A-5: having a radically polymerizable group) Synthesis of polyimide precursor)]
20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140 ° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, and 0.05 g of hydroquinone. , 20.4 g of pyridine (258 mmol) and 100 g of diglyme (moisture content 67 ppm), stirred at a temperature of 60 ° C. for 18 hours, 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Diester was produced. Next, the obtained diester was _{chlorinated with SOCL 2} , and then converted into a polyimide precursor with 4,4'-diamino-2,2'-dimethylbiphenyl by the same method as in Synthesis Example 1, and the same as in Synthesis Example 1. A polyimide precursor was obtained by the above method. The weight average molecular weight of this polyimide precursor was 19,000.

式（ＰＡ−１）中、各繰返し単位において＊と波線部がそれぞれ結合する。(Synthesis of branched polyimide precursor (specific polymer precursor))
<Synthesis example 6>
[Polyimide precursor from pyromellitic acid, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate, PA-1]
16.39 g (64.5 mmol) of pyromellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd., dried at 140 ° C. for 12 hours), 21.43 g (270.9 mmol) of pyridine and 150 mL of N-methylpyrrolidone. Dissolved. Then, 2.80 g (6.45 mmol) of the diester compound composed of pyromellitic anhydride / 2-hydroxyethyl methacrylate obtained before chlorination of Synthesis Example 2 was added and dissolved. The resulting mixture was cooled to −10 ° C. and 33.84 g (284.5 mmol) of SOCL ₂ was added over 10 minutes while keeping the temperature at −10 ± 4 ° C. After chlorination with SOCL ₂ , it was converted into a branched polyimide precursor with 4,4'-diaminodiphenyl ether by the same method as in Synthesis Example 1, and a polyimide precursor was obtained by the same method as in Synthesis Example 1. The weight average molecular weight of this polyimide precursor (PA-1) was 23,000.
PA-1 is presumed to be a resin in which three repeating units represented by the following formula (PA-1) are bonded.

In the formula (PA-1), * and the wavy line portion are combined in each repetition unit.

式（ＰＡ−２）中、各繰返し単位において＊と波線部がそれぞれ結合する。<Synthesis example 7>
[Pyromellitic acid, 2-hydroxyethyl methacrylate monoester, polyimide precursor from 4,4'-diaminodiphenyl ether, PA-2]
14.06 g (64.5 mmol) of pyromellitic dianhydride, 8.4 g (64.5 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone and 20.4 g of pyridine (258 mmol). ), 100 g of diglyme (diethylene glycol dimethyl ether), and 1.16 g (64.5 mmol) of water were mixed and stirred at a temperature of 60 ° C. for 18 hours. After cooling to room temperature, a pyromellitic acid / 2-hydroxyethyl methacrylate monoester was isolated by column chromatography (chloroform / methanol) (the monoester was synthesized by J. Org. Chem. 2008, 73, 4929). But it can be synthesized). Next, the obtained monoester _{was chlorinated with SOCL 2} , converted to a polyimide precursor with 4,4'-diaminodiphenyl ether by the same method as in Synthesis Example 1, and then converted into a polyimide precursor by the same method as in Synthesis Example 1. A body (PA-2) was obtained. The weight average molecular weight of this polyimide precursor was 23,000.
PA-2 is presumed to be a resin in which two repeating units represented by the following formula (PA-2) are bonded.

In the formula (PA-2), * and the wavy line portion are combined in each repetition unit.

式（ＰＡ−３）中、各繰返し単位において＊と波線部がそれぞれ結合する。<Synthesis Example 8>
[Polyimide precursors from 4,4'-oxydiphthalic acid, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate, PA-3]
20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride, 100 g of diglyme and 2.32 g (129 mmol) of water were mixed and stirred at a temperature of 60 ° C. for 18 hours. After cooling to room temperature, 4,4'-oxydiphthalic acid was isolated by column chromatography (chloroform / methanol).
22.33 g (64.5 mmol) of 4,4'-oxydiphthalic acid, 21.43 g (270.9 mmol) of pyridine and 150 mL of N-methylpyrrolidone were dissolved. Then, 2.80 g (6.45 mmol) of the diester compound composed of pyromellitic anhydride / 2-hydroxyethyl methacrylate obtained before chlorination of Synthesis Example 2 was added and dissolved. The resulting mixture was cooled to −10 ° C. and 33.84 g (284.5 mmol) of SOCL ₂ was added over 10 minutes while keeping the temperature at −10 ± 4 ° C. After chlorination with SOCL ₂ , it was converted into a branched polyimide precursor with 4,4'-diaminodiphenyl ether by the same method as in Synthesis Example 1, and a polyimide precursor was obtained by the same method as in Synthesis Example 1. The weight average molecular weight of this polyimide precursor PA-3 was 23,500.
It is presumed that PA-3 is a resin in which two repeating units represented by the following formula (PA-3) are bonded.

