TWI763883B - Thermosetting resin composition, cured film thereof, laminate, semiconductor device, and method for producing the same - Google Patents

Abstract

The present invention provides a thermosetting resin composition, cured film, laminate, A semiconductor device, and a method of manufacturing the same. A curable resin composition comprising a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, a salt comprising a cation derived from an amine compound and an anion derived from an acidic compound, and a solvent , the pKa of the conjugated acid of the amine compound and the pKa of the acidic compound are within the following formula 1, 3.5≤(pKa of the conjugated acid of the amine compound+pKa of the acidic compound)/2≤7.1 (Formula 1).

Description

Thermosetting resin composition, cured film thereof, laminate, semiconductor device, and methods for producing the same

The present invention relates to a thermosetting resin composition, a cured film, a method for producing a cured film, a layered product, a method for producing a layered product, a semiconductor device, and a method for producing a semiconductor device.

Since resins such as polyimide resins and polybenzoxazole resins that have been cured by cyclization are excellent in heat resistance and insulating properties, they are used in various applications (for example, see Non-Patent Document 1 and Non-Patent Document 2). The application is not particularly limited, and when a semiconductor device for actual mounting is exemplified, the use as a material for an insulating film or a sealing member can be mentioned. Moreover, it is also used as a base film, a cover film, etc. of a flexible substrate. The above-mentioned polyimide resin and the like generally have low solubility in solvents. Therefore, as an example of applying a polyimide resin or the like to a substrate, a polymer precursor before the cyclization reaction can be used, and specifically, a polyimide precursor resin or a polybenzoxy can be used. An example in which the state of the azole precursor resin is dissolved in a solvent and applied to a substrate or the like. Then, the polymer precursor is cyclized by heating, and a cured resin layer (cured film) can be formed.

Regarding the specific blending related to the composition of the above-mentioned polymer precursor, for example, Patent Document 1 discloses a mixture containing an N-aromatic glycine derivative and a polymer precursor, when several research examples are given. Photosensitive resin composition. Patent Document 2 discloses a polyimide precursor containing a polyimide precursor, a thermal base generator composed of a neutral compound of a second amine by thermal decomposition by heating at a temperature of 200° C. or lower, and a solvent. Imine precursor resin composition. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2006-282880 [Patent Document 2] Japanese Patent Laid-Open No. 2007-056196 [Non-Patent Document]

[Non-patent literature 1] Science & technology Co., Ltd. "High-functionalization and application technology of polyimide" April 2008 [Non-patent literature 2] Masaki Kakimoto/Supervisor, CMC Technical Library "Polyamide" "Basics and Development of Amine Materials" November 2011 issue

As mentioned above, there are several research examples regarding the component composition of the thermosetting resin composition. However, considering these various uses or new uses, it is difficult to say that it has been sufficiently studied in relation to the properties of the resin composition and the cured film after curing. Therefore, an object of the present invention is to provide a new thermosetting resin composition and realize enrichment of materials. In particular, the object is to provide a thermosetting resin composition, a cured film, a laminate, A semiconductor device, and a method of manufacturing the same.

R^B1 ～R^B3 分別獨立地表示氫原子或碳數1～20有機基，且可以彼此連結而形成環，其中，R^B1 ～R^B3 並不全是氫原子。 ＜5＞如＜4＞所述之熱硬化性樹脂組成物，其中 上述式（B1）的R^B1 及R^B2 分別獨立地係碳數1～6的直鏈或支鏈的烷基、環戊基或環己基，R^B3 係氫原子、碳數1～6的直鏈或支鏈的烷基、環戊基、環己基或吡啶基。 ＜6＞如＜1＞至＜5＞中任一項所述之熱硬化性樹脂組成物，其中 上述胺化合物中，與氮原子的距離最遠之碳原子的連結氮原子與上述碳原子之原子的數量係2～5。 ＜7＞如＜1＞至＜6＞中任一項所述之熱硬化性樹脂組成物，其中 上述酸性化合物的pKa係2以下。 ＜8＞如＜1＞至＜7＞中任一項所述之熱硬化性樹脂組成物，其中 上述酸性化合物由下述式（AC1）～（AC5）中的任1個表示， [化學式2]

