TW202024232A - Resin composition, cured film, laminate, cured film production method, and semiconductor device - Google Patents

Abstract

This resin composition contains at least one polymer precursor selected from polyimide precursors and polybenzoxazole precursors, wherein the total content of HNO2, NO2 -, HNO3, NO3 -, H2SO4, HSO4 -, SO4 2-, H2SO3, HSO3 -, and SO3 2- with respect to the total solid content of the resin composition is not less than 1 mass ppb but not more than 1000 mass ppm. The cured film, the laminate, the cured film production method, and the semiconductor device according to the present invention all use said resin composition.

Description

Resin composition, cured film, laminate, cured film manufacturing method, and semiconductor element

The present invention relates to a resin composition containing at least one polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors. In addition, the present invention relates to a method for manufacturing a cured film, a laminate, and a cured film using a resin composition containing the aforementioned polymer precursor, and a semiconductor element.

Cyclized and hardened resins such as polyimide resins and polybenzoxazole resins have excellent heat resistance and insulation properties, and are therefore suitable for various applications. The use is not particularly limited, but if a semiconductor element for actual mounting is taken as an example, the use as a material or protective film for an insulating film or a sealing material can be cited. (See Non-Patent Documents 1 and 2, etc.). It is also used as a base film or cover layer for flexible substrates. Such polyimide resins and the like generally have low solubility in solvents. Therefore, a method of dissolving a polymer precursor before the cyclization reaction, specifically, a polyimide precursor or a polybenzoxazole precursor in a solvent is often used. Thereby, excellent operability can be achieved, and when each product as described above is manufactured, it can be applied to a substrate or the like in various forms and processed. Then, heating and cyclizing the polymer precursor can form a hardened product. In addition to the high performance of polyimide resins, etc., from the viewpoint of excellent manufacturing adaptability, more and more industrial applications are expected.

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 alkali generator. Patent Document 1 describes that by adopting a specific one as a thermal base generator, the storage stability is good, and the cyclization reaction of a polyimide precursor and the like can be performed at a low temperature. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2015/199219 [Non-Patent Literature]

[Non-Patent Document 1] Science & technology Co., Ltd. "High-functionalization and application technology of polyimide" April 2008 [Non-Patent Document 2] Kakimoto Masaki/Supervisor, CMC Technical Library "Basic and Development of Polyimide Materials" issued in November 2011

With the technique of Patent Document 1, the storage stability of a resin composition containing a polymer precursor such as a polyimide precursor or a polybenzoxazole precursor is improved. On the other hand, in order to cope with the diversified characteristics required for resin compositions containing these polymer precursors in recent years, further research and development are required. For example, with regard to a cured film obtained from a resin composition containing a polymer precursor, it is necessary to further improve the moisture resistance.

Therefore, an object of the present invention is to provide a resin composition, a cured film, a laminate, a method of manufacturing a cured film, and a semiconductor element that can form a cured film with excellent storage stability and excellent moisture resistance.

The inventors of the present invention conducted in-depth research on a resin composition containing at least one polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors, and found that by the structure described below, The above objective is achieved, and the present invention is completed. The present invention provides the following.

式（1）中，A¹ 及A² 分別獨立地表示氧原子或NH，R¹¹¹ 表示2價有機基團，R¹¹⁵ 表示4價有機基團，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價有機基團。 ＜5＞如＜4＞所述之樹脂組成物，其中，式（1）的R¹¹³ 及R¹¹⁴ 中的至少一個包含自由基聚合性基團。 ＜6＞如＜1＞～＜5＞中任一項所述之樹脂組成物，其用於使用包含有機溶劑90質量%以上之顯影液進行顯影而形成圖案。 ＜7＞如＜1＞～＜6＞中任一項所述之樹脂組成物，其用於形成與金屬接觸之構件。 ＜8＞如＜1＞～＜7＞中任一項所述之樹脂組成物，其用於形成再配線層用層間絕緣膜。 ＜9＞一種硬化膜，其藉由硬化＜1＞～＜8＞中任一項所述之樹脂組成物而獲得。 ＜10＞如＜9＞所述之硬化膜，其膜厚為1～30μm。 ＜11＞一種積層體，其具有2層以上＜9＞或＜10＞所述之硬化膜，在2層硬化膜之間具有金屬層。 ＜12＞一種硬化膜的製造方法，其包括： 膜形成步驟，將＜1＞～＜8＞中任一項所述之樹脂組成物適用於基板而形成膜。 ＜13＞如＜12＞所述之硬化膜的製造方法，其具有： 曝光步驟，對膜進行曝光；及 顯影步驟，對膜進行顯影。 ＜14＞如＜12＞或＜13＞所述之硬化膜的製造方法，其包括在80～450℃加熱膜之步驟。 ＜15＞一種半導體元件，其具有＜9＞或＜10＞所述之硬化膜或＜11＞所述之積層體。 [發明效果]<1> A resin composition comprising a polyimide precursor and selected polybenzoxazole precursor㗁azole least one polymer precursor, ^{_{wherein, HNO 2, NO 2 -,}} HNO 3, NO 3 - _{, H 2 SO 4, 4 HSO} -, SO 4 2-, H 2 SO 3, HSO 3 - and SO ₃ ^2- total content of the resin composition with respect to the total solid content of 1 ppb by mass or more and 1000 ppm by mass . <2> The resin composition according to <1>, which further contains at least one selected from the group consisting of a silane coupling agent, a thermal base generator, a radical polymerization initiator, and a radical polymerizable compound. <3> The resin composition according to <1> or <2>, wherein the polymer precursor includes a polyimide precursor. <4> The resin composition according to <3>, wherein the polyimide precursor has a structural unit represented by the following formula (1). [Chemical formula 1]

In formula (1), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or 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 radical polymerizable group. <6> The resin composition according to any one of <1> to <5>, which is used to develop a pattern using a developer containing 90% by mass or more of an organic solvent. <7> The resin composition according to any one of <1> to <6>, which is used to form a member in contact with 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 described in any one of <1> to <8>. <10> The cured film as described in <9>, which has a film thickness of 1 to 30 μm. <11> A laminated body having two or more layers of the cured film described in <9> or <10>, and a metal layer between the two cured films. <12> A method for producing a cured film, comprising: a film forming step of applying the resin composition described in any one of <1> to <8> to a substrate to form a film. <13> The method for producing a cured film as described in <12>, which has: an exposure step to expose the film; and a development step to develop the film. <14> The method for producing a cured film as described in <12> or <13>, which includes the step of heating the film at 80 to 450°C. <15> A semiconductor element having the cured film described in <9> or <10> or the laminated body described in <11>. [Invention Effect]

According to the present invention, it is possible to provide a resin composition, a cured film, a laminate, a method for manufacturing a cured film, and a semiconductor element that have good storage stability and can form a cured film with excellent moisture resistance.

Hereinafter, the content of the present invention will be described. In addition, in this specification, "-" means that the numerical value described before and after it is used as a lower limit and an upper limit.

The description of the constituent elements of the present invention described below may be performed based on representative embodiments of the present invention, but the present invention is not limited to these embodiments. Regarding the label of the group (atomic group) in this specification, the label system that does not describe substituted and unsubstituted includes both those that do not have a substituent and those that have a substituent. For example, "alkyl" includes not only unsubstituted alkyl (unsubstituted alkyl), but also substituted alkyl (substituted alkyl). As long as "exposure" in this specification is not particularly limited, in addition to exposure with light, drawing with particle beams such as electron beams and ion beams is also included in exposure. In addition, as the light used for exposure, active rays or radiations such as extreme ultraviolet rays, extreme ultraviolet rays (EUV light), X-rays, electron beams, etc., represented by the bright-ray spectrum of mercury lamps and excimer lasers are usually cited. In this specification, "(meth)acrylate" means either or both of "acrylate" and "methacrylate", and "(meth)acrylic" means "acrylic" and "methacrylic". Both or either, "(meth)acryloyl" means both or either of "acryloyl" and "methacryloyl". In this specification, the term "step" is not only an independent step, but even if it cannot be clearly distinguished from other steps, if the desired effect of the step can be achieved, it is included in this term. Unless otherwise specified, the physical property values in the present invention are set to values at a temperature of 23° C. and an air pressure of 101325 Pa or less. In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are those measured by gel permeation chromatography (GPC measurement), and are defined as styrene conversion values. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be, for example, HLC-8220 (manufactured by TOSOH CORPORATION), and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super can be used as columns. HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION). In this measurement, unless otherwise specified, THF (tetrahydrofuran) is used as the eluent. In addition, as long as there is no special description, the detection is to use a UV ray (ultraviolet) wavelength 254 nm detector.

[Resin composition] The resin composition of the present invention contains at least one polymer precursor selected from polyimide precursors and polybenzoxazole precursors, and the resin composition is characterized by 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 relative to the total resin composition The solid content is 1 mass ppb or more and 1000 mass ppm or less. Hereinafter, ^{_{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- are also referred to as a specific component.

It is estimated that the content of the above-mentioned specific components in the resin composition of the present invention is 1 mass ppb or more with respect to the total solid content of the resin composition. Therefore, the reaction of the polymer precursor can be suppressed during storage, and as a result, excellent storage stability can be obtained. Sex. In addition, it is estimated that the content of the above-mentioned specific component relative to the total solid content of the resin composition is 1000 mass ppm or less. Therefore, even if the cured film is exposed to a high-humidity environment, it is not easily hydrolyzed. As a result, it can be formed with excellent moisture resistance. The hardened film.

In addition, when the resin composition of the present invention is used to form a member in 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 preferable as a member for forming contact with metal. Examples of members that contact the metal include interlayer insulating films for rewiring layers, insulating tubes, sealing films, substrate materials (base films or cover layers of flexible printed circuit boards, etc.). Interlayer insulating films for rewiring layers are relatively good.

In the resin composition of the present invention, from the viewpoints of the moisture resistance and metal corrosion resistance of the cured film obtained, the total content of the above-mentioned specific components relative to the total solid content of the resin composition is preferably less than 1000 mass ppm, 900 Mass ppm or less is more preferable, 800 mass ppm or less is more preferable, and 500 mass ppm or less is particularly preferable. Although the reason is not clear, the lower limit is relative to the total resin composition due to the ease of improving the storage stability of the resin composition and the moisture resistance of the film obtained by suppressing the reaction of components that promote deterioration. The solid content is preferably 1.0 mass ppb or more, more preferably 1.1 mass ppb or more, more preferably 1.2 mass ppb or more, and particularly preferably 1.5 mass ppb or more.

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- are each Relative to the total solid content of the resin composition, the content of is preferably 1000 ppm by mass or less, more preferably 900 ppm by mass or less, more preferably 800 ppm by mass or less, and particularly preferably 500 ppm by mass or less. Also, the total content of HNO ₂ and NO ₂ ^- relative to the total solid content of the resin composition is preferably 1000 mass ppm or less, more preferably 900 mass ppm or less, more preferably 800 mass ppm or less, and 500 mass ppm or less It is especially good. Also, the total content of HNO ₃ and NO ₃ ^- relative to the total solid content of the resin composition is preferably 1000 mass ppm or less, 900 mass ppm or less is more preferably, 800 mass ppm or less is more preferably, 500 mass ppm or less It is especially good. In addition, the total content of H ₂ SO ₄ , HSO ₄ ^- and SO ₄ ^2- with respect to the total solid content of the resin composition is preferably 1000 mass ppm or less, 900 mass ppm or less is more preferably, and 800 mass ppm or less is further Preferably, 500 ppm by mass or less is particularly preferred. Moreover, the total content of H ₂ SO ₃ , HSO ₃ ^- and SO ₃ ^2- is preferably 1000 mass ppm or less relative to the total solid content of the resin composition, more preferably 900 mass ppm or less, and further 800 mass ppm or less Preferably, 500 ppm by mass or less is particularly preferred.

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 the purification conditions of the resin composition or raw material.

In addition, in this specification, the content of specific components is analyzed by ion chromatography. Specifically, the measurement sample, a non-aqueous organic solvent, and water are mixed, and the amount of a specific component extracted into the aqueous solution by liquid separation or centrifugal separation is measured by ion chromatography, thereby calculating The content of specific ingredients. Further, the resin composition of the present invention, the specific component in the _{^{NO 2 -, NO 3 -,}} HSO 4 -, SO 4 2-, HSO 3 - and SO ₃ ^2- salts may exist in the state. In addition, HNO ₂ , HNO ₃ , H ₂ SO _4, and H ₂ SO ₃ among the above-mentioned specific components may also be ionized and exist as ions. There are no particular limitations on the atoms or atomic groups constituting the salt. 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 to form a pattern using a developer containing 90% by mass or more of an organic solvent.

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

＜Polymer precursors＞ The resin composition of the present invention comprises a polymer precursor selected from polyimide precursors and polybenzoxazole precursors. For the reason that the effect of the present invention is more easily and remarkably obtained, the polymer precursor-based polyimide precursor used in the present invention is preferred.

A¹ 及A² 分別獨立地表示氧原子或NH，R¹¹¹ 表示2價有機基團，R¹¹⁵ 表示4價有機基團，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價有機基團。<<Polyimine precursor>> As the polyimine precursor, it is preferable to include a structural unit represented by the following formula (1). With this structure, a resin composition with more excellent film strength can be obtained. [Chemical formula 2]

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

A ¹ and A ² are each independently an oxygen atom or NH, and an oxygen atom is preferred.

