JPWO2020066975A1 - Resin composition, cured film, laminate, method for manufacturing cured film, and semiconductor device - Google Patents

Abstract

A resin composition containing at least one polymer precursor selected from a polyimide precursor and a polybenzoxazol precursor, which is HNO2, NO2-, HNO3, NO3-, H2SO4, HSO4-, SO42-, H2SO3, HSO3-. A resin composition in which the total content of and SO32- is 1 mass ppb or more and 1000 mass ppm or less with respect to the total solid content of the resin composition. A cured film, a laminate, a method for producing a cured film, and a semiconductor device using a resin composition.

Description

The present invention relates to resin compositions containing at least one polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors. The present invention also relates to a cured film, a laminate, a method for producing a cured film, and a semiconductor device using the resin composition containing the polymer precursor described above.

Cyclized and cured resins such as polyimide resins and polybenzoxazole resins have excellent heat resistance and insulating properties, and are therefore applied to various applications. The application is not particularly limited, and examples of semiconductor devices for mounting include use as a material for an insulating film or a sealing material, or as a protective film (see Non-Patent Documents 1 and 2 and the like). It is also used as a base film and coverlay for flexible substrates.
Such a polyimide resin or the like generally has low solubility in a solvent. Therefore, a method of dissolving in a solvent in the state of a polymer precursor before the cyclization reaction, specifically, a polyimide precursor or a polybenzoxazole precursor, is often used. As a result, excellent handleability can be realized, and when each product as described above is manufactured, it can be applied to a substrate or the like in various forms and processed. The polymer precursor can then be heated to cyclize to form a cured product. In addition to the high performance of polyimide resins and the like, from the viewpoint of excellent manufacturing adaptability, the industrial application development is expected more and more.

Patent Document 1 describes an invention relating to a resin composition containing a polymer precursor such as a polyimide precursor or a polybenzoxazole precursor, and a thermal base generator. Patent Document 1 describes that by adopting a specific thermobase generator, storage stability is good and a cyclization reaction of a polyimide precursor or the like can be carried out at a low temperature.

International Publication No. 2015/199219

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

The technique of Patent Document 1 has made it possible to improve the storage stability of a resin composition containing a polymer precursor such as a polyimide precursor or a polybenzoxazole precursor.
On the other hand, further research and development is required to meet the recent diversified required properties required for resin compositions containing these polymer precursors. For example, with respect to a cured film obtained from a resin composition containing a polymer precursor, further improvement in moisture resistance is desired.

Therefore, an object of the present invention is to provide a resin composition, a cured film, a laminate, a method for producing a cured film, and a semiconductor device capable of forming a cured film having good storage stability and excellent moisture resistance. And.

The present inventor has diligently studied a resin composition containing at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor. We have found that we can achieve the above, and have completed the present invention. The present invention provides:

式（１）中、Ａ¹およびＡ²は、それぞれ独立に酸素原子またはＮＨを表し、Ｒ¹¹¹は、２価の有機基を表し、Ｒ¹¹⁵は、４価の有機基を表し、Ｒ¹¹³およびＲ¹¹⁴は、それぞれ独立に、水素原子または１価の有機基を表す。
＜５＞ 式（１）におけるＲ¹¹³およびＲ¹¹⁴の少なくとも一方がラジカル重合性基を含む、＜４＞に記載の樹脂組成物。
＜６＞ 有機溶剤を９０質量％以上含む現像液を用いて現像してパターンを形成するために用いられる、＜１＞〜＜５＞のいずれか１つに記載の樹脂組成物。
＜７＞ 金属と接触させる部材の形成に用いられる、＜１＞〜＜６＞のいずれか１つに記載の樹脂組成物。
＜８＞ 再配線層用層間絶縁膜の形成に用いられる、＜１＞〜＜７＞のいずれか１つに記載の樹脂組成物。
＜９＞ ＜１＞〜＜８＞のいずれか１つに記載の樹脂組成物を硬化して得られる硬化膜。
＜１０＞ 膜厚が１〜３０μｍである、＜９＞に記載の硬化膜。
＜１１＞ ＜９＞または＜１０＞に記載の硬化膜を２層以上有し、２層の硬化膜の間に金属層を有する、積層体。
＜１２＞ ＜１＞〜＜８＞のいずれか１つに記載の樹脂組成物を基板に適用して膜を形成する膜形成工程を含む、硬化膜の製造方法。
＜１３＞ 膜を露光する露光工程および膜を現像する現像工程を有する、＜１２＞に記載の硬化膜の製造方法。
＜１４＞ 膜を８０〜４５０℃で加熱する工程を含む、＜１２＞または＜１３＞に記載の硬化膜の製造方法。
＜１５＞ ＜９＞もしくは＜１０＞に記載の硬化膜または＜１１＞に記載の積層体を有する、半導体デバイス。<1> A resin composition containing at least one polymer precursor selected from a polyimide precursor and a polybenzoxazol precursor.
^{_{HNO 2, NO 2 -, HNO}} 3, NO 3 -, H 2 SO 4, HSO 4 -, SO 4 2-, H 2 SO 3, HSO 3 - and SO ₃ ^2-total content resin composition of A resin composition having a mass of 1 mass ppb or more and 1000 mass ppm or less with respect to the total solid content of the above.
<2> The resin composition according to <1>, further comprising at least one selected from a silane coupling agent, a thermal base generator, a radical polymerization initiator, and a radically polymerizable compound.
<3> The resin composition according to <1> or <2>, wherein the polymer precursor contains a polyimide precursor.
<4> The resin composition according to <3>, wherein the polyimide precursor has a structural 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 independently represents a hydrogen atom or a monovalent organic group.
<5> The resin composition according to <4>, wherein at least one ^{of R 113} and R ¹¹⁴ in the formula (1) contains a radically polymerizable group.
<6> The resin composition according to any one of <1> to <5>, which is used for developing with a developing solution containing 90% by mass or more of an organic solvent to form a pattern.
<7> The resin composition according to any one of <1> to <6>, which is used for forming a member to be brought into contact with a metal.
<8> The resin composition according to any one of <1> to <7>, which is used for forming an interlayer insulating film for a rewiring layer.
<9> A cured film obtained by curing the resin composition according to any one of <1> to <8>.
<10> The cured film according to <9>, which has a film thickness of 1 to 30 μm.
<11> A laminate having two or more cured films according to <9> or <10> and having a metal layer between the two cured films.
<12> A method for producing a cured film, which comprises a film forming step of applying the resin composition according to any one of <1> to <8> to a substrate to form a film.
<13> The method for producing a cured film according to <12>, which comprises an exposure step for exposing the film and a developing step for developing the film.
<14> The method for producing a cured film according to <12> or <13>, which comprises a step of heating the film at 80 to 450 ° C.
<15> A semiconductor device having the cured film according to <9> or <10> or the laminate according to <11>.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a resin composition, a cured film, a laminate, a method for producing a cured film, and a semiconductor device capable of forming a cured film having good storage stability and excellent moisture resistance.

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

The description of the components in the present invention described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the notation of a group (atomic group) in the present specification, the notation that does not describe substitution and non-substitution includes those having no substituent as well as those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, "exposure" includes not only exposure using light but also drawing using particle beams such as an electron beam and an ion beam, unless otherwise specified. Further, as the light used for exposure, generally, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation can be mentioned.
In the present specification, "(meth) acrylate" means both "acrylate" and "methacrylate", or either, and "(meth) acrylic" means both "acrylic" and "methacrylic", or. Representing either, "(meth) acryloyl" represents both "acryloyl" and "methacrylic", or either.
In the present specification, the term "process" is included in this term not only as an independent process but also as long as the desired action of the process is achieved even if it cannot be clearly distinguished from other processes. ..
Unless otherwise specified, the physical property values in the present invention are values at a temperature of 23 ° C. and an atmospheric pressure of 101325 Pa.
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured by gel permeation chromatography (GPC measurement) and are defined as polystyrene-equivalent values unless otherwise specified. In the present specification, for the weight average molecular weight (Mw) and the number average molecular weight (Mn), for example, HLC-8220 (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be obtained by using Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). In this measurement, THF (tetrahydrofuran) is used as the eluent unless otherwise specified. Unless otherwise specified, a detector having a wavelength of 254 nm for UV rays (ultraviolet rays) is used for detection.

[Resin composition]
The resin composition of the present invention is a resin composition comprising at least one polymer precursor selected from a polyimide precursor and polybenzoxazole ^{_{precursors, HNO 2, NO 2 -,}} HNO 3, NO 3 -, ^{_{H 2 SO 4, HSO 4 -}} , SO 4 2-, H 2 SO 3, HSO 3 - and SO ₃ 1 ppb by weight or more 1000 mass ppm total content of ^2- respect to the total solid content of the resin composition It is characterized by the following. It refers and SO ₃ also ^2- The combined specific component ^{- _{hereinafter, HNO 2, NO 2 -,}} HNO 3, NO 3 -, H 2 SO 4, HSO 4 -, SO 4 2-, H 2 SO 3, HSO 3 ..