In the equation (PA-3), * and the wavy line portion are combined in each repetition unit.

式（ＰＡ−４）中、各繰返し単位において＊と波線部がそれぞれ結合する。<Synthesis example 9>
[4,4'-oxydiphthalic anhydride / 2-hydroxyethylmethacrylate monoester, and polyimide precursor from 4,4'-diaminodiphenyl ether, PA-4]
20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride, 8.4 g (64.5 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone and 20.4 g of pyridine. (258 mmol), 100 g of diglyme and 2.32 g (129 mmol) of water were mixed and stirred at a temperature of 60 ° C. for 18 hours. After cooling to room temperature, a 4,4'-oxydiphthalic acid / 2-hydroxyethyl methacrylate monoester was isolated by column chromatography (chloroform / methanol). Next, the obtained monoester _{was chlorinated with SOCL 2} , converted to a polyimide precursor with 4,4'-diaminodiphenyl ether by the same method as in Synthesis Example 1, and then converted into a polyimide precursor by the same method as in Synthesis Example 1. I got a body. The weight average molecular weight of this polyimide precursor PA-4 was 23,000.
PA-4 is presumed to be a resin in which two repeating units represented by the following formula (PA-4) are bonded.

In the equation (PA-4), * and the wavy line portion are combined in each repetition unit.

式（ＰＡ−５）中、各繰返し単位において＊と波線部がそれぞれ結合する。<Synthesis Example 10>
[Branched polymer from 4,4'-oxydiphthalic acid and 4,4'-diaminodiphenyl ether, PA-5]
The 4,4'-oxydiphthalic acid isolated in Synthesis Example 8 is _{chlorinated with SOCL 2} , then amidated with 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example 1, and then in the same manner as in Synthesis Example 1. A branched polymer was obtained in. The weight average molecular weight of this branched polymer PA-5 was 18,000.
It is presumed that PA-5 is a resin in which two repeating units represented by the following formula (PA-5) are bonded.
The resin PA-5 does not form an imide even when heated, and is not a polyimide precursor.

In the formula (PA-5), * and the wavy line portion are combined in each repetition unit.

<Examples and comparative examples>
In each Example and Comparative Example, the components shown in Table 1 below were mixed to obtain each curable resin composition and a comparative composition. The obtained curable resin composition and comparative composition were pressure-filtered through a filter made of polytetrafluoroethylene having a pore width of 0.8 μm.
In Table 1, the numerical value in the column of "parts by mass" indicates the content (parts by mass) of each component.
Further, in Table 1, the description of "-" indicates that the corresponding component is not contained.
In Table 1, the description in the column of "content of branched structure" indicates "content of branched structure contained in the polyimide precursor (μmol / g) with respect to the total solid content of the composition".

The details of each component shown in Table 1 are as follows.

[Other polymer precursors]
-A-1 to A-5: A-1 to A-5 synthesized above.

[Specific polymer precursor]
-PA-1 to PA-5: PA-1 to PA-5 synthesized above

[Onium salt or other thermobase generator]
B-1 to B-5: Compounds with the following structure

[Radical polymerization initiator]
・ C-1: IRGACURE OXE 01 (manufactured by BASF)
・ C-2: IRGACURE OXE 02 (manufactured by BASF)
・ C-3: IRGACURE 369 (manufactured by BASF)

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

[Polymerization inhibitor]
E-1: 2,6-di-tert-butyl-4-methylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ E-2: Parabenzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ E-3: Paramethoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ E-4: 2-nitroso-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Migration inhibitor]
F-1 to F-4: Compounds with the following structure

[Metal adhesion improver]
G-1 to G-4: Compounds having the following structure. In the following structural formula, Et represents an ethyl group.

〔solvent〕
-I-1: γ-Butyrolactone (manufactured by Sanwa Yuka Co., Ltd.)
-I-2: Dimethyl sulfoxide (manufactured by Wako Pure Chemical Industries, Ltd.)
-I-3: N-methyl-2-pyrrolidone (manufactured by Ashland)

〔Additive〕
-J-1: N-Phenyldiethanolamine

<Evaluation>
In each Example and Comparative Example, the curable resin composition and the comparative composition shown in Table 2 were used to evaluate the storage stability, the resolution, and the elongation at break.
The details of the evaluation method in each evaluation are described below.