<<<R ¹¹¹ >>>> R ¹¹¹ represents a divalent organic group. Examples of divalent organic groups include linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, heteroaromatic groups or groups containing these combinations, linear aliphatic groups having 2 to 20 carbon atoms A group, a branched aliphatic group with 3 to 20 carbons, a cyclic aliphatic group with 3 to 20 carbons, an aromatic group with 6 to 20 carbons or a combination of these groups are preferred. The aromatic group of 6 to 20 is more preferable. R ¹¹¹ is preferably derived from diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used. Specifically, the diamine includes a linear aliphatic group having 2 to 20 carbons, a branched or cyclic aliphatic group having 3 to 20 carbons, an aromatic group having 6 to 20 carbons, or a group containing these combinations Groups are preferred, and diamines containing aromatic groups with 6 to 20 carbon atoms are more preferred. As an example of an aromatic group, the following aromatic groups can be mentioned.

[Chemical formula 3]

In the formula, A is a single bond or is selected from aliphatic hydrocarbon groups with 1 to 10 carbons which can be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -S(=O) _2- , -NHCO- and the combination of these groups are preferred, single bonds or selected from alkylene groups with 1 to 3 carbons which may be substituted by fluorine atoms, -O-, -C(=O)-, The groups in -S- and -SO ₂ -are more preferably selected from -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -and -C(CH _{3) 2} - group of the divalent group is further preferred.

As the diamine, specifically selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclopentane Cyclohexane or 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis (Aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethyl Cyclohexylmethane and isophorone diamine; m-phenylenediamine and p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl and 3,3'-diaminobiphenyl, 4 ,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4 ,4'-diaminodiphenyl sulfide and 3,3-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide and 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone 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-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy- 4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2 , 2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl) chrysene, bis(4-amino-3-hydroxyphenyl) chrysene, 4,4'-diamino-p-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfonate, bis[ 4-(3-aminophenoxy) phenyl] ash, bis[4-(2-aminophenoxy) phenyl] ash, 1,4-bis(4-aminophenoxy) benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl sulfide, 1,3-bis(4-aminophenoxy) ) Benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diamine Diphenylmethane, 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) sulfide, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfide, 3, 3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2-(3',5'-diaminobenzyloxy) ethyl methacrylate, 2 ,4-Diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p- Phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminopyridine, 2,5-di Aminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzaniline, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluoro Toluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl) Decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2, 2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl] Hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2- Trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-tri Fluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfide, 4,4'-bis(3-amino-5 -Trifluoromethylphenoxy)diphenyl sulfide, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3', 5,5'-Tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5 At least one diamine of 5',6,6'-hexafluorotolidine and 4,4'-diaminotetraphenyl.

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

[Chemical formula 4]

Moreover, as a preferable example, the diamine which has two or more alkylene glycol units in a main chain can also be mentioned. Preferably, it is a diamine that contains two or more of ethylene glycol chains and propylene glycol chains or both in combination in one molecule, and more preferably does not contain an aromatic ring. As specific examples, JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR- 148, JEFFAMINE (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy)ethyl (Oxy)propoxy)propane-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propane-2-amine, etc., but not limited For these. The following shows JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE ( Registered trademark) the structure of EDR-176.

[Chemical formula 5]

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

From the viewpoint of flexibility of the obtained cured film, R ¹¹¹ is preferably represented by -Ar ⁰ -L ⁰ -Ar ⁰ -. Among them, Ar ^{0 is} each independently an aromatic hydrocarbon group (the carbon number is preferably 6-22, 6-18 is more preferred, and 6-10 is particularly preferred), and phenylene is preferred. L ⁰ represents a single bond, an aliphatic hydrocarbon group of 1 to 10 carbons that can be substituted by a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) ₂ -, -NHCO- And a group selected from the combination of these. The meaning of the preferable range is the same as the above-mentioned A.

R⁵⁰ ～R⁵⁷ 分別獨立地為氫原子、氟原子或1價有機基團，R⁵⁰ ～R⁵⁷ 中的至少一個為氟原子、甲基、氟甲基、二氟甲基或三氟甲基。 作為R⁵⁰ ～R⁵⁷ 的1價有機基團，可舉出碳數1～10（較佳為碳數1～6）的未經取代的烷基、碳數1～10（較佳為碳數1～6）的氟化烷基等。 [化學式7]

R⁵⁸ 及R⁵⁹ 分別獨立地為氟原子、氟甲基、二氟甲基或三氟甲基。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, from the viewpoint of i-ray transmittance and easy availability, the divalent organic group represented by formula (61) is more preferable. [Chemical formula 6]

R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group . ^Examples of the monovalent organic groups of R ⁵⁰ to R ⁵⁷ include unsubstituted alkyl groups having 1 to 10 carbons (preferably 1 to 6 carbons), and 1 to 10 carbons (preferably carbons 1～6) Fluorinated alkyl groups, etc. [Chemical formula 7]

R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, fluoromethyl, difluoromethyl, or trifluoromethyl.

As the diamine compound imparted to the structure of the formula (51) or (61), dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4, 4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. One of these may be used, or two or more of them may be used in combination.

R¹¹² 的含義與A相同，較佳範圍亦相同。<<< R ¹¹⁵ >>> formula R ¹¹⁵ (1) represents a tetravalent organic group. As the tetravalent organic group, a group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable. [Chemical formula 8]

R ^{112 has} the same meaning as A, and the preferred range is also the same.

R¹¹⁵ 表示4價有機基團。R¹¹⁵ 的含義與式（1）的R¹¹⁵ 相同。Regarding the tetravalent organic group represented by R ¹¹⁵ in the formula (1), specifically, the tetracarboxylic acid residue remaining after removing the acid dianhydride group from the tetracarboxylic dianhydride and the like can be mentioned. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. Tetracarboxylic dianhydride is preferably a compound represented by the following formula (7). [Chemical formula 9]

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

Specific examples of tetracarboxylic dianhydride include those selected from pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3 ',4,4'-Diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-Diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-Diphenylmethyl Ketonetetracarboxylic dianhydride, 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3 ,3',4'-Biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxodiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2 ,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane- 3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3, 4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10 -Phenanthrene tetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1, At least one of 2,3,4-benzenetetracarboxylic dianhydride and alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

In addition, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below can also be cited as preferred examples. [Chemical formula 10]

<<<R ¹¹³ and R ¹¹⁴ >>> In the formula (1), R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group. It is preferred that at least one of R ¹¹³ and R ¹¹⁴ contains a radical polymerizable group, and it is more preferred that both of them contain a radical polymerizable group. The radical polymerizable group is a group capable of undergoing a crosslinking reaction by the action of a radical, and a preferable example includes 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, a group represented by the following formula (III), and the like.

[Chemical formula 11]

In the formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and a methyl group is more preferred. In formula (III), R ²⁰¹ represents an alkylene having 2 to 12 carbons, -CH ₂ CH(OH)CH ₂ -or a (poly)oxyalkylene having 4 to 30 carbons (as an alkylene, carbon The number is preferably from 1 to 12, more preferably from 1 to 6, and particularly preferably from 1 to 3; the repeating number is preferably from 1 to 12, more preferably from 1 to 6 and particularly preferably from 1 to 3). In addition, (poly)alkylene oxide means alkylene oxide or polyalkylene oxide. Preferred examples of R ²⁰¹ include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, Hexamethylene, octamethylene, dodecamethylene, -CH ₂ CH(OH)CH ₂ -, ethylene, propylene, trimethylene, -CH ₂ CH(OH)CH ₂ -are Better. 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, the monovalent organic group of R ¹¹³ or R ¹¹⁴ may have 1, 2 or 3 acid groups, preferably one acid group. Aliphatic group, aromatic group and aralkyl group etc. Specifically, an aromatic group having 6 to 20 carbon atoms having an acid group, and an aralkyl group having 7 to 25 carbon atoms having an acid group can be mentioned. More specifically, a phenyl group having an acid group and a benzyl group having an acid group can be mentioned. The acid group is more 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 developer can be preferably used. From the viewpoint of solubility to an aqueous developer, R ¹¹³ or R ¹¹⁴ is more preferably a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl, and 4-hydroxybenzyl.

From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. As the monovalent organic group, it is preferable to include a linear or branched alkyl group, a cyclic alkyl group, and an aromatic group, and an alkyl group substituted with an aromatic group is more preferable. The number of carbon atoms in the alkyl group is preferably 1 to 30 (in the case of a cyclic ring, 3 or more). The alkyl group may be any of linear, branched, and cyclic. Examples of straight-chain or branched alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl Alkyl, octadecyl, isopropyl, isobutyl, second butyl, tertiary butyl, 1-ethylpentyl and 2-ethylhexyl. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of monocyclic cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic cyclic alkyl groups include adamantyl, norbornyl, camphenyl, camphenyl (camphenyl), decahydronaphthyl, tricyclodecyl, tetracyclodecyl, and camphenyl. Diacyl, dicyclohexyl and pinenyl (pinenyl). In addition, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described below is preferable.

The aromatic group is specifically a substituted or unsubstituted aromatic hydrocarbon group (the cyclic structure constituting the group includes a benzene ring, a naphthalene ring, a biphenyl ring, a sulphur ring, a pentene ring, Indene ring, azulene ring, heptene ring, indenene ring, perylene ring, fused pentaphenyl ring, acenaphthylene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring, tetraphenyl ring, terylene ring, etc.) or substituted Or unsubstituted aromatic heterocyclic group (as the cyclic structure of the constituent group, pyridine ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, azole ring, thiazole ring, pyridine ring, pyridine ring 𠯤 ring, pyrimidine ring, da 𠯤 ring, indole ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinoline ring, quinoline ring, pyrimidine ring, naphthyridine Ring, quinoline ring, quinazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthracene ring, chromene ring, Kouyamaguchi ring, phenanthrene ring , Phenothidium ring or brown 𠯤 ring).

In addition, it is also preferable that the polyimide precursor has a fluorine atom in the structural unit. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less. The upper limit is not particularly limited, but is actually 50% by mass or less.

Furthermore, for the purpose of improving the adhesion to the substrate, the aliphatic group having a siloxane structure and the structural unit represented by formula (1) can be copolymerized. Specifically, examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

A¹¹ 及A¹² 表示氧原子或NH，R¹¹¹ 及R¹¹² 分別獨立地表示2價有機基團，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價有機基團，R¹¹³ 及R¹¹⁴ 中的至少一者係包含自由基聚合性基團之基團為較佳，自由基聚合性基團為更佳。The structural unit represented by formula (1) is preferably a structural unit represented by formula (1-A) or (1-B). [Chemical formula 12]

A ¹¹ and A ¹² represent an oxygen atom or NH, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, in R ¹¹³ and R ¹¹⁴ At least one of is preferably a group containing a radical polymerizable group, and more preferably a radical polymerizable group.

The meanings of the preferred ranges of A ¹¹ , A ¹² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ are the same as the preferred ranges of A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (1). In the preferred range of R is the same R ¹¹² meaning as in formula (5) ^112, wherein the oxygen atoms. In the formula, the bonding position of the carbonyl group on the benzene ring is preferably 4, 5, 3', 4'in the formula (1-A). In formula (1-B), 1, 2, 4, and 5 are preferred.

In the polyimide precursor, the constituent unit represented by formula (1) may be one type or two or more types. Furthermore, it may contain structural isomers of the structural unit represented by formula (1). Moreover, in addition to the structural unit of the above-mentioned formula (1), the polyimide precursor may contain other kinds of structural units.

As an embodiment of the polyimide precursor in the present invention, 50 mol% or more of the total structural unit can be exemplified, further 70 mol% or more, especially 90 mol% or more, represented by formula (1) The polyimide precursor of the constituent unit. As the upper limit, it is actually 100 mol% or less.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and still more preferably 10,000 to 50,000. In addition, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and still more preferably 4,000 to 25,000. The molecular weight dispersion of the polyimide precursor is preferably 1.5-3.5, more preferably 2-3.

The polyimide precursor can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative using a halogenating agent, and then reacting it with a diamine. In the production method of the polyimide precursor, it is preferable to use an organic solvent when performing the reaction. The organic solvent may be one type or two or more types. The organic solvent can be appropriately set according to the raw material, and pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone can be exemplified.

When manufacturing the polyimide precursor, it is preferable to include a step of separating out solids. Specifically, the polyimide precursor in the reaction liquid is precipitated in water, and the polyimide precursor such as tetrahydrofuran is dissolved in a soluble solvent, thereby enabling solid precipitation.

R¹²¹ 表示2價有機基團，R¹²² 表示4價有機基團，R¹²³ 及R¹²⁴ 分別獨立地表示氫原子或1價有機基團。<<Polybenzoxazole precursor>> It is preferable that the polybenzoxazole precursor contains a structural unit represented by the following formula (2). [Chemical formula 13]

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

R ¹²¹ represents a divalent organic group. As a divalent organic group, aliphatic group (carbon number 1-24 is preferred, 1-12 is more preferred, 1-6 is particularly preferred) and aromatic group (carbon number 6-22 is preferred, 6 ～14 is more preferable, 6-12 are particularly preferable) at least one group is preferable. Examples of the aromatic group constituting R ¹²¹ include R ¹¹¹ in the above formula (1). As the aforementioned aliphatic group, a straight-chain aliphatic group is preferred. Preferably, R ^{121 is} derived from 4,4'-oxobenzyl 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 preferred range is also the same. R ¹²² is preferably derived from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane. R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group, and have the same meaning as R ¹¹³ and R ¹¹⁴ in the above formula (1), and the preferred ranges are also the same.