式中，R^A1 表示羥基或1價有機基，R^A2 ～R^A13 分別獨立地表示氫原子或1價有機基。 ＜9＞如＜1＞至＜8＞中任一項所述之熱硬化性樹脂組成物，其中 上述酸性化合物的分子量係60～500。 ＜10＞如＜1＞至＜9＞中任一項所述之熱硬化性樹脂組成物，其中 上述聚醯亞胺前驅物具有由式（1）表示之重複單元， [化學式3]

A¹ 及A² 分別獨立地表示氧原子或NH，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價有機基，R¹¹⁵ 表示4價有機基，R¹¹¹ 表示2價有機基。 ＜11＞如＜10＞所述之熱硬化性樹脂組成物，其中 上述R¹¹³ 及R¹¹⁴ 中的至少一方係具有乙烯性不飽和鍵之基團。 ＜12＞如＜1＞至＜11＞中任一項所述之熱硬化性樹脂組成物，其還包含光自由基聚合起始劑。 ＜13＞如＜12＞所述之熱硬化性樹脂組成物，其中 上述光自由基聚合起始劑係肟化合物。 ＜14＞如＜1＞至＜13＞中任一項所述之熱硬化性樹脂組成物，其還包含自由基聚合性化合物。 ＜15＞如＜1＞至＜14＞中任一項所述之熱硬化性樹脂組成物，其還包含含有第4族元素之有機化合物。 ＜16＞如＜15＞所述之熱硬化性樹脂組成物，其中 上述第4族元素係選自包括鈦、鋯及鉿之群組中之至少一種元素。 ＜17＞如＜15＞或＜16＞所述之熱硬化性樹脂組成物，其中 上述第4族元素係選自包括鈦及鋯之群組中之至少一種元素。 ＜18＞如＜1＞至＜17＞中任一項所述之熱硬化性樹脂組成物，其為再配線層用層間絕緣膜形成用。 ＜19＞一種硬化膜，其由＜1＞至＜18＞中任一項所述之熱硬化性樹脂組成物形成。 ＜20＞一種積層體，其具有兩層以上的＜19＞所述之硬化膜。 ＜21＞如＜20＞所述之積層體，其具有3～7層上述硬化膜。 ＜22＞如＜20＞或＜21＞所述之積層體，其中 於上述硬化膜之間具有金屬層。 ＜23＞一種硬化膜的製造方法，其具有：層形成步驟，將＜1＞至＜18＞中任一項所述之熱硬化性樹脂組成物應用於基板而將其形成為層狀；加熱步驟，於50～500℃的溫度下對形成為層狀之上述熱硬化性樹脂組成物進行加熱。 ＜24＞一種硬化膜的製造方法，其具有：層形成步驟，將＜1＞至＜18＞中任一項所述之熱硬化性樹脂組成物應用於基板而將其形成為層狀；曝光步驟，對形成為層狀之上述熱硬化性樹脂組成物進行曝光；顯影處理步驟，對經曝光之上述熱硬化性樹脂組成物進行顯影處理；及加熱步驟，於50～500℃的溫度下對經曝光之上述熱硬化性樹脂組成物進行加熱。 ＜25＞一種積層體的製造方法，其於按＜23＞或＜24＞所述之硬化膜的製造方法形成硬化膜之後，還包括按＜23＞或＜24＞所述之硬化膜的製造方法形成硬化膜之步驟。 ＜26＞一種半導體裝置，其具有＜19＞所述之硬化膜或＜20＞至＜22＞中任一項所述之積層體。 ＜27＞一種半導體裝置的製造方法，其中 對＜19＞所述之硬化膜或＜20＞至＜22＞中任一項所述之積層體進行加工來作為半導體裝置。 ＜28＞一種熱硬化性樹脂組成物的製造方法，其包括以上述胺化合物的共軛酸的pKa與酸性化合物的pKa成為下述數式1的範圍之方式對選自聚醯亞胺前驅物及聚苯并㗁唑前驅物中之聚合物前驅物、胺化合物、酸性化合物及溶劑進行混合之步驟， 3.5≤（胺化合物的共軛酸的pKa+酸性化合物的pKa）/2≤7.1 （數式1）。 [發明效果]Based on the above-mentioned subject, as a result of intensive research, the present inventors found that the above-mentioned subject can be solved by blending a predetermined salt with the thermosetting resin composition. Specifically, the above-mentioned problems are solved by the following means <1>, preferably by means of <2> to <28>. <1> A thermosetting resin composition comprising: a polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors; cations derived from amine compounds and cations derived from acidic compounds; Salts of anions; and solvents, the pKa of the conjugated acid of the amine compound and the pKa of the acidic compound are within the range of the following formula 1, 3.5≤(pKa of the conjugated acid of the amine compound+pKa of the acidic compound)/2≤7.1 (Equation 1). <2> The thermosetting resin composition according to <1>, wherein the amount of the acid group of the acidic compound is 0.9 to 3.0 equivalents relative to the amount of the amine group of the amine compound. <3> The thermosetting resin composition according to <1> or <2>, wherein the molecular weight of the amine compound is 120 to 1000. <4> The thermosetting resin composition according to any one of <1> to <3>, wherein the amine compound is represented by the following formula (B1), [Chemical formula 1]