Since the content of the specific component of the resin composition of the present invention is 1 mass ppb or more with respect to the total solid content of the resin composition, it is possible to suppress the reaction of the polymer precursor during storage, and as a result, it is excellent. It is presumed that storage stability was obtained. Further, since the content of the specific component is 1000 mass ppm or less with respect to the total solid content of the resin composition, even if the cured film is exposed to a high humidity environment, it is difficult to be hydrolyzed, and as a result, the moisture resistance is improved. It is presumed that an excellent cured film could be formed.

Further, when the resin composition of the present invention is used for forming a member that comes into contact with a metal such as an interlayer insulating film for a rewiring layer, corrosion of the metal can be suppressed. Therefore, the resin composition of the present invention is suitable for use in forming a member to be brought into contact with a metal. Examples of the member to be brought into contact with the metal include an interlayer insulating film for the rewiring layer, an insulating tube, a sealing film, and a substrate material (such as a base film and a coverlay of a flexible printed circuit board). It is preferable that there is.

In the resin composition of the present invention, the total content of the specific components is less than 1000 mass ppm with respect to the total solid content of the resin composition from the viewpoint of moisture resistance of the obtained cured film and prevention of metal corrosion. It is preferably 900 mass ppm or less, more preferably 800 mass ppm or less, and particularly preferably 500 mass ppm or less. The lower limit is set to the total solid content of the resin composition because the cause is not clear, but it is easy to improve the storage stability of the resin composition, the moisture resistance of the obtained film, etc. by suppressing the component that promotes deterioration. On the other hand, it is preferably 1.0 mass ppb or more, more preferably 1.1 mass ppb or more, further preferably 1.2 mass ppb or more, and 1.5 mass ppb or more. Especially preferable.

In the resin composition of the present ^{_{invention, HNO 2, NO 2 -,}} HNO 3, NO 3 -, H 2 SO 4, HSO 4 -, SO 4 2-, H 2 SO 3, HSO 3 - and SO ₃ ^2-of The content of each is preferably 1000 mass ppm or less, more preferably 900 mass ppm or less, further preferably 800 mass ppm or less, and 500 mass ppm or less, based on the total solid content of the resin composition. The following is particularly preferable.
Further, HNO ₂ and NO ₂ ^- is preferably 1000 ppm by mass or less based on the total solid content of the total content of the resin composition of, more preferably at most 900 mass ppm, or less 800 ppm by weight Is more preferable, and it is particularly preferable that it is 500 mass ppm or less.
Further, HNO ₃ and NO ₃ ^- is preferably 1000 ppm by mass or less based on the total solid content of the total content of the resin composition of, more preferably at most 900 mass ppm, or less 800 ppm by weight Is more preferable, and 500 mass ppm or less is particularly preferable.
Moreover, H ₂ SO ₄ and HSO ₄ ^- it is preferred that the total content of the SO ₄ ^2-is 1000 mass ppm or less with respect to the total solid content of the resin composition is 900 mass ppm or less It is more preferably 800 mass ppm or less, and particularly preferably 500 mass ppm or less.
Moreover, H ₂ SO ₃ and HSO ₃ ^- and more it is preferable that the content of the SO ₃ ^2-total is less than 1000 ppm by mass of the total solid content of the resin composition is 900 mass ppm or less It is more preferably 800 mass ppm or less, and particularly preferably 500 mass ppm or less.

The content of the specific component can be adjusted by adjusting the blending amount of the specific component or the raw material containing the specific component, or by adjusting the resin composition, the purification conditions of the raw material, and the like.

In addition, in this specification, the content of a specific component was analyzed by an ion chromatograph method. Specifically, a measurement sample, a non-aqueous organic solvent, and water are mixed, and the amount of a specific component extracted into an aqueous solution by a liquid separation operation or centrifugation is measured by an ion chromatograph method in the measurement sample. The content of the specific component of was calculated.
Further, in the resin composition of the present invention, NO ₂ among the specific component ^{_{-, NO 3 -, HSO 4}} -, SO 4 2-, HSO 3 - and SO ₃ ^2-is present in the form of a salt There may be. In addition, among the above-mentioned specific components, HNO ₂ , HNO ₃ , H ₂ SO ₄ , and H ₂ SO ₃ may be present in the ionized state by ionization. The atom or group of atoms constituting the salt is not particularly limited. For example, alkali metals (lithium, potassium, sodium, etc.), alkaline earth metals (calcium, beryllium, magnesium, strontium, barium) and the like can be mentioned.

It is also preferable that the resin composition of the present invention is used for developing with a developing solution containing 90% by mass or more of an organic solvent to form a pattern.

Hereinafter, each component of the resin composition of the present invention will be described in detail.

<Polymer precursor>
The resin composition of the present invention contains a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor. The polymer precursor used in the present invention is preferably a polyimide precursor because the effects of the present invention can be more easily obtained.

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

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

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

<<< R ¹¹¹ >>>
R ¹¹¹ represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, a heteroaromatic group, or a group consisting of a combination thereof, which have 2 to 20 carbon atoms. A linear aliphatic group, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group consisting of a combination thereof. Preferably, an aromatic group having 6 to 20 carbon atoms is more preferable.
R ¹¹¹ is preferably derived from diamine. Examples of the diamine used for producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one kind of diamine may be used, or two or more kinds of diamines may be used.
Specifically, the diamine is derived from a linear aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof. It is preferably a diamine containing an aromatic group having 6 to 20 carbon atoms, and more preferably a diamine containing an aromatic group. Examples of aromatic groups include:

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

Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1 , 3-Diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4-) Aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; meta and paraphenylenediamine, diaminotoluene, 4,4'-and 3 , 3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'-and 3,3'-diaminodiphenylmethane, 4,4'-and 3,3'-diaminodiphenyl sulfone , 4,4'-and 3,3'-diaminodiphenyl sulfide, 4,4'-and 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'- Dimethyl-4,4'-diaminobiphenyl (4,4'-diamino-2,2'-dimethylbiphenyl), 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4-amino) Phenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) ) Hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxy) Phenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 4,4'-diaminoparatelphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) ) Phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (2-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 9,10- Bis (4-aminophenyl) anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl sulfone, 1,3-bis (4-aminophenoxy) Nzen, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenyl) benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl- 4,4'-Diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy)) Phenyl] Hexafluoropropane, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 3,3', 4,4'-tetraaminobiphenyl, 3,3', 4,4'-tetraaminodiphenyl ether , 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis (4-aminophenyl) fluorene, 4,4'-dimethyl- 3,3'-Diaminodiphenylsulfone, 3,3', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2- (3', 5'-diaminobenzoyloxy) ethyl methacrylate, 2,4- And 2,5-diaminocumen, 2,5-dimethyl-paraphenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-paraphenylenediamine, 2,4,6-trimethyl-metaphenylenediamine, bis ( 3-Aminopropyl) tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-aminophenyl) ethane, diaminobenzanilide, ester of diaminobenzoic acid, 1,5 -Diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis (4-aminophenyl) hexafluoropropane, 1,4-bis (4-aminophenyl) octafluorobutane, 1,5-bis (4-aminophenyl) Decafluoropentane, 1,7-bis (4-aminophenyl) tetradecafluoroheptane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (2) -Aminophenoxy) Phenyl] Hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] Hexafluoropropane, 2,2-bis [4- (4-Aminophenoxy) -3,5-bis (trifluoromethyl) phenyl] hexafluoropropane, parabis (4-amino-2-trifluoromethi) Ruphenoxy) Benzene, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4,4'- Bis (4-amino-2-trifluoromethylphenoxy) diphenyl sulfone, 4,4'-bis (3-amino-5-trifluoromethylphenoxy) diphenyl sulfone, 2,2-bis [4- (4-amino-) 3-Trifluoromethylphenoxy) phenyl] hexafluoropropane, 3,3', 5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoro) Included are at least one diamine selected from methyl) biphenyl, 2,2', 5,5', 6,6'-hexafluorotridin and 4,4'-diaminoquaterphenyl.

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

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

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

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

Ｒ⁵⁰〜Ｒ⁵⁷は、それぞれ独立に水素原子、フッ素原子または１価の有機基であり、Ｒ⁵⁰〜Ｒ⁵⁷の少なくとも１つはフッ素原子、メチル基、フルオロメチル基、ジフルオロメチル基、または、トリフルオロメチル基である。
Ｒ⁵⁰〜Ｒ⁵⁷の１価の有機基として、炭素数１〜１０（好ましくは炭素数１〜６）の無置換のアルキル基、炭素数１〜１０（好ましくは炭素数１〜６）のフッ化アルキル基等が挙げられる。

Ｒ⁵⁸およびＲ⁵⁹は、それぞれ独立にフッ素原子、フルオロメチル基、ジフルオロメチル基、または、トリフルオロメチル基である。From the viewpoint of i-ray transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, a divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-ray transmittance and availability.