In addition to the structural unit of the above-mentioned formula (2), the polybenzoxazole precursor may contain other kinds of structural units. From the viewpoint of being able to suppress the occurrence of warpage of the cured film accompanying ring closure, the polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of structural unit.

Z具有a結構和b結構，R^1s 為氫原子或碳數1～10的烴基（較佳為碳數1～6，更佳為碳數1～3），R^2s 為碳數1～10的烴基（較佳為碳數1～6，更佳為碳數1～3），R^3s 、R^4s 、R^5s 、R^6s 中的至少一個為芳香族基（較佳為碳數6～22，更佳為碳數6～18，特佳為碳數6～10），剩餘部分為氫原子或碳數1～30（較佳為碳數1～18，更佳為碳數1～12，特佳為碳數1～6）的有機基團，且可以分別相同亦可以不同。a結構及b結構的聚合可以為嵌段聚合或隨機聚合。Z部分中，較佳為a結構為5～95莫耳%，b結構為95～5莫耳%，a+b為100莫耳%。[Chemical formula 14]

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

In formula (SL), preferred Z includes those in which R ^5s and R ^6s in the structure b are phenyl groups. Furthermore, the molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. The molecular weight can be determined by the gel permeation chromatography method generally used. By setting the above-mentioned molecular weight in the above-mentioned range, it is possible to reduce the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure, and to suppress the warpage and improve the solubility.

When the diamine residue represented by the formula (SL) is included as another type of structural unit, the precursor further includes the tetracarboxylic acid remaining after removing the acid dianhydride group from the tetracarboxylic dianhydride from the viewpoint of improving alkali solubility The residue is preferably used as a structural unit. As an example of these tetracarboxylic acid residues, the example of R ¹¹⁵ in Formula (1) is mentioned.

The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and still more preferably 10,000 to 50,000. In addition, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and still more preferably 4,000 to 25,000. The molecular weight dispersion of the polybenzoxazole precursor is preferably 1.5 to 3.5, and more preferably 2 to 3.

The content of the polymer precursor in the resin composition of the present invention relative to the total solid content of the resin composition is preferably 20% by mass or more, more preferably 30% by mass or more, more preferably 40% by mass or more, The mass% or more is more preferable, 60 mass% or more is more preferable, and 70 mass% or more is more preferable. In addition, the content of the polymer precursor in the resin composition of the present invention is preferably 99.5% by mass or less relative to the total solid content of the resin composition, more preferably 99% by mass or less, and more preferably 98% by mass or less , 95% by mass or less is more preferable. The resin composition of the present invention may include only one type of polymer precursor, or may include two or more types. When two or more types are contained, the total amount is preferably in the above range.

<Thermal base generator> The resin composition of the present invention contains a thermal base generator. The type of the thermal base generator is not particularly limited, and it contains heat containing at least one selected from the group consisting of acidic compounds that generate bases when heated to 40°C or higher, and ammonium salts with pKa1 of 0-4 and ammonium cations. Alkali generators are preferred. 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 these compounds, the cyclization reaction of polymer precursors and the like can be carried out at low temperatures. In addition, the thermal alkali generator does not generate alkali if it is not heated. Therefore, 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 thermal base generator preferably contains at least one selected from the group consisting of an acidic compound (A1) that generates a base when heated to 40°C or higher, and an ammonium salt (A2) of an anion having a pKa1 of 0 to 4 and an ammonium cation (A2). The acidic compound (A1) and the ammonium salt (A2) generate alkali when heated. Therefore, the alkali generated from these compounds can promote the cyclization reaction of the polymer precursor, and the polymer precursor can be carried out at low temperature的cyclization. In addition, in this specification, the acidic compound refers to the following compound: Collect 1 g of the compound in a container, add 50 mL of a mixture of ion-exchanged water and tetrahydrofuran (mass ratio of water/tetrahydrofuran = 1/4), and stir at room temperature for 1 hour , The solution thus obtained is used for compounds with a value less than 7 measured at 20°C with a pH (power of hydrogen: acidity) meter.

The alkali generation temperature of the thermal alkali generator used in the present invention is preferably 40°C or higher, and more preferably 120 to 200°C. The upper limit of the alkali 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 alkali generation temperature is preferably 130°C or higher, and more preferably 135°C or higher. The alkali production temperature can be measured as follows: For example, using differential scanning calorimetry, heat the compound in a pressure capsule at 5°C/min to 250°C, read the peak temperature of the heat generating peak with the lowest temperature, and use the peak temperature as the alkali production temperature.

Alkaline secondary amines or tertiary amines produced by hot alkali generators are preferred, and tertiary amines are more preferred. The tertiary amine is highly basic, so it can make the cyclization temperature of the polymer precursor lower. In addition, the boiling point of the alkali produced by the thermal alkali generator is preferably 80°C or higher, more preferably 100°C or higher, and more preferably 140°C or higher. Furthermore, the molecular weight of the base produced is preferably 80-2000. The lower limit is more preferably 100 or more. The upper limit is more preferably 500 or less. In addition, the value of the molecular weight is the theoretical value obtained from the structural formula.

In this embodiment, the acidic compound (A1) preferably contains one or more selected from ammonium salts and compounds represented by formula (101) or (102) described below.

In this embodiment, the above-mentioned ammonium salt (A2)-based acidic compound is preferable. In addition, the above-mentioned 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 may be a compound other than if heated to 40°C or higher (preferably 120 to 200°C). ～200℃) will produce compounds other than base acidic compounds.

式（101）及式（102）中，R¹ ～R⁶ 分別獨立地表示氫原子或烴基，R⁷ 表示烴基。式（101）及式（102）中的R¹ 與R² 、R³ 與R⁴ 、R⁵ 與R⁶ 、R⁵ 與R⁷ 可以分別鍵結而形成環。In this embodiment, the ammonium salt means a salt of an ammonium cation and an anion represented by the following formula (101) or (102). The anion may be bonded to any part of the ammonium cation via a covalent bond, and may also be present outside the molecule of the ammonium cation, but it is preferably present outside the molecule of the ammonium cation. In addition, the presence of an anion outside the molecule of the ammonium cation means that the ammonium cation and the anion are not bonded by a covalent bond. Hereinafter, the anion outside the molecule of the cation part is also referred to as a counter anion. Formula (101) Formula (102) [Chemical formula 15]

In formula (101) and formula (102), R ¹ to R ⁶ each 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} formula (101) and formula (102) may be respectively bonded to form a ring.

The ammonium cation is preferably represented by any one of the following formulas (Y1-1) to (Y1-5). [Chemical formula 16]

In formulas (Y1-1) to (Y1-5), R ¹⁰¹ represents an n-valent organic group, and R ¹ and R ^{7 have} the same meanings as in 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 0-5.

In this embodiment, the ammonium salt preferably has an anion having a pKa1 of 0 to 4 and an ammonium cation. The upper limit of the pKa1 of the anion is more preferably 3.5 or less, and more preferably 3.2 or less. The lower limit is preferably 0.5 or more, and more preferably 1.0 or more. If 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. If pKa1 is 4 or less, the stability of the thermal alkali generator is good, and the generation of alkali without heating can be suppressed, and the stability of the resin composition is good. If pKa1 is 0 or more, the generated alkali is not easily neutralized, and the cyclization efficiency of the polymer precursor is good. The type of anion is preferably one selected from the group consisting of carboxylate anion, phenol anion, and phosphate anion, and carboxylate anion is more preferred from the viewpoint of compatibility of salt stability and thermal decomposition. That is, a salt of an ammonium cation and a carboxylate anion is more preferable. The carboxylate anion is preferably an anion of a divalent or more carboxylic acid having two or more carboxyl groups, and more preferably an anion of a divalent carboxylic acid. According to this aspect, it can be used as a thermal alkali generator that can further improve the stability, curability, and developability of the resin composition. In particular, by using an anion of a divalent carboxylic acid, the stability, curability, and developability of the resin composition can be further improved. In this embodiment, the anion of a carboxylic acid whose pKa1 of the carboxylate anion system is 4 or less is preferable. It is more preferable that pKa1 is 3.5 or less, and it is still more preferable that it is 3.2 or less. According to this aspect, the stability of the resin composition can be further improved. Among them, pKa1 represents the logarithm of the inverse of the dissociation constant of the first proton of the acid, which can be found in Determination of Organic Structures by Physical Methods (author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; editor: Braude , EA, Nachod, FC; Academic Press, New York, 1955) or Data for Biochemical Research (Author: Dawson, RMC et al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, the value calculated by the structural formula using software using ACD/pKa (manufactured by ACD/Labs) is used.

式（X1）中，EWG表示拉電子基團。The carboxylate anion is preferably represented by the following formula (X1). [Chemical formula 17]

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

In this embodiment, the electron withdrawing group refers to the one whose Hammett substituent constant σm represents a positive value. Among them, σm is described in detail in Yufu Tono, Journal of Synthetic Organic Chemistry, Japan Volume 23, No. 8 (1965) p.631-642. In addition, the electron withdrawing group in this embodiment is not limited to the substituents described in the above-mentioned documents. Examples of substituents in which σm represents a positive value include CF ₃ group (σm=0.43), CF ₃ CO group (σm=0.63), HC≡C group (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) Wait. In addition, 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 分別獨立地表示氫原子、烷基、烯基、芳基、羥基或羧基，Ar表示芳香族基。EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6). [Chemical formula 18]

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

式（XA）中，L¹⁰ 表示選自單鍵或伸烷基、伸烯基、芳香族基、-NR^X -及該等的組合中的2價的連結基，R^X 表示氫原子、烷基、烯基或芳基。In this embodiment, the carboxylate anion is preferably represented by the following formula (XA). Formula (XA) [Chemical Formula 19]

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

Specific examples of the carboxylate anion include maleate anion, phthalate anion, N-phenylimino diacetate anion, and oxalate anion. These can be used preferably.

[化學式21]

As specific examples of the thermal base generator, the following compounds can be given. [Chemical formula 20]

[Chemical formula 21]

[Chemical formula 22]

The content of the thermal base generator is preferably 0.1 to 50% by mass relative 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 more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and more preferably 20% by mass or less. One kind or two or more kinds of thermal base generators can be used. When two or more are used, the total amount is preferably in the above range.

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

＜＜Light radical polymerization initiator＞＞ The radical photopolymerization initiator is not particularly limited, and it can be appropriately selected from known radical photopolymerization initiators. For example, a radical photopolymerization initiator having photosensitivity to light from the ultraviolet region to the visible region is preferable. In addition, it can be an active agent that has some effect on the sensitizer excited by light and generates active free radicals. The photoradical polymerization initiator preferably contains at least one compound having at least about 50 molar absorption coefficient in the range of about 300 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of the compound can be measured by a known method. For example, it is better to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) and use an ethyl acetate solvent at a concentration of 0.01 g/L.

As the photoradical polymerization initiator, any known compound can be used arbitrarily. For example, halogenated hydrocarbon derivatives (e.g., compounds having a triazole skeleton, compounds having a diazole skeleton, compounds having a trihalomethyl group, etc.), phosphonium phosphine compounds such as oxyphosphine oxide, hexaaryl bis Oxime compounds such as imidazole and oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds, Metallocene compounds, organoboron compounds, iron arene complexes, etc. For details of these, refer to the descriptions in paragraphs 0165 to 0182 of JP 2016-027357 A, 0138 to 0151 of International Publication No. 2015/199219, which are incorporated into this specification.

As the ketone compound, for example, the compound described in paragraph 0087 of JP 2015-087611 A can be exemplified, and this content is incorporated in this specification. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

As the photoradical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in JP-A No. 10-291969 and the phosphine 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 Corporation) can be used. As the aminoacetophenone-based initiator, IRGACURE 907, IRGACURE 369, and IRGACURE 379 (manufactured by BASF Corporation), which are commercially available products, can be used. As the aminoacetophenone-based initiator, it is also possible to use compounds described in Japanese Patent Application Laid-Open No. 2009-191179 that have a maximum absorption wavelength that matches a light source with wavelengths such as 365 nm or 405 nm. Examples of the phosphine-based initiator include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide. In addition, IRGACURE-819 or IRGACURE-TPO (manufactured by BASF Corporation), which are commercially available products, can be used. As a metallocene compound, IRGACURE-784 (made by BASF Corporation) etc. are illustrated.