[Storage stability]
In each Example and Comparative Example, the viscosity (0 days) of each curable resin composition or each comparative composition was measured using an E-type viscometer. After allowing the curable resin composition or the comparative composition to stand at 25 ° C. for 14 days in a light-shielded airtight container, each of the curable resin compositions or each comparison after standing still using an E-type viscometer again. The viscosity (14 days) of the composition for use was measured. In each Example and each Comparative Example, the viscosity volatility was calculated from the following formula using the values of the viscosity (0 days) and the viscosity (14 days), respectively. The lower the viscosity volatility, the higher the storage stability. The evaluation was performed according to the following evaluation criteria. The evaluation results are described in the column of "storage stability" in Table 2.

Viscosity volatility (%) = 100 × {1- (viscosity (14 days) / viscosity (0 days))}
The viscosity was measured at 25 ° C., and the others were in accordance with JIS Z 8803: 2011.
-Evaluation criteria-
A: The viscosity volatility was 5% or less.
B: The viscosity volatility was more than 5% and 10% or less.
C: The viscosity volatility was more than 10% and 15% or less.
D: Viscosity volatility exceeded 15%.

[Resolution]
In each Example and Comparative Example, after filtering through a filter having a pore width of 0.8 μm, the curable resin composition or the comparative composition is applied in layers on a silicon wafer by a spin coating method. A curable resin composition layer or a comparative composition layer was formed. The film thickness (the film thickness (μm) of the unexposed portion before development) was set to 20 μm.
A silicon wafer to which the obtained curable resin composition layer or comparative composition layer is applied is dried on a hot plate at 100 ° C. for 5 minutes, and a uniform curable resin composition having a thickness of 15 μm is placed on the silicon wafer. A layer or a comparative composition layer was used. This was developed with cyclopentanone for 60 seconds, the film thickness after development (the film thickness after development (μm) of the unexposed portion) was measured, and the residual film ratio of the unexposed portion was determined by the following formula. The evaluation was performed according to the following evaluation criteria. It can be said that the smaller the unexposed portion residual film ratio, the better the resolution. The evaluation results are described in the "Resolution" column of Table 2.
Unexposed part residual film ratio (%) = (film thickness after development of unexposed part (μm) / film thickness before development of unexposed part (μm)) × 100
A: The unexposed portion residual film ratio was less than 10%.
B: The unexposed portion residual film ratio was 10% or more and less than 50%.
C: The unexposed portion residual film ratio was 50% or more.

[Fracture elongation rate]
In each Example and Comparative Example, each curable resin composition or comparative composition is applied in layers on a silicon wafer by a spin coating method to obtain a curable resin composition layer or a comparative composition layer. Formed. A silicon wafer to which the obtained curable resin composition layer or comparative composition layer is applied is dried on a hot plate at 100 ° C. for 5 minutes, and a uniform curable resin composition having a thickness of 20 μm is placed on the silicon wafer. A layer or a comparative composition layer was used. The curable resin composition layer or the comparative composition layer on the silicon wafer was exposed to an exposure energy of ^{500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C).} The exposed curable resin composition layer or comparative composition layer was heated at a heating rate of 10 ° C./min under a nitrogen atmosphere, reached 180 ° C., and then maintained at this temperature for 3 hours. A cured resin layer was obtained. The cured resin layer was immersed in a 4.9% hydrofluoric acid solution, and the resin layer was peeled off from the silicon wafer to obtain a resin film 1.

Using a tensile tester (Tensilon), the breaking elongation of the resin film 1 is set to a crosshead speed of 300 mm / min, a sample width of 10 mm, and a sample length of 50 mm. The elongation at break was measured in accordance with JIS-K6251: 2017 under the environment of (RH). The elongation at break is E _b (%) = (L _{b −} L ₀ ) / L ₀ × 100 (E _b : elongation at cutting, L ₀ : length of the test piece before the test, L _b : the test piece is cut. It was calculated by the length of the test piece at the time of the test). In the evaluation, the elongation at break in the longitudinal direction was measured 10 times, and _{the arithmetic mean value of the elongation at break (Eb} ) of a total of 10 pieces was used as an index value. The evaluation was performed according to the following evaluation criteria. It can be said _{that the larger the value of E b} , the better the elongation at break. The evaluation results are described in the column of "elongation rate at break" in Table 2.
-Evaluation criteria-
A: The above index value exceeded 60%.
B: The index value was more than 50% and 60% or less.
C: The index value was more than 40% and 50% or less.
D: The above index value was 40% or less.