R ^{50 to} R ⁵⁷ are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and ^{at least one of R 50 to} R ⁵⁷ is a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group, or It is a trifluoromethyl group.
As a ^{monovalent organic group of R 50 to} R ⁵⁷ , an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a hook having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkylated group.

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

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

Ｒ¹¹²は、Ａと同義であり、好ましい範囲も同じである。<<< R ¹¹⁵ >>>
^{R 115} in the formula (1) represents a tetravalent organic group. The tetravalent organic group is preferably a group containing an aromatic ring, and more preferably a group represented by the following formula (5) or formula (6).

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

Ｒ¹¹⁵は、４価の有機基を表す。Ｒ¹¹⁵は式（１）のＲ¹¹⁵と同義である。 ^{Specific examples of the tetravalent organic group represented by R 115} in the formula (1) include a tetracarboxylic acid residue remaining after removing the acid dianhydride group from the tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).

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

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

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

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

In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, with a methyl group being more preferred.
In the formula (III), R ²⁰¹ is an alkylene group having 2 to 12 carbon atoms, −CH ₂ CH (OH) CH ₂ − or a (poly) oxyalkylene group having 4 to 30 carbon atoms (the alkylene group has 1 carbon atom). ~ 12 is preferable, 1 to 6 is more preferable, and 1 to 3 are particularly preferable; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3). The (poly) oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.
Examples of suitable R ²⁰¹ are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butandyl group, 1,3-butandyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group. , -CH ₂ CH (OH) CH _{2-, and} more preferably an ethylene group, a propylene group, a trimethylene group, and -CH ₂ CH (OH) CH _2-.
Particularly preferably, R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethylene group.

As a preferred embodiment of the polyimide precursor in the present invention, an aliphatic group, an aromatic group and an aryl having one, two or three, preferably one acid group as the monovalent organic group of ^{R 113} or R ^114. Alkyl groups and the like can be mentioned. Specific examples thereof include an aromatic group having an acid group having 6 to 20 carbon atoms and an arylalkyl group having an acid group having 7 to 25 carbon atoms. More specifically, a phenyl group having an acid group and a benzyl group having an acid group can be mentioned. The acid group is preferably a hydroxyl group. That is, R ¹¹³ or R ¹¹⁴ is preferably a group having a hydroxyl group.
As the ^{monovalent organic group represented by R 113} or R ^114, a substituent that improves the solubility of the developing solution is preferably used.
It is more preferable that R ¹¹³ or R ¹¹⁴ is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl from the viewpoint of solubility in an aqueous developer.

From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and an alkyl group substituted with an aromatic group is more preferable.
The alkyl group preferably has 1 to 30 carbon atoms (3 or more in the case of a cyclic group). The alkyl group may be linear, branched or cyclic. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group and an octadecyl group. , Isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, and 2-ethylhexyl group. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Examples of the polycyclic cyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a phenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group and a pinenyl group. Can be mentioned. Further, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described below is preferable.

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. Ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphten ring, phenanthrene ring, anthracene ring, naphthalene ring, chrysen ring, triphenylene ring, etc.) or substituted or unsubstituted aromatic heterocyclic group (group) The cyclic structures constituting the ring include 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 indridin ring, an indole ring, and a benzofuran ring. Benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthylidine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridin ring, aclysine ring, phenanthroline ring, thiantolen ring, chromium ring, xanthene. Ring, phenoxatiin ring, phenothiazine ring or phenazine ring).

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

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

Ａ¹¹およびＡ¹²は、酸素原子またはＮＨを表し、Ｒ¹¹¹およびＲ¹¹²は、それぞれ独立に、２価の有機基を表し、Ｒ¹¹³およびＲ¹¹⁴は、それぞれ独立に、水素原子または１価の有機基を表し、Ｒ¹¹³およびＲ¹¹⁴の少なくとも一方は、ラジカル重合性基を含む基であることが好ましく、ラジカル重合性基であることがより好ましい。The structural unit represented by the formula (1) is preferably the structural unit represented by the formula (1-A) or (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 a monovalent. Representing an organic group, ^{at least one of R 113} and R ¹¹⁴ is preferably a group containing a radically polymerizable group, and more preferably a radically polymerizable group.

A ¹¹ , A ¹² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ have independent preferred ranges, which are synonymous with the preferred ranges ^{of A 1} , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in equation (1). ..
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 polyimide precursor, the structural unit represented by the formula (1) may be one kind, or two or more kinds. Further, the structural isomer of the structural unit represented by the formula (1) may be contained. Further, the polyimide precursor may contain other types of structural units in addition to the structural units of the above formula (1).

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

The weight average molecular weight (Mw) of the polyimide precursor is preferably 2000 to 500000, more preferably 5000 to 100,000, and even more preferably 1000 to 50000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2000 to 50000, and even more preferably 4000 to 25000.
The degree of dispersion of the molecular weight of the polyimide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.

The polyimide precursor can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, the dicarboxylic acid or the dicarboxylic acid derivative is obtained by halogenating it with a halogenating agent and then reacting it with a diamine.
In the method for producing a polyimide precursor, it is preferable to use an organic solvent in the reaction. The organic solvent may be one kind or two or more kinds.
The organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.

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

Ｒ¹²¹は、２価の有機基を表し、Ｒ¹²²は、４価の有機基を表し、Ｒ¹²³およびＲ¹²⁴は、それぞれ独立に、水素原子または１価の有機基を表す。<< Polybenzoxazole precursor >>
The polybenzoxazole precursor preferably contains a structural unit represented by the following formula (2).

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

R ¹²¹ represents a divalent organic group. The divalent organic group includes an aliphatic group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms) and an aromatic group (preferably 6 to 22 carbon atoms, 6 to 14 carbon atoms). Is more preferable, and a group containing at least one of (6 to 12 is particularly preferable) is preferable. Examples of the aromatic group constituting R ^{121 include R 111} of the above formula (1). As the aliphatic group, a linear aliphatic group is preferable. R ¹²¹ is preferably derived from 4,4'-oxydibenzoyl chloride.
In formula (2), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same ^{meaning as R 115} in the above formula (1), and the preferable range is also the same. R ¹²² is preferably derived from 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
R ¹²³ and R ¹²⁴ independently represent a hydrogen atom or a monovalent organic group, ^{which are synonymous with R 113} and R ¹¹⁴ in the above formula (1), and the preferable range is also the same.

The polybenzoxazole precursor may contain other types of structural units in addition to the structural units of the above formula (2).
The polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of structural unit in that the occurrence of warpage of the cured film due to ring closure can be suppressed.

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

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

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

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

The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2000 to 500000, more preferably 5000 to 100,000, and even more preferably 1000 to 50000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2000 to 50000, and even more preferably 4000 to 25000.
The degree of dispersion of the molecular weight of the polybenzoxazole precursor is preferably 1.5 to 3.5, more preferably 2 to 3.

The content of the polymer precursor in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and 40% by mass or more, based on the total solid content of the resin composition. It is even more preferably 50% by mass or more, even more preferably 60% by mass or more, and even more preferably 70% by mass or more. Further, the content of the polymer precursor in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, based on the total solid content of the resin composition. , 98% by mass or less, more preferably 95% by mass or less.
The resin composition of the present invention may contain only one type of polymer precursor, or may contain two or more types of polymer precursors. When two or more kinds are included, the total amount is preferably in the above range.

<Thermal base generator>
The resin composition of the present invention contains a thermobase generator. The type of thermal base generator is not particularly specified, but it is selected from an acidic compound that generates a base when heated to 40 ° C. or higher, and an ammonium salt having an anion having a pKa1 of 0 to 4 and an ammonium cation. It is preferable to include a thermobase generator containing at least one of these. _{Here, pKa1 represents the logarithm (-Log 10} Ka) of the dissociation constant (Ka) of the first proton of the acid, and the details will be described later.
By blending such a compound, a cyclization reaction of a polymer precursor or the like can be carried out at a low temperature. Further, since the thermal base generator does not generate a base unless it is heated, even if it coexists with the polymer precursor, the cyclization of the polymer precursor during storage can be suppressed, and the storage stability is excellent.

The thermobase generator contains at least one selected from an acidic compound (A1) that generates a base when heated to 40 ° C. or higher, and an ammonium salt (A2) having an anion having a pKa1 of 0 to 4 and an ammonium cation. Is preferable. Since the acidic compound (A1) and the ammonium salt (A2) generate bases when heated, the bases generated from these compounds can promote the cyclization reaction of the polymer precursor and cyclize the polymer precursor. It can be done at low temperature. In the present specification, the acidic compound means that 1 g of the compound is collected in a container, 50 mL of a mixed solution of ion-exchanged water and tetrahydrofuran (mass ratio is water / tetrahydrofuran = 1/4) is added, and the compound is added at room temperature for 1 hour. It means a compound having a value of less than 7 measured at 20 ° C. using a pH (power of hydrogen) meter for the solution obtained by stirring.