R ^B1 to R ^B3 each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms, and may be linked to each other to form a ring, but not all of R ^B1 to R ^B3 are hydrogen atoms. <5> The thermosetting resin composition according to <4>, wherein R ^B1 and R ^B2 of the above formula (B1) are each independently a linear or branched alkyl group having 1 to 6 carbon atoms, cyclopentane or cyclohexyl, R ^B3 represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a cyclopentyl group, a cyclohexyl group or a pyridyl group. <6> The thermosetting resin composition according to any one of <1> to <5>, wherein in the above-mentioned amine compound, the linking nitrogen atom of the carbon atom farthest from the nitrogen atom and the above-mentioned carbon atom; The number of atoms is 2 to 5. <7> The thermosetting resin composition according to any one of <1> to <6>, wherein the acidic compound has a pKa of 2 or less. <8> The thermosetting resin composition according to any one of <1> to <7>, wherein the acidic compound is represented by any one of the following formulae (AC1) to (AC5), [Chemical formula 2 ]

In the formula, R ^A1 represents a hydroxyl group or a monovalent organic group, and R ^A2 to R ^A13 each independently represent a hydrogen atom or a monovalent organic group. <9> The thermosetting resin composition according to any one of <1> to <8>, wherein the acidic compound has a molecular weight of 60 to 500. <10> The thermosetting resin composition according to any one of <1> to <9>, wherein the polyimide precursor has a repeating unit represented by formula (1), [Chemical formula 3]

A1 and A2 each independently represent ^an oxygen atom or NH, ^R113 and ^R114 each independently represent a ^hydrogen atom or a monovalent organic group, ^R115 represents a tetravalent organic group, and ^R111 represents a divalent organic group. <11> The thermosetting resin composition according to <10>, wherein at least one of the above R ¹¹³ and R ¹¹⁴ is a group having an ethylenically unsaturated bond. <12> The thermosetting resin composition according to any one of <1> to <11>, further comprising a photoradical polymerization initiator. <13> The thermosetting resin composition according to <12>, wherein the photoradical polymerization initiator is an oxime compound. <14> The thermosetting resin composition according to any one of <1> to <13>, which further contains a radically polymerizable compound. <15> The thermosetting resin composition according to any one of <1> to <14>, further comprising an organic compound containing a Group 4 element. <16> The thermosetting resin composition according to <15>, wherein the Group 4 element is at least one element selected from the group consisting of titanium, zirconium, and hafnium. <17> The thermosetting resin composition according to <15> or <16>, wherein the Group 4 element is at least one element selected from the group consisting of titanium and zirconium. <18> The thermosetting resin composition according to any one of <1> to <17>, which is for forming an interlayer insulating film for a rewiring layer. <19> A cured film formed from the thermosetting resin composition according to any one of <1> to <18>. <20> A laminate having two or more layers of the cured film described in <19>. <21> The laminated body as described in <20> which has 3-7 layers of the said cured film. <22> The laminated body as described in <20> or <21> which has a metal layer between the said cured films. <23> A method for producing a cured film comprising: a layer forming step of applying the thermosetting resin composition according to any one of <1> to <18> to a substrate to form a layer; heating In the step, the above-mentioned thermosetting resin composition formed into a layer is heated at a temperature of 50 to 500°C. <24> A method for producing a cured film comprising: a layer forming step of applying the thermosetting resin composition according to any one of <1> to <18> to a substrate to form a layer; exposing a step of exposing the thermosetting resin composition formed in a layered shape; a developing treatment step, developing treatment of the exposed thermosetting resin composition; and a heating step, at a temperature of 50-500 ℃ The above-mentioned thermosetting resin composition exposed to light is heated. <25> A method for producing a laminated body, which further includes the production of the cured film described in <23> or <24> after forming a cured film according to the method for producing a cured film described in <23> or <24> The method comprises the steps of forming a cured film. <26> A semiconductor device having the cured film described in <19> or the laminate described in any one of <20> to <22>. <27> The manufacturing method of a semiconductor device which processes the cured film as described in <19> or the laminated body as described in any one of <20> to <22> as a semiconductor device. <28> A method for producing a thermosetting resin composition, which comprises treating a polyimide precursor selected from the group consisting of a polyimide precursor such that the pKa of the conjugated acid of the amine compound and the pKa of the acidic compound are in the range of the following formula 1. and the step of mixing the polymer precursor, amine compound, acid compound and solvent in the polybenzoxazole precursor, 3.5≤(pKa of the conjugated acid of the amine compound + pKa of the acid compound)/2≤7.1 (the formula 1). [Inventive effect]