市售品中，還可較佳地使用IRGACURE OXE 01、IRGACURE OXE 02、IRGACURE OXE 03、IRGACURE OXE 04（以上為BASF公司製）、ADEKA OPTOMER N-1919（ADEKA CORPORATION製、日本特開2012-014052號公報中所記載之光自由基聚合起始劑2）。又，能夠使用TR-PBG-304（Changzhou Tronly New Electronic Materials CO.,LTD.製）、ADEKAARKLS NCI-831及ADEKAARKLS NCI-930（ADEKA CORPORATION製）。又，能夠使用DFI-091（DAITO CHEMIX Co.,Ltd.製）。 進而，還能夠使用具有氟原子之肟化合物。作為該等肟化合物的具體例，可舉出日本特開2010-262028號公報中記載之化合物、日本特表2014-500852號公報的0345段中記載之化合物24、36～40、日本特開2013-164471號公報的0101段中記載之化合物（C-3）等。 作為最佳之肟化合物，可舉出日本特開2007-269779號公報中所示出之具有特定取代基之肟化合物或日本特開2009-191061號公報中所示出之具有硫芳基之肟化合物等。As the photoradical polymerization initiator, an oxime compound is more preferable. By using oxime compounds, exposure latitude can be further effectively improved. Among the oxime compounds, the exposure latitude (exposure margin) is relatively wide, and it also functions as a photohardening accelerator, so it is particularly preferred. As specific examples of the oxime compound, the compound described in JP 2001-233842 A, the compound described in JP 2000-080068 A, and the compound described in JP 2006-342166 can be used . As preferred oxime compounds, for example, compounds having the following structures, 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-Propanoyloxyiminobutan-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1- Ketone, 2-benzyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one and 2-ethoxycarbonyl Oxyimino-1-phenylpropan-1-one, etc. In the resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as a photoradical polymerization initiator. The oxime-based photopolymerization initiator has a linking group >C=NOC(=O)- in the molecule. [Chemical formula 23]

Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are made by BASF), ADEKA OPTOMER N-1919 (made by ADEKA CORPORATION, Japanese Patent Publication 2012-014052 The photo-radical polymerization initiator described in No. 2). In addition, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKAARKLS NCI-831, and ADEKAARKLS NCI-930 (manufactured by ADEKA CORPORATION) can be used. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can be used. Furthermore, an oxime compound having a fluorine atom can also be used. Specific examples of these oxime compounds include the compounds described in JP 2010-262028 A, the compounds 24, 36 to 40 described in paragraph 0345 of JP 2014-500852 A, and JP 2013 -The compound (C-3) described in paragraph 0101 of Bulletin No. 164471. As the best oxime compound, oxime compounds having specific substituents shown in Japanese Patent Application Publication No. 2007-269779 or oximes having sulfur aryl groups shown in Japanese Patent Application Publication No. 2009-191061 can be cited Compound etc.

式（I）中，R^I00 係碳數1～20的烷基、藉由1個以上的氧原子而中斷之碳數2～20的烷基、碳數1～12的烷氧基、苯基、由碳數1～20的烷基、碳數1～12的烷氧基、鹵素原子、環戊基、環己基、碳數2～12的烯基藉由因1個以上的氧原子而中斷之碳數2～18的烷基及碳數1～4的烷基中的至少一個取代之苯基或聯苯基，R^I01 係由式（II）表示之基團，或者為與R^I00 相同的基團，R^I02 ～R^I04 各自獨立地為碳數1～12的烷基、碳數1～12的烷氧基或鹵素。 [化學式25]

式中，R^I05 ～R^I07 與上述式（I）的R^I02 ～R^I04 相同。From the viewpoint of exposure sensitivity, the photo-radical polymerization initiator is selected from the group consisting of trihalomethyl trimethyl ketal compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, and ketone compounds. Phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl -Benzene-iron complexes and their salts, halomethyl oxadiazole compounds, and 3-aryl substituted coumarin compounds. More preferable photo-radical polymerization initiators are trihalomethyl tri-ketone compounds, α-amino ketone compounds, phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and onium Salt compounds, benzophenone compounds, acetophenone compounds, selected from the group consisting of trihalomethyltriketone compounds, α-amino ketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds At least one compound among them is more preferable, and it is more preferable to use a metallocene compound or an oxime compound, and an oxime compound is still more preferable. In addition, the photoradical polymerization initiator can also use benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), etc. ,N'-Tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-porolinylphenyl)-butanone- Aromatic ketones such as 1,2-methyl-1-[4-(methylthio)phenyl]-2-endolinyl-acetone-1, alkylanthraquinones, etc. are condensed with aromatic rings Quinones, benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkylbenzoin, and benzyl derivatives such as benzyl dimethyl ketal. In addition, a compound represented by the following formula (I) can also be used. [Chemical formula 24]

In formula (I), R ^I00 is an alkyl group having 1 to 20 carbons, an alkyl group having 2 to 20 carbons interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbons, and a phenyl group. , The alkyl group with 1 to 20 carbons, alkoxy with 1 to 12 carbons, halogen atoms, cyclopentyl, cyclohexyl, and alkenyl with 2 to 12 carbons are interrupted by more than one oxygen atom A phenyl or biphenyl substituted with at least one of an alkyl group having 2 to 18 carbons and an alkyl group having 1 to 4 carbons, R ^I01 is a group represented by formula (II), or is the same as R ^I00 The groups of R ^I02 to R ^I04 are each independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or halogen. [Chemical formula 25]

In the formula, R ^I05 to R ^I07 are the same as R ^I02 to R ^{I04 in the} above formula (I).

In addition, the photoradical polymerization initiator can also use the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469.

When a photoradical polymerization initiator is included, its content is preferably 0.1-30% by mass relative to the total solid content of the resin composition of the present invention, more preferably 0.1-20% by mass, and still more preferably 0.5-15 The mass% is more preferably 1.0 to 10 mass %. The radical photopolymerization initiator may contain only one kind or two or more kinds. When two or more types of radical photopolymerization initiators are contained, the total amount is preferably in the above range.

＜＜Thermal radical polymerization initiator＞＞ The thermal radical polymerization initiator is a compound that generates free radicals by thermal energy and initiates or promotes the polymerization reaction of the polymerizable compound. By adding a thermal radical polymerization initiator, the cyclization of the polymer precursor can be performed, and the polymerization reaction of the polymer precursor can be performed, so that a higher degree of heat resistance can be achieved. As the thermal radical polymerization initiator, specifically, the compounds described in paragraphs 0074 to 0118 of JP 2008-063554 A can be cited.

When a thermal radical polymerization initiator is contained, its content is preferably 0.1-30% by mass relative to the total solid content of the resin composition of the present invention, more preferably 0.1-20% by mass, and still more preferably 5-15 quality%. The thermal radical polymerization initiator may contain only one type or two or more types. When two or more types of thermal radical polymerization initiators are contained, the total amount is preferably in the above range.

＜Polymerizable compound＞ ＜＜Free radical polymerizable compound＞＞ The resin composition of the present invention preferably contains a polymerizable compound. As the polymerizable compound, a radical polymerizable compound can be used. The radical polymerizable compound is a compound having a radical polymerizable group. Examples of radical polymerizable groups include groups having ethylenically unsaturated bonds such as vinyl groups, allyl groups, vinyl phenyl groups, and (meth)acrylic groups. The radical polymerizable group is preferably a (meth)acryloyl group.

The number of radical polymerizable groups possessed by the radical polymerizable compound may be one or two or more. The radical polymerizable compound preferably has two or more radical polymerizable groups, and has 3 More than one is better. 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 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 more radical polymerizable compound containing two or more polymerizable groups, and at least one trifunctional or more radical polymerizable compound The compound is more preferable. In addition, it may be a mixture of a bifunctional radical polymerizable compound and a trifunctional or more radical polymerizable compound. In addition, the number of functional groups of the radically polymerizable compound refers to the number of radically polymerizable groups in one molecule.

Specific examples of radically polymerizable compounds include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides , Preferably are esters of unsaturated carboxylic acids and polyol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. In addition, addition reactants of unsaturated carboxylic acid esters or amides having affinity substituents such as hydroxyl groups, amino groups, sulfhydryl groups, and monofunctional or polyfunctional isocyanates or epoxy groups can also be preferably used, Dehydration condensation reaction product with monofunctional or polyfunctional carboxylic acid, etc. In addition, addition reactants of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols, and halogen groups or toluene Substitution reactants of unsaturated carboxylic acid esters or amides having detachable substituents such as sulfonyloxy groups and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. As another example, instead of the above-mentioned unsaturated carboxylic acid, a group of compounds substituted with unsaturated phosphonic acid, vinyl benzene derivatives such as styrene, vinyl ether, allyl ether, and the like can be used. As a specific example, reference can be made to the description in paragraphs 0113 to 0122 of JP 2016-027357 A, and these contents are incorporated in this specification.

In addition, a radically polymerizable compound having a boiling point of 100°C or higher under normal pressure is also preferable. Examples thereof include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentylerythritol three (Meth) acrylate, neopentyl erythritol tetra (meth) acrylate, dine pentaerythritol penta (meth) acrylate, dine pentaerythritol hexa (meth) acrylate, hexanediol (meth) Base) acrylate, trimethylolpropane tris(acryloxypropyl) ether, tris(acryloxyethyl) isocyanurate, glycerin or trimethylolethane, etc. in multifunctional alcohol Compounds in which ethylene oxide or propylene oxide is added and then (meth)acrylated, Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, Japanese Patent Application Publication No. 51-037193 The (meth)acrylate urethanes described in JP-A 48-064183, JP-Sho 49-043191, and JP-A 52-030490 are polyester acrylates Types are polyfunctional acrylates or methacrylates such as epoxy acrylates, which are reaction products of epoxy resins and (meth)acrylic acid, and mixtures thereof. In addition, the compounds described in paragraphs 0254 to 0257 of JP 2008-292970 A are also preferable. Moreover, the polyfunctional (meth)acrylate etc. which are obtained by reacting the compound which has a cyclic ether group and ethylenic unsaturated bond, such as a polyfunctional carboxylic acid, glycidyl (meth)acrylate, etc. are mentioned. In addition, as preferred radical polymerizable compounds other than those described above, it is also possible to use those described in Japanese Patent Laid-Open No. 2010-160418, Japanese Patent Laid-Open No. 2010-129825, Japanese Patent No. 4364216, etc. A compound or cardo resin that has a ring and has two or more ethylenically unsaturated bond-containing groups. Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, Japanese Patent Publication No. 01-040336, and Japanese Patent Application Publication No. 02 Vinylphosphonic acid-based compounds and the like described in Bulletin -025493. In addition, the perfluoroalkyl group-containing compounds described in JP 61-022048 A can also be used. Furthermore, it is also possible to use those introduced as photocurable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pages 300 to 308 (1984).

In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese Patent Laid-Open No. 2015-034964 and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used. These contents are incorporated herein. In the manual.

In addition, the following compounds described as formula (1) and formula (2) in Japanese Patent Application Laid-Open No. 10-062986 and their specific examples can also be used as radically polymerizable compounds, which are added to a polyfunctional alcohol It is a compound formed by (meth)acrylate esterification after ethylene oxide or propylene oxide.

Furthermore, the compounds described in paragraphs 0104 to 0131 of JP 2015-187211 A can also be used as other radically polymerizable compounds, and these contents are incorporated in this specification.

As a radically polymerizable compound, dineopentaerythritol triacrylate (as a commercially available product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), and dineopentaerythritol tetraacrylate (as a commercially available product is KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd., dineopentyl pentaerythritol penta(meth)acrylate (as a commercially available product is KAYARAD D -310; manufactured by Nippon Kayaku Co., Ltd.), dineopentylerythritol hexa(meth)acrylate (as a commercial product is KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; Shin-Nakamura Chemical Co., Ltd.) and the structure in which these (meth)acrylic groups are bonded via ethylene glycol residues or propylene glycol residues are preferred. These oligomer types can also be used.

As commercially available products of radically polymerizable compounds, for example, SR-494, which is a 4-functional acrylate having 4 ethoxyl chains, manufactured by Sartomer Company, Inc., and 2 as 2 of 4 ethyleneoxy chains are mentioned. Functional methyl acrylate of SR-209, 231, 239 manufactured by Sartomer Company, Inc, DPCA-60 manufactured by Nippon Kayaku Co., Ltd. as a 6-functional acrylate with 6 pentoxyl chains, as having 3 Iso-butoxy chain trifunctional acrylate TPA-330, urethane oligomer UAS-10, UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD.), NK ester M-40G, NK Ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA- 306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.

As a radically polymerizable compound, as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765 Urethane acrylates, Japanese Japanese Patent Publication No. 58-049860, Japanese Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, Japanese Patent Publication No. 62-039418, which have cyclic Urethane compounds with oxyethane-based skeletons are also preferred. Furthermore, as the radically polymerizable compound, those described in JP-A 63-277653, JP-A 63-260909, and JP-A 01-105238 have an amino group in the molecule. Structure or sulfide structure compound.

The radical polymerizable compound may be a radical polymerizable compound having an acid group such as a carboxyl group and a phosphoric acid group. Among the radically polymerizable compounds having an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferred. The unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to have an acid group. A radical polymerizable compound is more preferable. Particularly preferably, the unreacted hydroxyl group of the aliphatic polyhydroxy compound reacts with a non-aromatic carboxylic anhydride to have an acid group. Among the radically polymerizable compounds, the aliphatic polyhydroxy compound is neopentylerythritol and/or dineopentaerythritol The compound. As a commercially available product, for example, M-510, M-520, etc. are mentioned as polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., Ltd.. The preferred acid value of the radically polymerizable compound having an acid group is 0.1-40 mgKOH/g, and particularly preferably 5-30 mgKOH/g. As long as the acid value of the radically polymerizable compound is within the above-mentioned range, it has excellent manufacturing and handling properties, and furthermore has excellent developability. In addition, the polymerizability is also good.