The base generation temperature of the thermal base generator used in the present invention is preferably 40 ° C. or higher, more preferably 120 to 200 ° C. The upper limit of the base generation temperature is preferably 190 ° C. or lower, more preferably 180 ° C. or lower, and even more preferably 165 ° C. or lower. The lower limit of the base generation temperature is preferably 130 ° C. or higher, more preferably 135 ° C. or higher. For the base generation temperature, for example, using differential scanning calorimetry, the compound is heated to 250 ° C. in a pressure resistant capsule at 5 ° C./min, the peak temperature of the lowest exothermic peak is read, and the peak temperature is measured as the base generation temperature. can do.

The base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, and more preferably a tertiary amine. Since the tertiary amine is highly basic, the cyclization temperature of the polymer precursor can be lowered. The boiling point of the base generated by the thermal base generator is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and even more preferably 140 ° C. or higher. The molecular weight of the generated base is preferably 80 to 2000. The lower limit is more preferably 100 or more. The upper limit is more preferably 500 or less. The value of the molecular weight is a theoretical value obtained from the structural formula.

In the present embodiment, the acidic compound (A1) preferably contains one or more selected from an ammonium salt and a compound represented by the formula (101) or (102) described later.

In the present embodiment, the ammonium salt (A2) is preferably an acidic compound. The ammonium salt (A2) may be a compound containing an acidic compound that generates a base when heated to 40 ° C. or higher (preferably 120 to 200 ° C.), or 40 ° C. or higher (preferably 120 to 200 ° C.). ) May be a compound excluding an acidic compound that generates a base when heated to).

式（１０１）および式（１０２）中、Ｒ¹〜Ｒ⁶は、それぞれ独立に、水素原子または炭化水素基を表し、Ｒ⁷は炭化水素基を表す。式（１０１）および式（１０２）におけるＲ¹とＲ²、Ｒ³とＲ⁴、Ｒ⁵とＲ⁶、Ｒ⁵とＲ⁷はそれぞれ結合して環を形成してもよい。In the present embodiment, the ammonium salt means a salt of an ammonium cation represented by the following formula (101) or formula (102) and an anion. The anion may be bonded to any part of the ammonium cation via a covalent bond, or may be held outside the molecule of the ammonium cation, but may be held outside the molecule of the ammonium cation. preferable. The fact that the anion is present outside the molecule of the ammonium cation means that the ammonium cation and the anion are not bonded via a covalent bond. Hereinafter, the extramolecular anion of the cation part is also referred to as a counter anion.
Equation (101) Equation (102)

In formulas (101) and (102), R ^{1 to} R ⁶ independently represent a hydrogen atom or a hydrocarbon group, and R ⁷ represents a hydrocarbon group. ^{R 1} and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , and R ⁵ and R ⁷ in formulas (101) and (102) may be combined to form a ring, respectively.

The ammonium cation is preferably represented by any of the following formulas (Y1-1) to (Y1-5).

In formulas (Y1-1) to (Y1-5), R ¹⁰¹ represents an n-valent organic group, and R ¹ and R ⁷ are synonymous with formula (101) or formula (102).
In formulas (Y1-1) to (Y1-5), Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group, n represents an integer of 1 or more, and m represents an integer of 0 to 5. ..

In the present embodiment, the ammonium salt preferably has an anion having a pKa1 of 0 to 4 and an ammonium cation. The upper limit of pKa1 of the anion is more preferably 3.5 or less, and even more preferably 3.2 or less. The lower limit is preferably 0.5 or more, and more preferably 1.0 or more. When the pKa1 of the anion is in the above range, the polymer precursor can be cyclized at a lower temperature, and the stability of the resin composition can be improved. When pKa1 is 4 or less, the stability of the thermobase generator is good, the generation of bases can be suppressed without heating, and the stability of the resin composition is good. When pKa1 is 0 or more, the generated base is not easily neutralized, and the cyclization efficiency of the polymer precursor is good.
The type of anion is preferably one selected from a carboxylic acid anion, a phenol anion, and a phosphate anion, and a carboxylic acid anion is more preferable because both salt stability and thermal decomposability can be achieved at the same time. 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 carboxyl groups, and more preferably a divalent carboxylic acid anion. According to this aspect, it is possible to obtain a thermobase generator capable of further improving the stability, curability and developability of the resin composition. In particular, by using a divalent carboxylic acid anion, the stability, curability and developability of the resin composition can be further improved.
In the present embodiment, the carboxylic acid anion is preferably an anion of a carboxylic acid having a pKa1 of 4 or less. The pKa1 is more preferably 3.5 or less, and even more preferably 3.2 or less. According to this aspect, the stability of the resin composition can be further improved.
Here, pKa1 represents the logarithm of the reciprocal of the dissociation constant of the first proton of the acid, and is Determination of Organic Structures by Physical Methods (author: Brown, HC, McDaniel, D.H., Hafli). , Nachod, F.C .; Compilation: Braude, E.A., Nachod, F.C .; Academic Press, New York, 1955) and Data for Biochemical Research (Author: D. al; Oxford, Clarendon Press, 1959) can be referred to. 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.

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-attracting group.

In the present embodiment, the electron-attracting group means that Hammett's substituent constant σm shows a positive value. Here, σm is a review by Yusuke Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965), p. It is described in detail in 631-642. The electron-attracting 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 CO groups (σm = 0.63), HC≡C groups (σm = 0.21), CH. ₂ = CH group (σm = 0.06), Ac group (σm = 0.38), MeOCO group (σm = 0.37), MeCOCH = CH group (σm = 0.21), PhCO group (σm = 0) .34), H ₂ NCOCH ₂ group (σm = 0.06), and the like. Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group.

式（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、ヒドロキシル基またはカルボキシル基を表し、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 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 hydroxyl group or a carboxyl group, and Ar is an aromatic group. Represents.

式（ＸＡ）において、Ｌ¹⁰は、単結合、または、アルキレン基、アルケニレン基、芳香族基、−ＮＲ^X−およびこれらの組み合わせから選ばれる２価の連結基を表し、Ｒ^Xは、水素原子、アルキル基、アルケニル基またはアリール基を表す。In the present embodiment, the carboxylic acid anion is preferably represented by the following formula (XA).
Equation (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 linking group selected from these combinations, R ^X is a 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 oxalate anion. These can be preferably used.

Specific examples of the thermobase generator include the following compounds.

The content of the thermal base generator is preferably 0.1 to 50% by mass with respect to the total solid content of the resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less. As the thermobase generator, one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.

<Radical polymerization initiator>
The resin composition of the present invention preferably contains a radical polymerization initiator. In particular, when a polymer precursor containing a radically polymerizable group or a radically polymerizable compound is used, the resin composition of the present invention preferably contains a radical polymerization initiator. Examples of the radical polymerization initiator include a photoradical polymerization initiator and a thermal radical polymerization initiator. The radical polymerization initiator used in the resin composition of the present invention is preferably a photoradical polymerization initiator.

<< Photo-Radical Polymerization Initiator >>
The photoradical polymerization initiator is not particularly limited and may be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. Further, it may be an activator that produces an active radical by causing some action with the photoexcited sensitizer.
The photoradical polymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 in the range of about 300 to 800 nm (preferably 330 to 500 nm). The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

As the photoradical polymerization initiator, a known compound can be arbitrarily used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives and the like. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. Can be mentioned. For details thereof, the description in paragraphs 0165 to 0182 of JP2016-027357 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 JP2015-087611A 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-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 (manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (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 (manufactured by BASF) can be used.
Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF).

市販品ではＩＲＧＡＣＵＲＥ ＯＸＥ ０１、ＩＲＧＡＣＵＲＥ ＯＸＥ ０２、ＩＲＧＡＣＵＲＥ ＯＸＥ ０３、ＩＲＧＡＣＵＲＥ ＯＸＥ ０４（以上、ＢＡＳＦ社製）、アデカオプトマーＮ−１９１９（（株）ＡＤＥＫＡ製、特開２０１２−０１４０５２号公報に記載の光ラジカル重合開始剤２）も好適に用いられる。また、ＴＲ−ＰＢＧ−３０４（常州強力電子新材料有限公司製）、アデカアークルズＮＣＩ−８３１およびアデカアークルズＮＣＩ−９３０（（株）ＡＤＥＫＡ製）も用いることができる。また、ＤＦＩ−０９１（ダイトーケミックス株式会社製）を用いることができる。
さらに、また、フッ素原子を有するオキシム化合物を用いることも可能である。そのようなオキシム化合物の具体例としては、特開２０１０−２６２０２８号公報に記載されている化合物、特表２０１４−５００８５２号公報の段落０３４５に記載されている化合物２４、３６〜４０、特開２０１３−１６４４７１号公報の段落０１０１に記載されている化合物（Ｃ−３）などが挙げられる。
最も好ましいオキシム化合物としては、特開２００７−２６９７７９号公報に示される特定置換基を有するオキシム化合物や、特開２００９−１９１０６１号公報に示されるチオアリール基を有するオキシム化合物などが挙げられる。The photoradical polymerization initiator is more preferably an oxime compound. By using the oxime compound, the exposure latitude can be improved more effectively. The oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a photocuring accelerator.
As specific examples of the oxime compound, the compound described in JP-A-2001-233842, the compound described in JP-A-2000-080068, 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-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, and 2-acetoxy. Iminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one , And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like. In the resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as the photoradical polymerization initiator. Oxime-based photopolymerization initiators have a> C = N—O—C (= O) − linking group in the molecule.

Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), ADEKA PUTMER N-1919 (manufactured by ADEKA Corporation, Japanese Patent Application Laid-Open No. 2012-014052). A radical polymerization initiator 2) is also preferably used. Further, TR-PBG-304 (manufactured by Changshu Powerful Electronics New Materials Co., Ltd.), ADEKA ARCLUS NCI-831 and ADEKA ARCULDS NCI-930 (manufactured by ADEKA Corporation) can also be used. Further, DFI-091 (manufactured by Daito Chemix Co., Ltd.) can be used.
Furthermore, it is also possible to use an oxime compound having a fluorine atom. Specific examples of such an oxime compound include compounds described in JP-A-2010-262028, compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013. Examples thereof include the compound (C-3) described in paragraph 0101 of JP-A-164471.
The most preferable oxime compound includes an oxime compound having a specific substituent shown in JP-A-2007-269779 and an oxime compound having a thioaryl group shown in JP-A-2009-191061.

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

式中、Ｒ^I05〜Ｒ^I07は、上記式（Ｉ）のＲ^I02〜Ｒ^I04と同じである。From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, or a triaryl. Selected from the group consisting of imidazole dimer, onium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halomethyloxaziazole compound, 3-aryl substituted coumarin compound. Compounds are preferred.
More preferable photoradical polymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds and acetophenone compounds. At least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferable, and metallocene compounds or oxime compounds are even more preferable, and oxime compounds are even more preferable. Is even more preferable.
The photoradical polymerization initiator is N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone). -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 alkoxyl group having 1 to 12 carbon atoms, a phenyl group, and the like. Alkyl group with 1 to 20 carbon atoms, alkoxyl group with 1 to 12 carbon atoms, halogen atom, cyclopentyl group, cyclohexyl group, alkenyl group with 2 to 12 carbon atoms, carbon number 2 to interrupted by one or more oxygen atoms 18 alkyl group and at least one substituted phenyl group of the alkyl group having 1 to 4 carbon atoms or a biphenyl,, R ^I01 is a group represented by formula (II), the same as R ^I00 It is a group, and R ^{I02 to} R ^I04 are independently alkyl having 1 to 12 carbon atoms and alkoxy or halogen having 1 to 12 carbon atoms, respectively.

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

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

When the photoradical 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 resin composition of the present invention. Yes, more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. Only one type of photoradical polymerization initiator may be contained, or two or more types may be contained. When two or more kinds of photoradical polymerization initiators are contained, the total is preferably in the above range.

<< Thermal Radical Polymerization Initiator >>
A thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, it is possible to proceed with the polymerization reaction of the polymer precursor as well as the cyclization of the polymer precursor, so that a higher degree of heat resistance can be achieved. Specific examples of the thermal radical polymerization initiator include 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 resin composition of the present invention. Yes, more preferably 5 to 15% by mass. Only one type of thermal radical polymerization initiator may be contained, or two or more types may be contained. When two or more types of thermal radical polymerization initiators are contained, the total is preferably in the above range.

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

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

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

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

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

Further, as the radically polymerizable compound, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable. Examples include polyethylene glycol di (meth) acrylate, trimethyl ethanetri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol. Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylpropantri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin, trimethylolethane, etc. A compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, is described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 50-006034, and Japanese Patent Application Laid-Open No. 51-037193. Such urethane (meth) acrylates, polyester acrylates described in JP-A-48-064183, JP-A-49-043191, and JP-A-52-030490, epoxy resins and (meth) acrylics. Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acids, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Further, a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether group such as glycidyl (meth) acrylate and a compound having an ethylenically unsaturated bond can also be mentioned.
Further, as a preferable radically polymerizable compound other than the above, it has a fluorene ring and has an ethylenically unsaturated bond, which is described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216 and the like. It is also possible to use a compound having two or more groups having the above, or a cardo resin.
Further, as other examples, the specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Square Root 01-040337, Japanese Square Root 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 Japanese Patent Application Laid-Open No. 10-062986 together with specific examples as formulas (1) and (2) after addition of ethylene oxide or propylene oxide to a polyfunctional alcohol is also (meth) acrylated. It can be used as a radically polymerizable compound.

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

Examples of 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 (meth) Acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and these (meth) acryloyl groups via ethylene glycol residues or propylene glycol residues. Bonded structures are preferred. 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 Application Laid-Open No. 02-032293, and Japanese Patent Application Laid-Open No. 02-016765. , Urethane compounds having an ethylene oxide-based skeleton described in 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 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 carboxyl 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 hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. A radically polymerizable compound having a group is more preferable. Particularly preferably, in a radical polymerizable compound in which an unreacted hydroxyl group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to have an acid group, the aliphatic polyhydroxy compound is pentaerythritol or dipenta. It is a compound that is erythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
The acid value of the radically polymerizable compound having an acid group is preferably 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When the acid value of the radically polymerizable compound is within the above range, it is excellent in manufacture and handling, and further excellent in developability. Moreover, the polymerizable property is good.

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

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

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

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

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

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

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

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

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

Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (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, dimethyllBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (manufactured by Honshu Kagaku Kogyo Co., Ltd.), NIKALAC MX-290 (Sanwa Chemical Co., Ltd.) , 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol and the like.

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 (manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (manufactured by Asahi Organic Materials Industry Co., Ltd.), NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW- 100LM (manufactured by Sanwa Chemical Co., Ltd.) can be mentioned.

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

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

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

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

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

Preferred examples of the benzoxazine compound include BA type benzoxazine, Bm type benzoxazine (manufactured by Shikoku Kasei Kogyo Co., Ltd.), a benzoxazine adduct of a polyhydroxystyrene resin, and a phenol novolac type dihydrobenzoxazine compound. .. 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 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.
When a radically 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 resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.
One type of the polymerizable compound may be used alone, or two or more types may be mixed and used. When two or more types are used in combination, the total amount is preferably in the above range.

<Solvent>
The resin composition of the present invention preferably contains a solvent. As the solvent, a known solvent can be arbitrarily used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.
Examples of esters include ethyl acetate, -n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone. , Δ-Valerolactone, alkylalkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.) )), 3-alkyloxypropionic acid alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-). Methyl ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate) Etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyloxy-2-methylpropion Methyl acetate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, pyruvin Suitable examples include propyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutate and the like.
Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol. Suitable examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.
As the ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like are preferable.
As the aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene and the like are preferable.
As the sulfoxides, for example, dimethyl sulfoxide is preferable.
As the amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like are preferable.

As the solvent, a form in which two or more kinds are mixed is also preferable from the viewpoint of improving the coating surface properties.
In the present invention, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ- Consists of one solvent selected from butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, or two or more. The mixed solvent to be mixed is preferable. The combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

From the viewpoint of coatability, the solvent content is preferably such that the total solid content concentration of the resin composition of the present invention is 5 to 80% by mass, and is preferably 5 to 75% by mass. More preferably, the amount is 10 to 70% by mass, 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 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 resin composition layer.
The migration inhibitor is not particularly limited, but a heterocycle (pyran ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isooxazole ring, isothiazole ring, tetrazole ring, pyridine ring, etc. Pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring, piperazine ring, morpholin ring, 2H-pyran ring and 6H-pyran ring, triazine ring), thiourea and sulfanyl group compounds, hindered phenol compounds , Salicylic acid derivative compound, hydrazide derivative compound and the like. In particular, triazole-based compounds such as 1,2,4-triazole and benzotriazole, and tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

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

Examples of other migration inhibitors include rust preventives described in paragraph 0094 of JP2013-015701, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-059656. The compounds described in paragraph 0052, the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520A, the compounds 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 resin composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, preferably 0.05 to 2% by mass, based on the total solid content of the resin composition. It is more preferably 0.0% by mass, and even more preferably 0.1 to 1.0% by mass. The migration inhibitor may be only one type or two or more types. When there are two or more types of migration inhibitors, the total is preferably in the above range.