According to the present invention, it is possible to provide a novel thermosetting resin composition and to realize enrichment of materials. In particular, it is possible to provide a thermosetting resin composition, a cured film, a laminate, and a semiconductor, which is excellent in the time-dependent variation in the film thickness of the film formed from the thermosetting resin composition and which is excellent in strength as a cured film. devices, and methods for producing the same.

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

The description of the constituent elements in the present invention described below may be based on representative embodiments of the present invention, but the present invention is not limited to these embodiments. Regarding the labels of groups (atomic groups) in the present specification, labels that are not substituted and unsubstituted include both those having no substituent and those having a substituent. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). In this specification, "exposure" is not particularly limited, and in addition to exposure with light, drawing with particle beams such as electron beams and ion beams is also included in exposure. Moreover, as light used for exposure, the bright-line spectrum of a mercury lamp, and active rays such as extreme ultraviolet rays, extreme ultraviolet rays (EUV light), X-rays, and electron beams represented by excimer lasers, X-rays, and electron beams, and radiation are generally mentioned. In this specification, "(meth)acrylate" means both or either one of "acrylate" and "methacrylate", and "(meth)acrylic acid" means "acrylic acid" and "methacrylic acid" Both or any one of them, "(meth)acryloyl group" means both or either one of "acryloyl group" and "methacryloyl group". In this specification, the term "step" is not only an independent step, but also included in the term if it can achieve the expected effect of the step even if it cannot be clearly distinguished from other steps. In the present specification, the solid content refers to the mass percentage of components other than the solvent in the total mass of the composition. In addition, unless otherwise stated, the solid content concentration refers to the concentration at 25°C. In this specification, unless otherwise stated, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as styrene-equivalent values based on gel permeation chromatography (GPC measurement). 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 HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) were obtained. Unless otherwise stated, the eluent was measured by THF (tetrahydrofuran). In addition, unless otherwise stated, the detection is made by using a detector with a wavelength of 254 nm of UV rays (ultraviolet rays). Unless otherwise specified, the physical property values in the present invention are assumed to be values of a temperature of 25° C. and an air pressure of 1013.25 hPa.

The thermosetting resin composition of the present invention (hereinafter, sometimes simply referred to as "the composition of the present invention" and "the resin composition of the present invention") contains a precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor. Among them, the polymer precursor, the thermosetting resin composition comprising the salt of the cation derived from the amine compound and the anion derived from the acidic compound, and the solvent are characterized by the pKa of the conjugate acid of the amine compound and the pKa of the acidic compound. pKa is within the range of the following formula 1. 3.5≤(pKa of the conjugated acid of the amine compound+pKa of the acidic compound)/2≤7.1 (Formula 1) With these constitutions, it is possible to provide a time-dependent change in film thickness of a film formed from a thermosetting resin composition Thermosetting resin composition that is small and has excellent strength when used as a cured film. That is, as a result of research conducted by the present inventors, it was confirmed that the acidic compound contributes to the time-dependent variation in the film thickness of the film mainly formed of the composition, and that the amine compound contributes to the film strength after curing. However, there is an unexpected point in the blending balance, which was observed through various experimental confirmations and analyses, based on the pKa of the two compounds, and by specifying the blending balance.