From the viewpoint of suppressing the warpage accompanying the control of the modulus of elasticity of the cured film, the resin composition of the present invention can preferably use a monofunctional radical polymerizable compound as the radical polymerizable compound. As the monofunctional radical polymerizable compound, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxy Ethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, etc. (meth)acrylic acid Derivatives, N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, allyl glycidyl ether, diallyl phthalate, triallyl trimellitate Allyl compounds such as esters. As the monofunctional radical polymerizable compound, in order to suppress volatilization before exposure, a compound having a boiling point of 100°C or higher under normal pressure is also preferable.

＜＜Polymerizable compounds other than the above radically polymerizable compounds＞＞ The resin composition of the present invention can also contain polymerizable compounds other than the aforementioned radical polymerizable compounds. Examples of polymerizable compounds other than the above-mentioned radical polymerizable compounds include compounds having methylol, alkoxymethyl, or oxomethyl; epoxy compounds; oxetane compounds; and benzo 㗁𠯤 Compound.

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

（式中，t表示1～20的整數，R¹⁰⁴ 表示碳數1～200的t價有機基團，R¹⁰⁵ 表示由-OR¹⁰⁶ 或-OCO-R¹⁰⁷ 表示之基團，R¹⁰⁶ 表示氫原子或碳數1～10的有機基團，R¹⁰⁷ 表示碳數1～10的有機基團。）[Chemical formula 26]

(In the formula, t represents an integer from 1 to 20, R ¹⁰⁴ represents a t-valent organic group with a carbon number of 1 to 200, R ¹⁰⁵ represents a group represented by -OR ¹⁰⁶ or -OCO-R ¹⁰⁷ , and R ¹⁰⁶ represents a hydrogen atom Or an organic group with 1 to 10 carbons, R ¹⁰⁷ represents an organic group with 1 to 10 carbons.)

（式中，R⁴⁰⁴ 表示碳數1～200的2價有機基團，R⁴⁰⁵ 表示由-OR⁴⁰⁶ 或-OCO-R⁴⁰⁷ 表示之基團，R⁴⁰⁶ 表示氫原子或碳數1～10的有機基團，R⁴⁰⁷ 表示碳數1～10的有機基團。）[Chemical formula 27]

(In the formula, R ⁴⁰⁴ represents a divalent organic group with 1 to 200 carbons, R ⁴⁰⁵ represents a group represented by -OR ⁴⁰⁶ or -OCO-R ⁴⁰⁷ , and R ⁴⁰⁶ represents a hydrogen atom or an organic group with 1 to 10 carbons. Group, R ⁴⁰⁷ represents an organic group with 1 to 10 carbons.)

（式中，u表示3～8的整數，R⁵⁰⁴ 表示碳數1～200的u價有機基團，R⁵⁰⁵ 表示由-OR⁵⁰⁶ 或、-OCO-R⁵⁰⁷ 表示之基團，R⁵⁰⁶ 表示氫原子或碳數1～10的有機基團，R⁵⁰⁷ 表示碳數1～10的有機基團。）[Chemical formula 28]

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

Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (manufactured by ASAHI YUKIZAI CORPORATION), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (Sanwa Chemical Co., Ltd. . System), 2,6-dimethoxymethyl-4-t-butylphenol (2,6-dimethoxymethyl-4-t-butylphenol), 2,6-dimethoxymethyl-p-cresol (2,6- Dimethoxymethyl-p-cresol), 2,6-diacetoxymethyl-p-cresol (2,6-diacetoxymethyl-p-cresol), etc.

Also, as specific examples of the compound represented by the formula (AM5), TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML- TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (manufactured by ASAHI YUKIZAI CORPORATION), NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW- 100LM (manufactured by Sanwa Chemical Co., Ltd.).

＜＜＜Epoxy compound (compound with epoxy group)＞＞＞ As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. The epoxy group undergoes a crosslinking reaction below 200°C, and it is difficult to cause shrinkage of the film because it does not cause a dehydration reaction from crosslinking. Therefore, by containing the epoxy compound, low-temperature hardening and warpage of the composition can be effectively suppressed.

The epoxy compound preferably contains a polyethylene oxide group. With this, the modulus of elasticity is further reduced, and warpage can be suppressed. The polyethylene oxide group means that the number of structural units of ethylene oxide is 2 or more, and the number of structural units is preferably 2-15.

Examples of epoxy compounds include bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether; polypropylene glycol diglycidyl ether and other poly Alkylene glycol type epoxy resin; epoxy-containing silicone such as polymethyl (glycidoxypropyl) silicone, etc., but not limited to these. Specifically, EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP- 4700, EPICLON (registered trademark) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered Trademarks) EXA-4850-150, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822 (manufactured by DIC Corporation), RIKARESIN (registered trademark) BEO-60E (Manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S (manufactured by ADEKA CORPORATION), etc. Among these, the epoxy resin containing a polyethylene oxide group is preferable in terms of suppressing warpage and excellent heat resistance. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, and RIKARESIN (registered trademark) BEO-60E contain polyethylene oxide groups and are therefore preferred.

＜＜＜Oxetane compound (compound with oxetanyl group)＞＞＞ Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethoxetane, 1,4-bis{ [(3-Ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4- Benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl] ester, etc. As a specific example, the ARON OXETANE series (for example, OXT-121, OXT-221, OXT-191, OXT-223) manufactured by TOAGOSEI CO., LTD. can be preferably used, and these can be used alone or in combination. More than species.

＜＜＜Benzo 㗁𠯤 compound (compound with polybenzo azole group)＞＞> Since the benzoxa compound is derived from the cross-linking reaction of the ring-opening addition reaction, it does not produce outgassing during hardening, thereby reducing thermal shrinkage and suppressing warpage, which is therefore preferred.

Preferable examples of the benzophenone compound include Ba-type benzophenone, Bm-type benzophenone (manufactured by Shikoku Chemicals Corporation), benzophenone adducts of polyhydroxystyrene resin, and phenolic aldehydes. Varnish-type dihydrobenzo 㗁𠯤 compound. These can be used alone, or two or more can be mixed.

When a polymerizable compound is contained, its content is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and more preferably 30% by mass or less. Moreover, when it contains a radically polymerizable compound, it is preferable that its content is more than 0 mass% and 60 mass% or less with respect to the total solid content of the resin composition of this invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and more preferably 30% by mass or less. The other polymerizable compounds may be used alone or in combination of two or more. When two or more are used at the same time, the total amount is preferably in the above-mentioned range.

＜Solvent＞ The resin composition of the present invention preferably contains a solvent. As the solvent, any known solvent can be used. The solvent is preferably an organic solvent. Examples of organic solvents include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfenes, and amines. As esters, for example, preferred ones include ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate Ester, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxy acetate (for example, methyl alkoxy acetate, Ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate Etc.)), 3-alkoxy propionic acid alkyl esters (for example, 3-alkoxy methyl propionate, 3-alkoxy ethyl propionate, etc. (for example, 3-methoxy propionic acid methyl ester , Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkoxypropionic acid alkyl esters (for example, 2- Methyl alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate , 2-methoxypropionic acid propyl ester, 2-ethoxypropionic acid methyl ester, 2-ethoxypropionic acid ethyl ester)), 2-alkoxy-2-methylpropionic acid methyl ester and 2- Ethyl alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate Ester, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc. As ethers, for example, preferred ones 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, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropylene Ether acetate etc. As the ketones, for example, preferred ones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and the like. As aromatic hydrocarbons, for example, preferable ones include toluene, xylene, anisole, limonene and the like. As the sulfenite, for example, a preferable one includes dimethyl sulfenite. As the amides, preferred ones include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N- Dimethylformamide and so on.

Regarding the solvent, from the viewpoint of improvement of coating surface properties, etc., a form in which two or more types are mixed is also preferable. In the present invention, it is selected from 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-butyrolactone, dimethyl sulfene, ethyl carbitol acetate, butyl carbitol One solvent or a mixed solvent composed of two or more of acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable. It is particularly preferable to use dimethyl sulfoxide and γ-butyrolactone at the same time.

Regarding the content of the solvent, from the viewpoint of coatability, the total solid content of the resin composition of the present invention is preferably 5 to 80% by mass, and more preferably 5 to 75% by mass. Preferably, it is more preferable to set it as 10-70 mass %, and it is still more preferable to set it as 40-70 mass %. The content of the solvent can be adjusted according to the desired thickness and coating method. The solvent may contain only one type or two or more types. When two or more kinds of solvents are contained, the total of them 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 transfer of metal ions originating from the metal layer (metal wiring) into the resin composition layer. The migration inhibitor is not particularly limited, and examples include heterocycles (pyrrole ring, furan ring, thiophene ring, imidazole ring, azole ring, thiazole ring, pyrazole ring, isoazole ring, isothiazole ring, tetra Azole ring, pyridine ring, pyran ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, oromoline ring, 2H-pyran ring and 6H-pyran ring, tri-pyran ring) compound, with Thiourea and sulfhydryl compounds, hindered phenol compounds, salicylic acid derivative compounds, hydrazine derivative compounds. 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.

In addition, ion scavengers that trap anions such as halogen ions can also be used.

As other migration inhibitors, the rust inhibitor described in paragraph 0094 of JP 2013-015701 A, the compounds described in paragraphs 0073 to 0076 of JP 2009-283711, and JP 2011-059656 can be used. The compound described in paragraph 0052 of JP 2012-194520, the compound described in paragraphs 0114, 0116, and paragraph 0118 of JP 2012-194520, the compound described in paragraph 0166 of International Publication No. 2015/199219, and the like.

As specific examples of migration inhibitors, the following compounds can be given. [Chemical formula 29]

When the resin composition has a migration inhibitor, the content of the migration inhibitor relative to the total solid content of the resin composition is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and more preferably 0.1 to 1.0% by mass. good. There may be only one type of migration inhibitor, or two or more types. When there are two or more migration inhibitors, it is preferable that the total of them is in the above range.

<Polymerization inhibitor> The resin composition of the present invention preferably contains a polymerization inhibitor. As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-tertiary butyl-p-cresol, pyrogallol, p-tertiary butylcatechol, 1 ,4-Benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 2,2'-methylenebis(4-methyl -6-tertiary butyl phenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothionine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine Tetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquine Phenol, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamine)phenol, N- Nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tertiarybutyl)phenylmethane, etc. In addition, the polymerization inhibitor described in paragraph 0060 of JP 2015-127817 A and the compound described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used. In addition, the following compounds (Me is a methyl group) can also be used. [Chemical formula 30]

When the resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor relative to the total solid content of the resin composition of the present invention is preferably 0.01-5 mass%, more preferably 0.02-3 mass%, and 0.05- 2.5% by mass is more preferable. There may be only one type of polymerization inhibitor, or two or more types. When there are two or more polymerization inhibitors, it is preferable that the sum total is the above range.

＜Metal adhesion improver＞ The resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion with metal materials used for electrodes, wiring, and the like. As the metal adhesion improver, a silane coupling agent and the like can be mentioned.

Examples of silane coupling agents include the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of JP 2014-191002, and International Publication No. 2011/080992 The compounds described in paragraphs 0063 to 0071, the compounds described in paragraphs 0060 to 0061 of JP 2014-191252, the compounds described in paragraphs 0045 to 0052 of JP 2014-041264, International Publication No. The compound described in paragraph 0055 of No. 2014/097594. In addition, it is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP 2011-128358 A. Moreover, it is also preferable to use the following compound as a silane coupling agent. In the following formulae, Et represents an ethyl group. [Chemical formula 31]

In addition, as the metal adhesion improver, compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A, and sulfide compounds described in paragraphs 0032 to 0043 of JP 2013-072935 A can also be used.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the polymer precursor, more preferably in the range of 0.5 to 15 parts by mass, and still more preferably in the range of 0.5 to 5 parts by mass. By setting it as the above-mentioned lower limit or more, the adhesiveness of the cured film after a hardening process and a metal layer becomes favorable, and by setting it as below the said upper limit, the heat resistance and mechanical characteristics of the cured film after a hardening process become favorable. There may be only one type of metal adhesion improver, or two or more types. When two or more types are used, it is preferable that the sum total is the above-mentioned range.

＜Other additives＞ The resin composition of the present invention can add various additives, such as thermal acid generators, sensitizing dyes, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic Particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, aggregation inhibitors, etc. are 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 thermal acid generator. When the specific thermal base generator has a protective group, the thermal acid generator is used to remove the protective group.

The content of the thermal acid generator is preferably 0.01 parts by mass or more with respect to 100 parts by mass of the polymer precursor, and more preferably 0.1 parts by mass or more. By containing 0.01 parts by mass or more of the thermal acid generator, the crosslinking reaction and the cyclization of the polymer precursor are promoted, and therefore the mechanical properties and chemical resistance of the cured film can be further improved. Also, from the viewpoint of the electrical insulation of the cured film, the content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and more preferably 10 parts by mass or less. Only one type of thermal acid 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.

＜＜Sensitizing pigment＞＞ The resin composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs specific active radiation and becomes an electronically excited state. The sensitizing dye in an electronically excited state comes into contact with a thermal hardening accelerator, a thermal radical polymerization initiator, a photo radical polymerization initiator, etc., to generate electron transfer, energy transfer, heat generation, and the like. Thereby, the thermal hardening accelerator, the thermal radical polymerization initiator, and the photo radical polymerization initiator undergo chemical changes to decompose, and generate radicals, acids, or bases. For the details of the sensitizing dye, refer to the description in paragraphs 0161 to 0163 of JP 2016-027357 A, and the contents are incorporated into this specification.