<Polymerization inhibitor>
The 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 resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass, preferably 0, based on the total solid content of the resin composition of the present invention. It is more preferably .02 to 3% by mass, and even more preferably 0.05 to 2.5% by mass. 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 resin composition of the present invention preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like. Examples of the metal adhesiveness improving agent include a silane coupling agent.

Examples of the silane coupling agent include the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, paragraphs of International Publication No. 2011/080992. Compounds described in 0063 to 0071, compounds described in paragraphs 0060 to 0061 of JP-A-2014-191252, compounds described in paragraphs 0045-0052 of JP-A-2014-041264, International Publication No. 2014/0975994. Examples include the compounds described in paragraph 0055. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A. Further, it is also preferable to use the following compounds as the silane coupling agent. In the following formula, Et represents an ethyl group.

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

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

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

<< Thermal Acid Generator >>
The resin composition of the present invention may contain a thermoacid generator. The thermoacid generator is used for elimination of the protecting group when the specific thermobase generator has a protecting group.

The content of the thermoacid generator is preferably 0.01 part by mass or more, and more preferably 0.1 part by mass or more with respect to 100 parts by mass of the polymer precursor. By containing 0.01 part by mass or more of the thermal acid generator, the cross-linking reaction and the cyclization of the polymer precursor are promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved. The content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 10 parts by mass or less from the viewpoint of electrical insulation of the cured film.
Only one type of thermoacid generator may be used, or two or more types may be used. When two or more types are used, the total amount is preferably in the above range.

<< Sensitive Dye >>
The resin composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs a specific active radiation and becomes an electron-excited state. The sensitizing dye in the electron-excited state comes into contact with a thermal curing accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and acts such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal curing accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo a chemical change and decompose to generate radicals, acids, or bases. For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP-A-2016-0273557 can be referred to, and this content is incorporated in the present specification.

When the resin composition of the present invention contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01 to 20% by mass with respect to the total solid content of the resin composition of the present invention. It is more preferably 1 to 15% by mass, and even more preferably 0.5 to 10% by mass. The sensitizing dye may be used alone or in combination of two or more.

<< Chain Transfer Agent >>
The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pp. 683-684. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals. In particular, a thiol compound can be preferably used.
Further, as the chain transfer agent, the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219 can also be used.

When the resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, preferably 1 to 20 parts by mass, based on 100 parts by mass of the total solid content of the resin composition of the present invention. 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.

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

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

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

<< Higher fatty acid derivatives >>
In the resin composition of the present invention, in order to prevent polymerization inhibition due to oxygen, higher fatty acid derivatives such as behenic acid and behenic acid amide are added, and the resin composition is unevenly distributed on the surface of the composition in the process of drying after application. You may let me.
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 resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass with respect to the total solid content of the resin composition of the present invention. 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 resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass from the viewpoint of coating surface properties.

From the viewpoint of insulating properties, the metal content of the 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. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are contained, the total of these metals is preferably in the above range.
Further, as a method for reducing metal impurities unintentionally contained in the resin composition of the present invention, a raw material having a low metal content is selected as a raw material constituting the resin composition of the present invention. Examples thereof include a method of filtering the raw materials constituting the product, a method of lining the inside of the device with polytetrafluoroethylene or the like, and performing distillation under conditions in which contamination is suppressed as much as possible.

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

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

[Preparation of resin composition]
The resin composition of the present invention can be prepared by mixing each of the above components. The mixing method is not particularly limited, and a conventionally known method can be used.
Further, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the composition. The filter pore diameter is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When using a plurality of types of filters, filters having different pore diameters or materials may be used in combination. In addition, various materials may be filtered a plurality of times. When filtering a plurality of times, circulation filtration may be used. Moreover, you may pressurize and perform filtration. When pressurizing and filtering, the pressurizing pressure is preferably 0.05 MPa or more and 0.3 MPa or less.
In addition to filtration using a filter, impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

[Cured film, laminate, semiconductor device, and 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 resin composition of the present invention. The film thickness of the cured film of the present invention can be, for example, 0.5 μm or more, and can be 1 μm or more. Further, the upper limit value can be 100 μm or less, and can be 30 μm or less. The film thickness of the cured film of the present invention is preferably 1 to 30 μm.

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

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

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

The method for producing a cured film of the present invention includes using the resin composition of the present invention. Specifically, it is preferable to include the following steps (a) to (d).
(A) Film forming step of applying the resin composition to the substrate to form a film (b) Exposure step of exposing the film after the film forming step (c) Development treatment of the exposed resin composition layer (D) Heating step of heating the developed resin composition at 80 to 450 ° C. As in this embodiment, the exposed resin layer can be further cured by heating after development. ..

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. The method for producing the laminated body of the present embodiment is the step (a), the steps (a) to (c), or (a) after forming the cured film according to the above-mentioned method for producing the cured film. )-(D). In particular, it is preferable to carry out each of the above steps a plurality of times, for example, 2 to 5 times (that is, 3 to 6 times in total) in order. By laminating the cured film in this way, a laminated body can be obtained. In the present invention, it is particularly preferable to provide a metal layer on the portion provided with the cured film, between the cured films, or both. 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 resin composition is applied to a substrate to form a film (layered).
The type of substrate can be appropriately determined depending on the application, but semiconductor fabrication substrates such as silicon, silicon nitride, polysilicon, polysilicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, thin film, and magnetic film. , Reflective film, metal substrate such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, plasma display panel (PDP) electrode plate, and the like are not particularly limited. In the present invention, a semiconductor-made substrate is particularly preferable, and a silicon substrate is more preferable.
When the resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer serves as a substrate.
Coating is preferable as a means for applying the 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 resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an inkjet method are more preferable. A resin layer having a desired thickness can be obtained by adjusting an appropriate solid content concentration and coating conditions according to the method. The coating method can be appropriately selected depending on the shape of the substrate. For circular substrates such as wafers, the spin coating method, spray coating method, inkjet method, etc. are preferable, and for rectangular substrates, the slit coating method, spray coating method, inkjet, etc. The method or the like is preferable. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 2000 rpm for about 10 seconds to 1 minute.

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

<Exposure process>
The production method of the present invention may include an exposure step of exposing the resin composition layer. Exposure is not particularly limited so long as it can be cured a resin composition, for example, it is preferable to irradiate 100~10000mJ / cm ² at an exposure energy conversion at a wavelength 365 nm, to irradiate 200~8000mJ / cm ² More preferred.
The exposure wavelength can be appropriately determined in the range of 190 to 1000 nm, preferably 240 to 550 nm.
The exposure wavelengths are as follows: (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength 436 nm), h. Line (wavelength 405 nm), i-line (wavelength 365 nm), broad (3 wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer Examples thereof include a laser (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), and (6) electron beam. For the resin composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferable, and exposure with an i-line is particularly preferable. As a result, particularly high exposure sensitivity can be obtained.

<Development process>
The production method of the present invention may include a development treatment step of performing a development treatment on the exposed resin composition layer. By developing, the unexposed portion (non-exposed portion) is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and for example, a developing method such as paddle, spray, immersion, or ultrasonic wave can be adopted.
Development is performed using a developing solution. The developer can be used without particular limitation as long as the unexposed portion (non-exposed portion) is removed. The developer preferably contains an organic solvent, and more preferably the developer contains 90% or more of the organic solvent. In the present invention, the developer preferably contains an organic solvent having a ClogP value of −1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting a structural formula in ChemBioDraw.
Examples of the organic solvent include ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and γ-butyrolactone. , Ε-caprolactone, δ-valerolactone, alkylalkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, (Ethyl ethoxyacetate, etc.)), alkyl esters of 3-alkyloxypropionic acid (eg, methyl 3-alkyloxypropionic acid, ethyl 3-alkyloxypropionic acid, etc.), etc. (eg, methyl 3-methoxypropionate, 3-methoxypropionic acid, etc.) Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl) Propyl oxypropionate and the like (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvin Ethyl acetate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. As ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene. Etc., 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 developing solution preferably contains 50% by mass or more of an organic solvent, more preferably 70% by mass or more of an organic solvent, and further preferably 90% by mass or more of an organic solvent. Further, the developing solution may be 100% by mass of an organic solvent.

The development time is preferably 10 seconds to 5 minutes. The temperature of the developing solution at the time of development is not particularly specified, but is usually 20 to 40 ° C.
After the treatment with the developing solution, further rinsing may be performed. The rinsing is preferably performed with a solvent different from that of the developing solution. For example, it can be rinsed with the solvent contained in the resin composition. The rinsing time is preferably 5 seconds to 1 minute.