From the above results, it can be seen that the curable resin composition containing the specific polymer precursor according to the present invention is excellent in the elongation at break of the obtained cured film.
The comparative compositions according to Comparative Examples 1 to 4 do not contain a specific polymer precursor. It can be seen that the curable resin compositions according to Comparative Examples 1 to 4 are inferior in elongation at break.

<Example 101>
The curable resin composition described in Example 1 was spun and applied to the surface of the resin base material on which the copper thin layer was formed so that the film thickness was 20 μm. The curable resin composition applied to the resin substrate was dried at 100 ° C. for 2 minutes and then exposed using a stepper (NSR1505 i6, manufactured by Nikon). The exposure was performed through a mask of a square pattern (a square pattern having a length of 100 μm and a width of 100 μm, a number of repetitions of 10) at a wavelength of 365 nm and an exposure amount of 400 mJ / cm2 to create a square remaining pattern. After exposure, it was developed with cyclopentanone for 30 seconds and rinsed with PGMEA for 20 seconds to obtain a pattern.
Then, it was heated at 230 ° C. for 3 hours to form an interlayer insulating film for the rewiring layer. The interlayer insulating film for the rewiring layer was excellent in insulating property. Moreover, when a semiconductor device was manufactured using these interlayer insulating films for the rewiring layer, it was confirmed that the semiconductor device operated without any problem.

Claims (17)

It has at least one branched structure selected from the group consisting of the branched structure represented by the following formula (A-1) and the branched structure represented by the following formula (A-2), and has. , A curable resin composition containing a polyimide precursor having a branched chain having a repeating unit as a branched chain bonded to the branched structure;

In formula (A-1) or formula (A-2), R ¹¹⁵ represents a tetravalent organic group ^{, RA 21} represents a hydrogen atom or a monovalent organic group, and * is an independent structure with another structure. Represents the binding site of. The curable resin composition according to claim 1, wherein the content of the branched structure contained in the polyimide precursor is 0.01 to 10 μmol / g with respect to the total solid content of the composition. The curable resin composition according to any one of claims 1 or 2, wherein the polyimide precursor has a repeating unit represented by the following formula (1).

In formula (1), A ¹ and A ² independently represent an oxygen atom or -NH-, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, and * ¹ and * ² each independently represent a bonding site with another structure. The curable resin composition according to claim 3, wherein at least one ^{of R 113} and R ¹¹⁴ in the formula (1) contains a radically polymerizable group. The curable resin composition according to claim 3 or 4, ^{wherein R 115} in the formula (1) is a group containing an aromatic ring. The curable resin composition according to any one of claims 3 to 5, ^{wherein R 111} in the formula (1) is represented by −Ar ⁰ −L ⁰ −Ar ^{0 −.}
Ar ⁰ represents an aromatic group independently, and L ⁰ is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, −O−, −C (= O). -, -S-, -S (= O) _2- , -NHC (= O)-, and a group in which two or more of these are combined are represented. ^{The curable resin composition according to any one of claims 3 to 6, wherein R 111} in the formula (1) is represented by the following formula (51) or the formula (61);

In the formula (51) or the formula (61), R ^{50 to} R ⁵⁷ independently represent 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 and a methyl group. , Fluoromethyl group, difluoromethyl group or trifluoromethyl group, R ⁵⁸ and R ⁵⁹ independently represent a fluorine atom, fluoromethyl group, difluoromethyl group or trifluoromethyl group, and * independently represent each. Represents a site of binding to other structures. The one according to any one of claims 1 to 7, wherein at least one of the repeating units contained in the branched chain is the same as at least one of the repeating units contained in the main chain of the polyimide precursor. Curable resin composition. The curable resin composition according to any one of claims 1 to 8, further comprising a radical polymerization initiator, a radically polymerizable compound, a silane coupling agent, and an onium salt. The curable resin composition according to any one of claims 1 to 9, further comprising another heterocyclic-containing polymer precursor different from the polyimide precursor. The curable resin composition according to any one of claims 1 to 10, which is used for forming an interlayer insulating film for a rewiring layer. A cured film obtained by curing the curable resin composition according to any one of claims 1 to 11. A laminated body containing two or more cured films according to claim 12 and containing a metal layer between any of the cured films. A method for producing a cured film, which comprises a film forming step of applying the curable resin composition according to any one of claims 1 to 11 to a substrate to form a film. The method for producing a cured film according to claim 14, further comprising an exposure step for exposing the film and a developing step for developing the film. The method for producing a cured film according to claim 14 or 15, which comprises a heating step of heating the film at 80 to 450 ° C. A semiconductor device comprising the cured film according to claim 12 or the laminate according to claim 13.