When the resin composition of the present invention contains a sensitizing dye, the content of the sensitizing dye relative to the total solid content of the resin composition of the present invention is preferably 0.01-20% by mass, more preferably 0.1-15% by mass, and 0.5- 10% by mass is more preferable. The sensitizing dye may be used singly, or two or more may be used at the same time.

＜＜Chain transfer agent＞＞ The resin composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in pages 683-684 of the third edition of the Polymer Dictionary (Edited by The Society of Polymer Science (Japan), 2005). As the chain transfer agent, for example, a compound group having SH, PH, SiH, and GeH in the molecule is used. These low-activity free radicals are supplied with hydrogen to generate free radicals, or after oxidation, free radicals can be generated by deprotonation. In particular, thiol compounds can be preferably used. In addition, 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 contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01-20 parts by mass relative to 100 parts by mass of the total solid content of the resin composition of the present invention, and more preferably 1-10 parts by mass , 1 to 5 parts by mass is more preferable. The chain transfer agent may be only one type or two or more types. When there are two or more chain transfer agents, it is preferable that the total range is the above range.

<<Surfactant>> From the viewpoint of further improving coatability, various surfactants can be added to the resin composition of the present invention. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used. In addition, the following surfactants are also preferable. [Chemical formula 32]

In addition, as the surfactant, the compounds 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 relative to the total solid content of the resin composition of the present invention, and more preferably 0.005 to 1.0% by mass. The surfactant may be only one type or two or more types. When there are two or more surfactants, it is preferable that the total range thereof is the above range.

＜＜Higher fatty acid derivatives＞＞ In order to prevent polymerization inhibition caused by oxygen, higher fatty acid derivatives such as behenic acid or behenic acid amide can be added to the resin composition of the present invention, and the composition is biased during the drying process after coating. surface. In addition, the higher fatty acid derivatives can also use the compounds described in paragraph 0155 of International Publication No. 2015/199219. When the resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the resin composition of the present invention. There may be only one type of higher fatty acid derivative, or two or more types. When there are two or more higher fatty acid derivatives, the total range thereof is preferably the above range.

＜Restrictions on other contained substances＞ From the viewpoint of coating surface properties, the moisture content of the resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and more preferably less than 0.6% by mass.

From the viewpoint of insulation, it is preferable that the metal content of the resin composition of the present invention is less than 5 mass ppm (parts per million), less than 1 mass ppm is more preferable, and less than 0.5 mass ppm is more preferable. good. Examples of metals 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. In addition, as a method of reducing the metal impurities accidentally included in the resin composition of the present invention, it is possible to exemplify the selection of a raw material with a lower metal content as the raw material constituting the resin composition of the present invention. The raw material is filtered through a filter, the inside of the device is lined with polytetrafluoroethylene, etc., and distillation is carried out under the condition of suppressing pollution as much as possible.

Considering the use as a semiconductor material and from the viewpoint of wiring corrosion, 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 Further better. Among them, less than 5 mass ppm is preferred in the state of halogen ions, less than 1 mass ppm is more preferred, and less than 0.5 mass ppm is more preferred. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of the chlorine atom and the bromine atom or the chlorine ion and the bromine ion be in the above-mentioned ranges.

As the storage container of the resin composition of the present invention, a conventionally known storage container can be used. In addition, as a storage container, for the purpose of suppressing the mixing of impurities into the raw material or composition, it is also preferable to use a multilayer bottle in which the inner wall of the container is composed of 6 types of 6-layer resins, and a bottle in which 6 types of resins are formed into a 7-layer structure. As such a container, for example, the container described in JP 2015-123351 A can be cited.

[Preparation of resin composition] The resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and it can be performed by a conventionally known method. In addition, for the purpose of removing foreign substances such as garbage or particles in the composition, it is preferable to perform filtration using a filter. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter can be cleaned with an organic solvent in advance. In the filtration step of the filter, multiple filters can be used in parallel or in series. When multiple filters are used, filters with different pore sizes or materials can be used in combination. In addition, various materials can be filtered multiple times. When filtering for multiple times, it can be cyclic filtering. Furthermore, filtration may be performed after pressurization. When filtering is performed after pressurization, the pressurization pressure is preferably 0.05 MPa or more and 0.3 MPa or less. In addition to filtration using filters, it can also be used to remove impurities using adsorbents. It can also be combined with filter filtration and impurity removal treatment using adsorbent materials. As the adsorbent, a known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be cited.

[Cured film, laminate, semiconductor element, and methods of manufacturing them] Next, the cured film, the laminate, the semiconductor element, and the manufacturing method thereof 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 this invention can be 0.5 micrometer or more, for example, and can be 1 micrometer or more. Moreover, as an upper limit, it can be 100 micrometers or less, and can also be 30 micrometers or less. The thickness of the cured film of the present invention is preferably 1 to 30 μm.

Two or more layers of the cured film of the present invention can be laminated, and 3 to 7 layers can be laminated as a laminated body. The laminated body having two or more layers of the cured film of the present invention preferably has a metal layer between the cured films. Such a metal layer can be preferably used as a metal wiring such as a rewiring layer.

As a field to which the cured film of this invention can be applied, the insulating film of a semiconductor element, the interlayer insulating film for rewiring layers, a stress buffer film, etc. are mentioned. In addition, examples include sealing films, substrate materials (base films or cover layers of flexible printed circuit boards, and interlayer insulating films), or patterning of insulating films for actual mounting purposes by etching. For these uses, for example, you can refer to Science & Technology Co., Ltd. "High-functionalization and Application Technology of Polyimide" April 2008, Kakimoto Masaki/Supervisor, CMC Technical Library "Polyimide Materials The foundation and development of "Polyimine" issued in November 2011, Japan Polyimine and Aromatic Polymer Research Society/Edition "The latest polyimine basics and applications" NTS, August 2010, etc.

In addition, the cured film in the present invention can also be used in the production of offset printing plates or screen plates, the use of molded parts, and the production of protective paints and dielectric layers in electronics, especially microelectronics.

The manufacturing method of the cured film of this invention includes using the resin composition of this invention. Specifically, it is preferable to include the following steps (a) to (d). (A) Film forming step of applying resin composition to substrate to form film (B) After the film formation step, the exposure step of exposing the film (C) The developing step of developing the exposed resin composition layer (D) Heating step of heating the developed resin composition at 80～450℃ Like this embodiment, the exposed resin layer can be further hardened by heating after development.

The manufacturing method of the laminated body of the preferable embodiment of this invention includes the manufacturing method of the cured film of this invention. The manufacturing method of the laminated body of this embodiment follows the above-mentioned manufacturing method of the cured film, after forming the cured film, the step (a) or the steps (a) to (c) or (a) to (d) are performed again. )A step of. In particular, it is preferable to sequentially perform the above-mentioned steps a plurality of times, for example, 2 to 5 times (that is, 3 to 6 times in total). By laminating the cured film in this way, a laminate can be formed. In the present invention, it is particularly preferable to provide a metal layer on the part where the cured film is provided, between the cured films, or both. In addition, in the production of the laminate, it is not necessary to repeat all the steps (a) to (d). As described above, it is possible to perform at least (a), preferably (a) to (c) or (a) multiple times. Step to (d) to obtain a laminate of cured film.

<Film formation step (layer formation step)> The manufacturing method of the preferred embodiment of the present invention includes a film forming step (layer forming step) of applying a resin composition to a substrate to form a film (layered). The type of substrate can be appropriately set according to the application, but is not particularly limited. Examples include semiconductor substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, and vapor-deposited films. , Magnetic films, reflective films, Ni, Cu, Cr, Fe and other metal substrates, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, plasma display panel (PDP) electrode plates, etc. In the present invention, semiconductor substrates are particularly preferred, and silicon substrates are more preferred. In addition, 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 becomes a substrate. As a method of applying the resin composition to the substrate, coating is preferred. Specifically, as applicable methods, there can be exemplified dip coating methods, air knife coating methods, curtain coating methods, wire bar coating methods, gravure coating methods, extrusion coating methods, spray coating methods, spin coating methods, Slit coating method and inkjet method, etc. 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. By adjusting the appropriate solid content concentration or coating conditions according to the method, a resin layer of a desired thickness can be obtained. In addition, the coating method can be appropriately selected according to the shape of the substrate. As long as it is a round substrate such as a wafer, spin coating, spray coating, inkjet, etc. are preferred, and as long as it is a rectangular substrate, the slit coating method Or spraying method, inkjet method, etc. are 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 step＞ The manufacturing method of the present invention may further include a step of drying in order to remove the solvent after the resin composition layer is formed, and after the film formation step (layer formation step). The preferred drying temperature is 50-150°C, more preferably 70-130°C, and even more preferably 90-110°C. As the drying time, 30 seconds to 20 minutes are exemplified, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.

<Exposure Step> The manufacturing method of the present invention may include an exposure step of exposing the above-mentioned resin composition layer. The exposure amount is not particularly limited as long as it can harden the resin composition. For example, it is preferable to irradiate 100 to 10000 mJ/cm ² in terms of exposure energy at a wavelength of 365 nm, and more preferably to irradiate 200 to 8000 mJ/cm ² . The exposure wavelength can be appropriately set in the range of 190-1000 nm, preferably 240-550 nm. Regarding the exposure wavelength, if it is described in terms of the relationship with the light source, (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g Ray (wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), wide (3 wavelengths of g, h, and i rays), (4) excimer laser, KrF excimer laser (wavelength 248nm) , ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beam, etc. Regarding the resin composition of the present invention, exposure based on a high-pressure mercury lamp is particularly preferred, and exposure based on i-rays is particularly preferred. In this way, particularly high exposure sensitivity can be obtained.

<Development process steps> The manufacturing method of the present invention may include a development process step of developing the exposed resin composition layer. By developing, the unexposed part (non-exposed part) is removed. The development method is not particularly limited as long as a desired pattern can be formed. For example, development methods such as spin immersion, spray, dipping, and ultrasonic waves can be used. The development is performed using a developer. Regarding the developer, as long as the unexposed part (non-exposed part) can be removed, it can be used without particular limitation. It is preferable that the developer contains an organic solvent, and it is more preferable that the developer contains 90% or more of an organic solvent. In the present invention, the developer preferably contains an organic solvent with a ClogP value of -1 to 5, and more preferably contains an organic solvent with a ClogP value of 0 to 3. The ClogP value can be calculated as a calculated value by inputting the structural formula in ChemBioDraw (Chemical Biological Diagram). Regarding organic solvents, as esters, for example, ethyl acetate, n-butyl acetate, pentyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyric acid can be suitably mentioned. Ethyl ester, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (example: methyl alkoxyacetate , Ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate Esters, etc.)), 3-alkoxypropionic acid alkyl esters (e.g. 3-alkoxy methyl propionate, 3-alkoxy ethyl propionate, etc. (e.g. 3-methoxy propionate methyl Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkoxypropionic acid alkyl esters (example: 2 -Methyl alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate Ester, 2-Methoxy Propionate, 2-Ethoxy Propionate, 2-Ethoxy Propionate)), 2-Alkoxy-2-Methyl Propionate and 2 -Ethyl alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), pyruvic acid Methyl ester, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, for example Suitable examples 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, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as Ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc. can be suitably mentioned, and as aromatic hydrocarbons For example, toluene, xylene, anisole, limonene, etc. can be suitably mentioned, and as the sulfenite, dimethyl sulfenite can be suitably mentioned. In the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred. It is preferable that 50% by mass or more of the developer is an organic solvent, more preferably 70% by mass or more is an organic solvent, and more than 90% by mass is an organic solvent. In addition, 100% by mass of the developer may be an organic solvent.

As the development time, 10 seconds to 5 minutes are preferred. The temperature of the developing solution during development is not particularly limited, and it can usually be performed at 20 to 40°C. After treatment with developer, it can be rinsed. Rinsing is preferably performed with a solvent different from the developer. For example, the solvent contained in the resin composition can be used for rinsing. The washing time is preferably 5 seconds to 1 minute.

＜Heating step＞ The manufacturing method of the present invention preferably includes a step of heating after the film formation step (layer formation step), drying step, or development step. In the heating step, the cyclization reaction of the polymer precursor proceeds. As the heating temperature (maximum heating temperature) of the layer in the heating step, 50°C or higher is preferred, 80°C or higher is more preferred, 140°C or higher is even more preferred, 150°C or higher is even more preferred, and 160°C or higher is still further Preferably, 170°C or higher is even more preferable. As the upper limit, 500°C or less is preferred, 450°C or less is more preferred, 350°C or less is more preferred, 250°C or less is even more preferred, and 220°C or less is still more preferred. Regarding heating, it is preferable to perform heating at a temperature increase rate of 1-12°C/min from the temperature at the start of heating to the maximum heating temperature, more preferably 2-10°C/min, and still more preferably 3-10°C/min. By setting the heating rate to 1°C/min or more, it is possible to prevent excessive volatilization of amine while ensuring productivity, and by setting the heating rate to 12°C/min or less, the residual stress of the cured film can be alleviated. The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the step of heating to the highest heating temperature. For example, when the resin composition is applied to a substrate and dried, the temperature of the film (layer) after drying is, for example, gradually from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition It is better to increase the temperature. The heating time (heating time at the highest heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and more preferably 30 to 240 minutes. In particular, when forming a multilayer laminate, from the viewpoint of the adhesion between the layers of the cured film, it is preferable to heat at a heating temperature of 180°C to 320°C, and more preferably to heat at 180°C to 260°C. Although the reason is not certain, it is thought that the reason is as follows. That is, by setting the temperature at this temperature, the ethynyl groups of the polymer precursors between the layers undergo a crosslinking reaction.