<Heating process>
The production method of the present invention preferably includes a step of heating after a film forming step (layer forming step), a drying step, or a developing step. In the heating step, the cyclization reaction of the polymer precursor proceeds. The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, further preferably 140 ° C. or higher, and 150 ° C. or higher. Is even more preferable, 160 ° C. or higher is even more preferable, and 170 ° C. or higher is even more preferable. The upper limit is preferably 500 ° C. or lower, more preferably 450 ° C. or lower, further preferably 350 ° C. or lower, further preferably 250 ° C. or lower, and preferably 220 ° C. or lower. Even more preferable.
The heating is preferably performed at a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min. By setting the temperature rise rate to 1 ° C./min or more, it is possible to prevent excessive volatilization of amine while ensuring productivity, and by setting the temperature rise rate to 12 ° C./min or less, the cured film can be prevented. Residual stress can be relaxed.
The temperature at the start of heating is preferably 20 ° C. to 150 ° C., more preferably 20 ° C. to 130 ° C., and even more preferably 25 ° C. to 120 ° C. The temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature is started. For example, when the resin composition is applied onto a substrate and then dried, the temperature of the film (layer) after drying is, for example, 30 to 200 ° C. lower than the boiling point of the solvent contained in the resin composition. It is preferable to gradually raise the temperature from the temperature.
The heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and even more preferably 30 to 240 minutes.
In particular, when forming a multi-layered laminate, the heating temperature is preferably 180 ° C. to 320 ° C., more preferably 180 ° C. to 260 ° C., from the viewpoint of adhesion between layers of the cured film. The reason is not clear, but it is considered that the ethynyl groups of the polymer precursors between the layers are undergoing a cross-linking reaction at this temperature.

Heating may be performed in stages. As an example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min and held at 180 ° C. for 60 minutes, the temperature is raised from 180 ° C. to 200 ° C. at 2 ° C./min, and held at 200 ° C. for 120 minutes. , Etc. may be performed. The heating temperature as the pretreatment step is preferably 100 to 200 ° C., more preferably 110 to 190 ° C., and even more preferably 120 to 185 ° C. In this pretreatment step, it is also preferable to perform the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547. It is possible to improve the characteristics of the film by such a pretreatment step. The pretreatment step is preferably performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps, for example, the pretreatment step 1 may be performed in the range of 100 to 150 ° C., and then the pretreatment step 2 may be performed in the range of 150 to 200 ° C.
Further, 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 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 resin composition layer after the development treatment.
As the metal layer, existing metal species can be used without particular limitation, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified, copper and aluminum are more preferable, and copper is preferable. More preferred.
The method for forming the metal layer is not particularly limited, and an existing method can be applied. For example, the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a combination method thereof can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electroplating can be mentioned.
The thickness of the metal layer is preferably 0.1 to 50 μm, more preferably 1 to 10 μm at the thickest portion.

<Laminating process>
The production method of the present invention preferably further includes a laminating step.
The laminating step is a step of (a) film forming step (layer forming step), (b) exposure step, (c) developing process step, and (d) heating step again on the surface of the cured film (resin layer) or metal layer. Is a series of steps including performing in this order. However, the mode may be such that 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 resin composition layers 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 steps of (d) are collectively performed after laminating a predetermined number of times. Heating may be performed. Needless to say, the laminating step may further include the drying step, the heating step, and the like as appropriate.
When the laminating step is further performed after the laminating step, the surface activation treatment step may be further performed after the heating step, the exposure step, or the metal layer forming step. An example of the surface activation treatment is plasma treatment.
The laminating step is preferably performed 2 to 5 times, more preferably 3 to 5 times.
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 resin composition so as to cover the metal layer after providing the metal layer. Specifically, a mode 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 resin composition layer (resin) and the metal layer forming step, the resin composition layer (resin layer) and the metal layer can be laminated alternately.

The present invention also discloses a semiconductor device having the cured film or laminate of the present invention. As specific examples of the semiconductor device in which the 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 can be referred to. These contents are incorporated in the present specification.

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.

<Specific component ^{_{(HNO 2, NO 2 -,}} HNO 3, NO 3 -, H 2 SO 4, HSO 4 -, SO 4 2-, H 2 SO 3, HSO 3 - and SO ₃ ^2-) of the content of Measurement method>
20 g of the measurement sample, 50 g of tetrahydrofuran as a non-aqueous organic solvent, and 50 g of ultrapure water were mixed. If the solid is precipitated by adding water, the solid is removed by centrifugation, and if the solid is not precipitated, the organic layer and the aqueous layer are separated (separation operation), and the content of the specific component extracted into the aqueous solution is determined. It was measured by the ion chromatograph method. As a measuring device, Shimadzu HIC-20A (manufactured by Shimadzu Corporation) was used.

<Synthesis example 1>
[Synthesis of polyimide precursor (A-1: polyimide precursor having no radical polymerizable group) from pyromellitic acid dianhydride, 4,4'-diaminodiphenyl ether and benzyl alcohol]
14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C. for 12 hours) and 14.22 g (131.58 mmol) of benzyl alcohol were suspended in 50 mL of N-methylpyrrolidone. , Dryed with a molecular sieve. The suspension was heated at 100 ° C. for 3 hours. The reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) of pyridine and 90 mL of N-methylpyrrolidone were added. The reaction mixture was then cooled to −10 ° C. and 16.12 g (135.5 mmol) of SOCL ₂ was added over 10 minutes while keeping the temperature at −10 ± 4 ° C. Viscosity increased while adding SOCL _2. After diluting with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, a solution prepared by dissolving 11.08 g (58.7 mmol) of 4,4′-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at −5 to 0 ° C. over 20 minutes. Then, the reaction mixture was reacted at 0 ° C. for 1 hour, 70 g of ethanol was added, and the mixture was stirred at room temperature overnight. The polyimide precursor was then precipitated in 5 L of water and the water-polyimide precursor mixture was stirred at a rate of 5000 rpm for 15 minutes.
The obtained wet solid was dissolved in 300 mL of tetrahydrofuran (THF), then 300 mL of water was added, and the liquid separation operation was repeated 3 times. The resulting THF / polyimide precursor solution was reprecipitated with 5 L of water. The polyimide precursor was removed by filtration, stirred again in 4 L of water for 30 minutes and filtered again. The obtained polyimide precursor was then dried under reduced pressure at 45 ° C. for 3 days. The weight average molecular weight of this polyimide precursor was 18,000. Furthermore, certain components of the polyimide precursor ^{_{(HNO 2, NO 2 -,}} HNO 3, NO 3 -, H 2 SO 4, HSO 4 -, SO 4 2-, H 2 SO 3, HSO 3 - and SO ₃ ^When the content of 2-) was measured by ion chromatography, no specific component was detected.

A-1

<Synthesis example 2>
[Synthesis of polyimide precursor (A-2: polyimide precursor having radical polymerizable group) from pyromellitic acid dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate]
14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, and 20 .4 g of pyridine (258 mmol) and 100 g of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at a temperature of 60 ° C. for 18 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Next, the obtained diester is _{chlorinated with SOCL 2} , converted to a polyimide precursor with 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example 1, and the polyimide precursor is converted into a polyimide precursor in the same manner as in Synthesis Example 1. Obtained. The weight average molecular weight of this polyimide precursor was 19,000. Furthermore, certain components of the polyimide precursor ^{_{(HNO 2, NO 2 -,}} HNO 3, NO 3 -, H 2 SO 4, HSO 4 -, SO 4 2-, H 2 SO 3, HSO 3 - and SO ₃ ^When the content of 2-) was measured by ion chromatography, no specific component was detected.

A-2

<Synthesis example 3>
[Synthesis of polyimide precursor (A-3: polyimide precursor having radical polymerizable group) from 4,4'-oxydiphthalic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate]
20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140 ° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, and 0.05 g of hydroquinone. , 20.4 g of pyridine (258 mmol) and 100 g of diglime were mixed and stirred at a temperature of 60 ° C. for 18 hours to prepare a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. .. Next, the obtained diester is _{chlorinated with SOCL 2} , converted to a polyimide precursor with 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example 1, and the polyimide precursor is converted into a polyimide precursor in the same manner as in Synthesis Example 1. Obtained. Furthermore, certain components of the polyimide precursor ^{_{(HNO 2, NO 2 -,}} HNO 3, NO 3 -, H 2 SO 4, HSO 4 -, SO 4 2-, H 2 SO 3, HSO 3 - and SO ₃ ^When the content of 2-) was measured by ion chromatography, no specific component was detected.

A-3

<Synthesis example 4>
[4,4'-oxydiphthalic anhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (orthotridin) and polyimide precursor from 2-hydroxyethyl methacrylate (A-4: 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 diglime were mixed and stirred at a temperature of 60 ° C. for 18 hours to prepare a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. .. Next, the obtained diester was _{chlorinated with SOCL 2} and then converted into a polyimide precursor with 4,4'-diamino-2,2'-dimethylbiphenyl in the same manner as in Synthesis Example 1, and the same as in Synthesis Example 1. A polyimide precursor was obtained by the above method. The weight average molecular weight of this polyimide precursor was 19,000. Furthermore, certain components of the polyimide precursor ^{_{(HNO 2, NO 2 -,}} HNO 3, NO 3 -, H 2 SO 4, HSO 4 -, SO 4 2-, H 2 SO 3, HSO 3 - and SO ₃ ^When the content of 2-) was measured by ion chromatography, no specific component was detected.