Heating can be carried out in stages. As an example, it is possible to perform the treatment before raising the temperature from 25°C to 180°C at 3°C/min, and keeping it at 180°C for 60 minutes, heating it from 180°C to 200°C at 2°C/min, and keeping it at 200°C for 120 minutes step. The heating temperature as a pretreatment step is preferably 100 to 200°C, more preferably 110 to 190°C, and even more preferably 120 to 185°C. In this pretreatment step, it is also preferable to perform treatment while irradiating ultraviolet rays as described in U.S. Patent No. 9159547. The characteristics of the film can be improved by these pretreatment steps. The pretreatment step may be carried out in a short time of about 10 seconds to 2 hours, and 15 seconds to 30 minutes is more preferable. The pretreatment may be a two-stage or more step. 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. Furthermore, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5°C/min.

Regarding the heating step, from the viewpoint of preventing the decomposition of the polymer precursor, it is preferable to perform it in a low oxygen concentration environment by flowing inert gas such as nitrogen, helium, and argon. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

＜Metal layer formation steps＞ The manufacturing 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. The metal layer is not particularly limited, and existing metal types can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper and aluminum are more preferable, and copper is more preferable. The method of forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in Japanese Patent Application Publication No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Publication No. 2004-214501, and Japanese Patent Application Publication No. 2004-101850 can be used. For example, methods such as photolithography, peeling, electrolytic plating, electroless plating, etching, printing, and combinations can be considered. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electrolytic plating can be cited. The thickness of the metal layer is preferably 0.1 to 50 μm at the thickest part, and more preferably 1 to 10 μm.

＜Layering steps＞ Preferably, the manufacturing method of the present invention further includes a layering step. The lamination step includes the surface of the cured film (resin layer) or the metal layer, and then successively perform (a) film formation step (layer formation step), (b) exposure step, (c) development treatment step, and (d) heating step. A series of steps. Among them, it may be an aspect in which only the film forming step of (a) is repeated. In addition, the heating step (d) may be performed collectively at the end or in the middle of the build-up. That is, it can also be set as the aspect in which the steps (a) to (c) are repeated a predetermined number of times, and then the heating of (d) is performed, thereby collectively curing the laminated resin composition layers. In addition, (c) the development step may include (e) the metal layer forming step. In this case, the heating of (d) may be performed each time, or the heating of (d) may be collectively performed after a predetermined number of laminations. It goes without saying that the above-mentioned drying step, heating step, etc. can also be appropriately included in the layering step. When the layering step is further performed after the layering step, the surface activation treatment step may be further performed after the heating step, and after the exposure step, or after the metal layer forming step. As the surface activation treatment, plasma treatment is exemplified. The above-mentioned layering step is preferably performed 2 to 5 times, and more preferably 3 to 5 times. For example, a resin layer such as a resin layer/metal layer/resin layer/metal layer/resin layer/metal layer is preferably a structure having 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 by covering the metal layer after the metal layer is provided. Specifically, it can be mentioned that (a) film formation step, (b) exposure step, (c) development step, (e) metal layer formation step, (d) heating step are repeated in sequence, or (a) ) Film formation step, (b) exposure step, (c) development step, (e) metal layer formation step, and (d) heating step is set 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 alternately laminated.

The present invention also discloses a semiconductor element having the cured film or laminate of the present invention. As a specific example of a semiconductor element in which the resin composition of the present invention is used in the formation of an interlayer insulating film for a rewiring layer, refer to the description in paragraphs 0213 to 0218 of JP 2016-027357 A and the description in FIG. 1. And these contents are incorporated into this manual. [Example]

Hereinafter, the present invention will be described in further detail with examples. The materials, usage amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are quality standards.

Determination of (and ^{_{SO 3 2- HNO 2, NO 2}} -, HNO 3, NO 3 -, H 2 SO 4, HSO 4 - -, SO 4 2-, H 2 SO 3, HSO 3) of the <specific component Method> 20 g of a measurement sample, 50 g of tetrahydrofuran as a non-aqueous organic solvent, and 50 g of ultrapure water were mixed. When the solid is precipitated by the addition of water, the solid is removed by centrifugal separation. When the solid is not precipitated, the organic layer and the water layer are separated (liquid separation operation), and the content of the specific component extracted into the aqueous solution is determined by ion chromatography了定。 The determination. As a measuring device, Shimadzu HIC-20A (manufactured by Shimadzu Corporation) was used.

<Synthesis Example 1> [Polyimine precursor derived from pyromellitic dianhydride, 4,4'-diaminodiphenyl ether, and benzyl alcohol (A-1: without radical polymerizable group) Synthesis of polyimide precursor] 14.06g (64.5 millimoles) of pyromellitic dianhydride (dried at 140°C for 12 hours) and 14.22g (131.58 millimoles) of benzyl alcohol were suspended in 50 mL The N-methylpyrrolidone was dried with molecular sieves. The suspension was heated at 100°C for 3 hours. The reaction mixture was cooled to room temperature, and 21.43 g (270.9 millimoles) of pyridine and 90 mL of N-methylpyrrolidone were added. Next, the reaction mixture was cooled to -10°C, and 16.12 g (135.5 millimoles) of SOCl _{2 was} added over 10 minutes while maintaining the temperature at -10±4°C. During the addition of SOCl ₂ , the viscosity increased. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, 11.08 g (58.7 millimoles) of 4,4'-diaminodiphenyl ether was dissolved in 100 mL of N-methylpyrrolidone into the reaction mixture at -5～0°C for 20 minutes. From the solution. Next, after reacting the reaction mixture at 0°C for 1 hour, 70 g of ethanol was added and stirred at room temperature overnight. Next, the polyimide precursor was precipitated in 5 L of water, and the water-polyimine precursor mixture was stirred for 15 minutes at a speed of 5000 rpm. The obtained wet solid was dissolved in 300 mL of tetrahydrofuran (THF), and then 300 mL of water was added to repeat the liquid separation operation 3 times. The obtained THF/polyimide precursor solution was reprecipitated with 5L of water. The polyimide precursor was removed by filtration, stirred again in 4L of water for 30 minutes, and filtered again. Next, under reduced pressure, the obtained polyimide precursor was dried at 45°C for 3 days. The weight average molecular weight of the polyimide precursor was 18,000. Further, the polyimide precursor of the 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-) content by an ion chromatography measurement results, the specific component is not detected.

A-1 [Chemical formula 33]

<Synthesis Example 2> [Polyimide precursor derived from pyromellitic dianhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate (A-2: Free [Synthesis of polyimide precursor based on polymerizable group]] 14.06g (64.5 millimoles) of pyromellitic dianhydride (dried at 140°C for 12 hours), 16.8g (129 millimoles) ) 2-hydroxyethyl methacrylate, 0.05g hydroquinone, 20.4g pyridine (258 millimoles) and 100g diglyme (diethylene glycol dimethyl ether) are mixed , Stirred at a temperature of 60°C for 18 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Next, after chlorinating the obtained diester by SOCl _2, it was converted into a polyimide precursor with 4,4'-diaminodiphenyl ether in the same way as in Synthesis Example 1, and the result was compared with Synthesis Example 1. 1 The same method is used to obtain the polyimide precursor. The weight average molecular weight of the polyimide precursor was 19,000. Further, the polyimide precursor of the 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-) content by an ion chromatography measurement results, the specific component is not detected.

A-2 [Chemical formula 34]

<Synthesis Example 3> [Polyimide precursor derived from 4,4'-oxydiphthalic anhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate ( A-3: Synthesis of polyimide precursor with radical polymerizable groups] 20.0 g (64.5 millimoles) of 4,4'-oxydiphthalic anhydride (dried at 140°C) For 12 hours), 16.8g (129 millimoles) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 20.4g of pyridine (258 millimoles) and 100g of diethylene glycol dimethyl The ether was mixed and stirred at a temperature of 60°C for 18 hours to produce a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Next, after chlorinating the obtained diester by SOCl _2, it was converted into a polyimide precursor with 4,4'-diaminodiphenyl ether in the same way as in Synthesis Example 1, and the result was compared with Synthesis Example 1. 1 The same method is used to obtain the polyimide precursor. Further, the polyimide precursor of the 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-) content by an ion chromatography measurement results, the specific component is not detected.

A-3 [Chemical formula 35]

<Synthesis example 4> [From 4,4'-oxydiphthalic anhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (o-xylene) and methacrylic acid- Synthesis of polyimide precursor of 2-hydroxyethyl ester (A-4: polyimide precursor with radical polymerizable group)] 20.0 g (64.5 millimoles) of 4,4'- Oxydiphthalic anhydride (dried at 140°C for 12 hours), 16.8g (129 millimoles) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 20.4g of pyridine ( 258 millimoles) and 100 g of diglyme were mixed, and stirred at 60°C for 18 hours to produce 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate The diester. Next, after chlorinating the obtained diester with SOCl _2, it was converted into polyimide using 4,4'-diamino-2,2'-dimethylbiphenyl in the same manner as in Synthesis Example 1. The precursor, and the polyimide precursor was obtained by the same method as in Synthesis Example 1. The weight average molecular weight of the polyimide precursor was 19,000. Further, the polyimide precursor of the 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-) content by an ion chromatography measurement results, the specific component is not detected.

A-4 [Chemical formula 36]

<Synthesis Example 5> [Polybenzoxazole precursor derived from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 4,4'-oxodibenzyl chloride Synthesis of (A-5)] To 100 mL of N-methyl-2-pyrrolidone, 13.92 g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was added and stirred and dissolved. Next, 11.21 g of 4,4'-oxodityl chloride was added dropwise over 10 minutes while maintaining the temperature at 0 to 5°C, and then stirring was continued for 60 minutes. Next, the polybenzoxazole precursor was precipitated in 6 liters of water, and the water-polybenzoxazole precursor mixture was stirred for 15 minutes at a speed of 5000 rpm. The polybenzoxazole precursor was removed by filtration, stirred again in 6 liters of water for 30 minutes, and filtered again. Next, the obtained polybenzoxazole precursor was dried at 45°C for 3 days under reduced pressure. The weight average molecular weight of this polybenzoxazole precursor was 15,000. Further, the polybenzoxazole precursor㗁oxadiazol-specific component is not detected ^{_{(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- ).

A-5 [Chemical formula 37]

<Examples and Comparative Examples> The components described in the following table were mixed to obtain each resin composition. Regarding components other than the polymer precursor, purification methods such as distillation and crystallization were repeated for the components described in the following table. As a result of confirming the content of specific components in these components by ion chromatography, it was confirmed that the specific components were not contained in these components. The obtained resin composition was filtered under pressure through a filter having a pore width of 0.8 μm. Then, sodium nitrite, nitrate, sodium sulfate, potassium bisulfate, sodium sulfite, sulfate, sulfite and sodium hydrogen sulfite and the ^{_{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- is adjusted to the content of the content described in the following table, the resin composition of Examples and Comparative Examples prepared thereby. Regarding the content of the above-mentioned components, those added to the resin composition and subjected to water extraction were measured by ion chromatography.

[Table 1] Polymer precursor Thermal alkali generator Free radical polymerization initiator Radical polymerizable compound Polymerization inhibitor Migration inhibitor Metal adhesion improver Solvent The sum of HNO ² and NO ^2- The sum of HNO ³ and NO ^3- The sum of H ₂ SO ₄ , HSO ₄ ^- and SO ₄ ^2- The sum of H ₂ SO ₃ , HSO ₃ ^- and SO ₃ ^2- Total content of specific ingredients species Mass parts species Mass parts species Mass parts species Mass parts species Mass parts species Mass parts species Mass parts species Mass parts species Mass parts Mass ppm Mass ppm Mass ppm Mass ppm Mass ppm Composition 1 A-1 33.6 B-1 0.3 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-2 0.63 I-1 45 I-2 15 5 5 2 2 14 Composition 2 A-1 33.6 B-1 0.3 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-2 0.63 I-1 45 I-2 15 0.1 10 3 7 20.1 Composition 3 A-1 33.6 B-1 0.3 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-2 0.63 I-1 45 I-2 15 0 3 50 1 54 Composition 4 A-1 33.6 B-1 0.3 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-2 0.63 I-1 45 I-2 15 0.05 2 0 0.05 2.1 Composition 5 A-1 33.6 B-1 0.3 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-2 0.63 I-1 45 I-2 15 230 250 185 275 940 Composition 6 A-1 33.6 B-1 0.3 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-2 0.63 I-1 45 I-2 15 0 0 0.002 0 0.002 Composition 7 A-1 33.6 B-1 0.3 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-2 0.63 I-1 45 I-2 15 0.01 0 0 0 0.01 Composition 8 A-1 33.6 B-1 0.3 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-2 0.63 I-1 45 I-2 15 0 0.003 0.01 0 0.013 Composition 9 A-1 33.6 B-1 0.3 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-2 0.63 I-1 45 I-2 15 0 0 0 0.01 0.01 Composition 10 A-2 33.6 B-2 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-2 0.126 G-1 0.63 I-1 45 I-2 15 2 3 0.5 1.5 7 Composition 11 A-3 33.6 B-3 0.3 C-1 1.26 D-1 5.88 E-2 0.084 F-1 0.126 G-1 0.63 I-1 45 I-2 15 3.5 5 1.3 0.7 10.5 Composition 12 A-4 33.6 B-3 0.75 C-1 1.26 D-1 5.88 E-2 0.084 F-1 0.126 G-1 0.63 I-1 45 I-2 15 10 0 0.5 1.5 12 Composition 13 A-5 33.6 B-4 0.3 C-1 1.26 D-2 5.88 E-1 0.084 F-1 0.126 G-1 0.63 I-1 45 I-2 15 15 1.5 0 1 17.5 Composition 14 A-3 33.6 B-5 0.75 C-2 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-3 0.63 I-1 45 I-2 15 2 2 2.5 1 7.5 Composition 15 A-3 33.6 B-4 0.75 C-1 1.26 D-3 5.88 E-1 0.084 F-1 0.126 G-1 0.63 I-1 45 I-2 15 0.5 1 0.5 2 4 Composition 16 A-3 33.6 B-4 0.75 C-3 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 I-1 45 I-3 15 0.5 0.5 0.5 10 11.5 Composition 17 A-3 33.6 B-4 0.75 C-1 1.26 D-1 5.88 E-3 0.084 F-1 0.126 G-2 0.63 I-1 45 I-2 15 0 5 0 1.5 6.5 Composition 18 A-5 33.6 B-5 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-3 0.126 G-1 0.63 I-1 45 I-2 15 1 0.5 0.3 0.1 1.9 Composition 19 A-3 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-4 0.126 G-1 0.63 I-1 45 I-3 15 0.01 0.5 1 0.1 1.61 Composition 20 A-3 33.6 B-2 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-3 0.63 I-1 45 I-2 15 0.5 1.5 0 15 17 Composition 21 A-3 33.6 B-5 0.75 C-3 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 I-1 45 I-3 15 9 3 2.5 10 24.5

[Table 2] Polymer precursor Thermal alkali generator Free radical polymerization initiator Radical polymerizable compound Polymerization inhibitor Migration inhibitor Metal adhesion improver Solvent The sum of HNO ² and NO ^2- The sum of HNO ³ and NO ^3- The sum of H ₂ SO ₄ , HSO ₄ ^- and SO ₄ ^2- The sum of H ₂ SO ₃ , HSO ₃ ^- and SO ₃ ^2- Total content of specific ingredients species Mass parts species Mass parts species Mass parts species Mass parts species Mass parts species Mass parts species Mass parts species Mass parts species Mass parts Mass ppm Mass ppm Mass ppm Mass ppm Mass ppm Composition 22 A-1 33.6 B-1 0.3 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-2 0.63 I-1 45 I-2 15 0 0 0 0 0 Composition 23 A-1 33.6 B-1 0.3 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-2 0.63 I-1 45 I-2 15 500 330 260 100 1190 Composition 24 A-1 33.6 B-1 0.3 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-2 0.63 I-1 45 I-2 15 0 0 1100 20 1120 Composition 25 A-2 33.6 B-2 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-2 0.126 G-1 0.63 I-1 45 I-2 15 160 220 280 380 1040 Composition 26 A-3 33.6 B-3 0.3 C-1 1.26 D-1 5.88 E-2 0.084 F-1 0.126 G-1 0.63 I-1 45 I-2 15 430 185 230 210 1055 Composition 27 A-4 33.6 B-3 0.75 C-1 1.26 D-1 5.88 E-2 0.084 F-1 0.126 G-1 0.63 I-1 45 I-2 15 100 190 335 415 1040 Composition 28 A-5 33.6 B-4 0.3 C-1 1.26 D-2 5.88 E-1 0.084 F-1 0.126 G-1 0.63 I-1 45 I-2 15 255 325 200 250 1030 Composition 29 A-3 33.6 B-5 0.75 C-2 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-3 0.63 I-1 45 I-2 15 330 320 190 220 1060 Composition 30 A-3 33.6 B-4 0.75 C-1 1.26 D-3 5.88 E-1 0.084 F-1 0.126 G-1 0.63 I-1 45 I-2 15 550 300 285 100 1235 Composition 31 A-3 33.6 B-4 0.75 C-3 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 I-1 45 I-3 15 80 170 450 305 1005 Composition 32 A-3 33.6 B-4 0.75 C-1 1.26 D-1 5.88 E-3 0.084 F-1 0.126 G-2 0.63 I-1 45 I-2 15 250 280 310 170 1010 Composition 33 A-5 33.6 B-5 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-3 0.126 G-1 0.63 I-1 45 I-2 15 600 55 215 155 1025 Composition 34 A-3 33.6 B-1 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-4 0.126 G-1 0.63 I-1 45 I-3 15 110 115 360 520 1105 Composition 35 A-3 33.6 B-2 0.75 C-1 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-3 0.63 I-1 45 I-2 15 500 100 150 290 1040 Composition 36 A-3 33.6 B-5 0.75 C-3 1.26 D-1 5.88 E-1 0.084 F-1 0.126 G-1 0.63 I-1 45 I-3 15 300 330 280 170 1080

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

(Polymer precursor) A-1～A-5: The above polymer precursors A-1～A-5

(Thermal base generator) B-1～B-5: Compounds of the following structure [Chemical formula 38]

(Free radical polymerization initiator) C-1: IRGACURE OXE 01 (made by BASF) C-2: IRGACURE OXE 02 (made by BASF) C-3: IRGACURE 369 (made by BASF)

D-3：A-TMMT（Shin Nakamura Chemical Co.,Ltd.製）(Radical polymerizable compound) D-1: A-DPH (manufactured by Shin Nakamura Chemical Co., Ltd.) D-2: SR-209 (manufactured by Sartomer Company inc., compound with the following structure) [Chemical formula 39]

D-3: A-TMMT (manufactured by Shin Nakamura Chemical Co., Ltd.)

(Polymerization inhibitor) E-1: 2,6-Di-tert-butyl-4-methylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) E-2: p-benzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) E-3: p-Methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)

(Migration inhibitor) F-1 to F-4: Compounds of the following structure [Chemical formula 40]

(Metal Adhesion Improver) G-1 to G-3: Compounds of the following structure. In the following structural formulae, Et represents an ethyl group. [Chemical formula 41]

(Solvent) I-1: γ-Butyrolactone (manufactured by SANWAYUKA INDUSTRY CORPORATION) I-2: Dimethyl sulfide (manufactured by Wako Pure Chemical Industries, Ltd.) I-3: N-methyl-2-pyrrolidone (manufactured by Ashland)

＜Evaluation of storage stability＞ The viscosity (0 day) of the resin composition of compositions 1 to 36 was measured using an E-type viscometer. After allowing the resin composition to stand at 25°C for 14 days in an airtight container, the viscosity was again measured with an E-type viscometer (14 days). The viscosity change rate was calculated based on the following formula. The lower the viscosity change rate, the higher the storage stability. Viscosity rate of change=|100×{1-(Viscosity (14 days)/Viscosity (0 days))}| The measurement of viscosity was performed at 25°C, and otherwise, it was performed in accordance with JIS Z 8803:2011. A: The viscosity change rate is less than 5% B: Viscosity change rate exceeds 5% and less than 10% C: The viscosity change rate exceeds 10% and 15% or less D: Viscosity change rate exceeds 15% and 20% or less

＜Evaluation of moisture resistance＞ The resin composition of compositions 1 to 36 was applied to a silicon wafer by a spin coating method, and dried on a hot plate at 100° C. for 5 minutes, thereby forming a resin composition layer with a thickness of about 15 μm. The resin composition layer was heated at a temperature increase rate of 10°C/min under a nitrogen atmosphere, and after reaching 250°C, it was heated for 3 hours to form a cured film. The silicon wafer on which the cured film is formed was placed in 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, crack) occurrence area was observed to evaluate the resistance Wetness. A: The modified area is less than 2% of the area of the cured film B: The modified location is 2% or more and less than 5% of the area of the cured film C: The modified location is 5% or more and less than 10% of the area of the cured film D: The modified area is more than 10% of the area of the cured film

＜Copper Corrosion＞ The resin composition of compositions 1 to 36 was applied to a copper wafer by a spin coating method, and dried on a hot plate at 100° C. for 5 minutes, thereby forming a resin composition layer with a thickness of about 15 μm. The resin composition layer was heated at a temperature increase rate of 10°C/min under a nitrogen atmosphere, and after reaching 250°C, it was 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 at a temperature of 85°C and a humidity of 85% for 24 hours, and the corrosion occurred on the copper wafer was observed with an optical microscope. The copper corrosivity was evaluated by observing the percentage of the area of the corrosion occurrence site with respect to the area of one side surface of the hardened film on which the copper wafer was provided. A: The area where the corrosion occurs is less than 5% relative to the area of one side surface of the hardened film on which the copper wafer is provided B: The area of the location where corrosion occurs is 5% or more and less than 10% relative to the area of one side surface of the cured film on which the copper wafer is provided C: The area of the location where the corrosion occurs is 10% or more and less than 20% relative to the area of one side surface of the cured film on which the copper wafer is provided D: The area where the corrosion occurs is 20% or more relative to the area of one side surface of the cured film on which the copper wafer is provided

[table 3] Resin composition used Storage stability Moisture resistance Copper corrosion Example 1 Composition 1 A A A Example 2 Composition 2 A A A Example 3 Composition 3 A A A Example 4 Composition 4 A A A Example 5 Composition 5 A A B Example 6 Composition 6 A B A Example 7 Composition 7 A A A Example 8 Composition 8 A A A Example 9 Composition 9 A A A Example 10 Composition 10 A A A Example 11 Composition 11 A A A Example 12 Composition 12 A A A Example 13 Composition 13 A A A Example 14 Composition 14 A A A Example 15 Composition 15 A A A Example 16 Composition 16 A A A Example 17 Composition 17 A A A Example 18 Composition 18 A A A Example 19 Composition 19 A A A Example 20 Composition 20 A A A Example 21 Composition 21 A A A Comparative example 1 Composition 22 B B A Comparative example 2 Composition 23 C D C Comparative example 3 Composition 24 C D C Comparative example 4 Composition 25 B C C Comparative example 5 Composition 26 B C C Comparative example 6 Composition 27 B C C Comparative example 7 Composition 28 B C C Comparative example 8 Composition 29 B C C Comparative example 9 Composition 30 D D D Comparative example 10 Composition 31 B C C Comparative example 11 Composition 32 B C C Comparative example 12 Composition 33 B C C Comparative example 13 Composition 34 B C C Comparative example 14 Composition 35 B C C Comparative example 15 Composition 36 B C C

Based on the above results, the resin composition of the example has good storage stability and can form a cured film with excellent moisture resistance. Furthermore, the evaluation of copper corrosivity is also good. In addition, although Examples 1 to 9 and Comparative Examples 1 to 3 are test examples using resin compositions that differ only in the content of specific components, the content of specific components is 1 mass relative to the total solid content of the resin composition. Examples 1 to 9 of compositions 1 to 9 having ppb or more and 1000 mass ppm or less are compared with Comparative Examples 1 to 3 using resin compositions of compositions 22 to 24 whose content of specific components is outside the above range. The stability evaluation was excellent at 1 rank or higher. In addition, regarding moisture resistance and copper corrosion resistance, it is shown that it is equal to or better than 1 rank. In addition, from 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, and Example 15 and Comparative Example 9. , 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, Example 21 and Comparative Example 15 Results , Also shows the same tendency.

no

no

no.

Claims (15)

A resin composition comprising a polyimide precursor and selected polybenzoxazole precursor㗁azole least one polymer precursor, wherein the ^{_{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 relative to the total solid content of the resin composition is 1 ppb by mass or more and 1000 ppm or less by mass. The resin composition described in item 1 of the scope of the patent application further contains at least one selected from the group consisting of a silane coupling agent, a thermal salt generator, a radical polymerization initiator, and a radical polymerizable compound. Such as the resin composition described in item 1 or item 2 of the scope of patent application, wherein The polymer precursor includes a polyimide precursor. The resin composition described in item 3 of the scope of patent application, wherein the polyimide precursor has a structural unit represented by the following formula (1),

In formula (1), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or Monovalent organic group. The resin composition according to item 4 of the patent application, wherein at least one of R ¹¹³ and R ¹¹⁴ of the formula (1) contains a radical polymerizable group. The resin composition described in item 1 or item 2 of the scope of the patent application is used to develop a pattern by using a developer containing 90% by mass or more of an organic solvent. The resin composition described in item 1 or item 2 of the scope of patent application is used to form a member in contact with metal. The resin composition described in item 1 or item 2 of the scope of patent application is used to form an interlayer insulating film for a rewiring layer. A cured film obtained by curing the resin composition described in any one of items 1 to 8 of the scope of patent application. The cured film as described in item 9 of the scope of patent application has a film thickness of 1 μm to 30 μm. A laminate having two or more layers of the cured film described in item 9 of the scope of patent application, and a metal layer is provided between the two cured films. A method for manufacturing a hardened film, which includes: In the film forming step, the resin composition described in any one of the first to eighth patent applications is applied to a substrate to form a film. The method for manufacturing a cured film as described in item 12 of the scope of patent application has: The exposure step is to expose the film; and In the developing step, the film is developed. The method for producing a cured film as described in item 12 of the scope of patent application includes the step of heating the film at 80°C to 450°C. A semiconductor element having the cured film described in item 9 of the scope of patent application.