A-4

<Synthesis example 5>
[Synthesis of polybenzoxazole precursor (A-5) from 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 4,4'-oxydibenzoyl chloride]
To 100 mL of N-methyl-2-pyrrolidone, 13.92 g of 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added and dissolved by stirring. Subsequently, 11.21 g of 4,4'-oxydibenzoyl chloride was added dropwise over 10 minutes while maintaining the temperature at 0 to 5 ° C., and then stirring was continued for 60 minutes. The polybenzoxazole precursor was then precipitated in 6 liters of water and the water-polybenzoxazole precursor mixture was stirred at a rate of 5000 rpm for 15 minutes. The polybenzoxazole precursor was filtered off and stirred again in 6 liters of water for 30 minutes and filtered again. The resulting polybenzoxazole precursor was then dried under reduced pressure at 45 ° C. for 3 days. The weight average molecular weight of this polybenzoxazole precursor was 15,000. Also, certain components in the polybenzoxazole precursor ^{_{(HNO 2, NO 2 -,}} HNO 3, NO 3 -, H 2 SO 4, HSO 4 -, SO 4 2-, H 2 SO 3, HSO 3 - And SO ₃ ^2- ) were not detected.

A-5

<Examples and Comparative Examples>
The components listed in the table below were mixed to obtain each resin composition. For the components other than the polymer precursor, purification methods such as distillation and crystallization were repeated for the components listed in the table below. When the content of the specific component in these components was confirmed by ion chromatography, it was confirmed that these components did not contain the specific component. The obtained resin composition was pressure-filtered through a filter having a pore width of 0.8 μm. Then sodium nitrite, nitrate, sodium nitrate, sulfate, potassium hydrogen sulfate, sodium sulfate, sulfite water, HNO _2, NO ₂ by addition of sodium bisulfite and sodium sulfite ^{_{-, HNO 3, NO 3 -}} , H 2 SO ^{_{4, HSO 4 -, sO 4}} 2-, H 2 sO 3, HSO 3 - and sO ₃ ^2-content content and adjusting the resin compositions of examples and Comparative examples so as shown in the following table The thing was prepared. The content of the above components was measured by adding to the resin composition and extracting with water by an ion chromatograph method.

The raw materials listed in the above table are as follows.

(Polymer precursor)
A-1 to A-5: Polymer precursors A-1 to A-5 described above

(Thermal base 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)

Ｄ−３：Ａ−ＴＭＭＴ（新中村化学工業（株）製）(Radical polymerizable compound)
D-1: A-DPH (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
D-2: SR-209 (manufactured by Sartmer, compound with 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.)

(Migration inhibitor)
F-1 to F-4: Compounds with the following structure

(Metal adhesion improver)
G-1 to G-3: 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)

<Evaluation of storage stability>
The viscosity (0 days) of the resin compositions of compositions 1 to 36 was measured using an E-type viscometer. After allowing the resin composition to stand in a closed container at 25 ° C. for 14 days, the viscosity (14 days) was measured again using an E-type viscometer. The viscosity volatility was calculated from the following formula. The lower the viscosity volatility, the higher the storage stability.
Viscosity 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.
A: Viscosity volatility is 5% or less B: Viscosity volatility is more than 5% and 10% or less C: Viscosity volatility is more than 10% and 15% or less D: Viscosity volatility is more than 15% and 20% Less than

<Evaluation of moisture resistance>
The resin compositions of compositions 1 to 36 were applied onto a silicon wafer by a spin coating method and dried at 100 ° C. for 5 minutes using a hot plate to form a resin composition layer having a thickness of about 15 μm. This resin composition layer was heated at a heating rate of 10 ° C./min under a nitrogen atmosphere, reached 250 ° C., and then heated for 3 hours to form a cured film. The silicon wafer on which this cured film was formed was put into a constant temperature and humidity layer at a temperature of 85 ° C. and a humidity of 85% for 24 hours, and the area of the modified (whitening, cracking) occurrence portion with respect to the area of the cured film was observed. The moisture resistance was evaluated.
A: The location where denaturation occurs is less than 2% of the area of the cured film B: The location where denaturation occurs is 2% or more and less than 5% of the area of the cured membrane C: The location where denaturation occurs is 5% or more 10% of the area of the cured membrane Less than% D: The location where denaturation occurs is 10% or more of the area of the cured film.

<Copper corrosiveness>
The resin compositions of the compositions 1-36 were applied onto a copper wafer by a spin coating method and dried at 100 ° C. for 5 minutes using a hot plate to form a resin composition layer having a thickness of about 15 μm. This resin composition layer was heated at a heating rate of 10 ° C./min under a nitrogen atmosphere, reached 250 ° C., and then heated for 3 hours to form a cured film. The copper wafer on which the cured film was formed was put into a constant temperature and humidity layer having a temperature of 85 ° C. and a humidity of 85% for 24 hours, and the corrosion occurrence points on the copper wafer were observed with an optical microscope. The copper corrosiveness was evaluated by observing the percentage of the area where corrosion occurred with respect to the area of the surface of the copper wafer on the side where the cured film was provided.
A: The area of the corrosion-occurring part is less than 5% of the area of the surface of the copper wafer on the side where the cured film is provided. Is 5% or more and less than 10% C: The area of the corrosion occurrence portion is 10% or more and less than 20% with respect to the area of the surface on the side where the cured film of the copper wafer is provided D: The side where the cured film of the copper wafer is provided 20% or more of the area where corrosion occurs with respect to the area of the surface

From the above results, the resin composition of the example was able to form a cured film having good storage stability and excellent moisture resistance. Furthermore, the evaluation of copper corrosiveness was also good.
Further, Examples 1 to 9 and Comparative Examples 1 to 3 are test examples using resin compositions in which only the content of the specific component is different, but the content of the specific component is the total solid content of the resin composition. On the other hand, in Examples 1 to 9 using the compositions 1 to 9 having 1 mass ppb or more and 1000 mass ppm or less, the resin compositions of the compositions 22 to 24 in which the content of the specific component was out of the above range were used. It is shown that the evaluation of storage stability is superior to that of Comparative Examples 1 to 3 by one rank or more. It has also been shown that moisture resistance and copper corrosiveness are equivalent or one rank or higher.
In addition, Example 10 and Comparative Example 4, Example 11 and Comparative Example 5, Example 12 and Comparative Example 6, Example 13 and Comparative Example 7, Example 14 and Comparative Example 8, Example 15 and Comparative Example 9, From the results of Example 16 and Comparative Example 10, Example 17 and Comparative Example 11, Example 18 and Comparative Example 12, Example 19 and Comparative Example 13, Example 20 and Comparative Example 14, and Example 21 and Comparative Example 15. Shows a similar tendency.

Claims (15)

A resin composition containing at least one polymer precursor selected from a polyimide precursor and a polybenzoxazol precursor.
^{_{HNO 2, NO 2 -, HNO}} 3, NO 3 -, H 2 SO 4, HSO 4 -, SO 4 2-, H 2 SO 3, HSO 3 - and SO ₃ ^2-sum said resin composition content of A resin composition having a mass of 1 mass ppb or more and 1000 mass ppm or less with respect to the total solid content of the substance. The resin composition according to claim 1, further comprising at least one selected from a silane coupling agent, a thermobase generator, a radical polymerization initiator and a radically polymerizable compound. The resin composition according to claim 1 or 2, wherein the polymer precursor contains a polyimide precursor. The resin composition according to claim 3, wherein the polyimide precursor has a structural 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 independently represents a hydrogen atom or a monovalent organic group. The resin composition according to claim 4, ^{wherein at least one of R 113} and R ¹¹⁴ in the formula (1) contains a radically polymerizable group. The resin composition according to any one of claims 1 to 5, which is used for developing with a developing solution containing 90% by mass or more of an organic solvent to form a pattern. The resin composition according to any one of claims 1 to 6, which is used for forming a member to be brought into contact with a metal. The resin composition according to any one of claims 1 to 7, which is used for forming an interlayer insulating film for a rewiring layer. A cured film obtained by curing the resin composition according to any one of claims 1 to 8. The cured film according to claim 9, which has a film thickness of 1 to 30 μm. A laminate having two or more cured films according to claim 9 or 10, and having a metal layer between the two cured films. A method for producing a cured film, which comprises a film forming step of applying the resin composition according to any one of claims 1 to 8 to a substrate to form a film. The method for producing a cured film according to claim 12, 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 12 or 13, which comprises a step of heating the film at 80 to 450 ° C. A semiconductor device having the cured film according to claim 9 or 10 or the laminate according to claim 11.