<Polymer Precursor> The thermosetting resin composition of the present invention contains a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor. As the polymer precursor, a polyimide precursor is more preferable, and a polyimide precursor containing a repeating unit represented by formula (1) described later is further preferable.

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，R¹¹⁵ 表示4價有機基，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價有機基。<<Polyimide precursor>> As the polyimide precursor, it is preferable to contain a repeating unit represented by the following formula (1). [Chemical formula 4]

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 a monovalent organic group. organic base.

A ¹ and A ² in the formula (1) are each independently an oxygen atom or NH, preferably an oxygen atom. R ¹¹¹ in formula (1) represents a divalent organic group. Examples of the divalent organic group include linear or branched aliphatic groups, cyclic aliphatic groups, aromatic groups (including heterocyclic groups), or groups composed of combinations of these, and linear or branched carbon atoms having 2 to 20 carbon atoms are exemplified. Chain aliphatic groups, branched chain aliphatic groups with 3 to 20 carbon atoms, cyclic aliphatic groups with 3 to 20 carbon atoms, aromatic groups with 6 to 20 carbon atoms, or groups composed of these combinations are preferred , and aromatic groups with 6 to 20 carbon atoms are more preferred.

R ¹¹¹ is preferably derived from a diamine. As a diamine used for manufacture of a polyimide precursor, a linear or branched aliphatic, cyclic aliphatic, or aromatic diamine etc. are mentioned. Only one type of diamine may be used, or two or more types may be used. Specifically, the diamine contains a linear aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof. A group is preferable, and a diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable. As an example of an aromatic group, the following aromatic group is mentioned.

[Chemical formula 5]

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

Specific examples of the diamine include 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 isophoronediamine; 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, 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) bis(4-amino-3-hydroxyphenyl) bis(4-amino-3-hydroxyphenyl) bis(4-amino-3-hydroxyphenyl), 4,4'-diamino-terphenyl, 4,4'-bis(4- Aminophenoxy) biphenyl, bis[4-(4-aminophenoxy)phenyl]sine, bis[4-(3-aminophenoxy)phenyl]sine, bis[4-( 2-Aminophenoxy)phenyl] benzene, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-bis Methyl-4,4'-diaminodiphenyl benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene 3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diphenylmethane Aminodiphenylmethane, 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-amino) Phenyl) phenyl, 4,4'-dimethyl-3,3'-diaminodiphenyl, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenyl Phenylmethane, 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-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzylaniline, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, Diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4- Aminophenyl) decafluoropentane, 1,7-bis(4-aminophenyl)tetrafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexa Fluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-di Methylphenyl]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-amine yl-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl, 4,4'-bis(3 -Amino-5-trifluoromethylphenoxy)diphenyl, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2 ,2',5,5',6,6'-hexafluorobenzidine and at least one diamine in 4,4'-diaminotetraphenyl.

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

[Chemical formula 6]

[Chemical formula 7]

Moreover, as a preferable example, the diamine which has at least 2 or more alkylene glycol units in a main chain is also mentioned. Preferably, it is a diamine containing either one or both of two or more ethylene glycol chains and propylene glycol chains in combination in one molecule, and more preferably a diamine that does not contain an aromatic ring. Specific examples include JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR- 148. JEFFAMINE (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (the above are product names, manufactured by HUNTSMAN), 1-(2-(2-(2-amino) Propoxy)ethoxy)propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, etc. , but not limited to 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) registered trademark) Structure of EDR-176.

[Chemical formula 8]

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

From the viewpoint of the flexibility of the cured film obtained, R ¹¹¹ is preferably represented by -Ar ⁰ -L-Ar ⁰ -. Among them, Ar ⁰ is each independently an aromatic hydrocarbon group (the number of carbon atoms is preferably 6-22, more preferably 6-18, and particularly preferably 6-10), and L is a group containing 1-10 carbon atoms that can be substituted by fluorine atoms. aliphatic hydrocarbon group, -O-, -CO-, -S-, -SO ₂ - or -NHCO-, and a group comprising a combination of two or more of the above. Ar ⁰ is preferably a phenylene group, and L is an aliphatic hydrocarbon group having 1 to 3 carbon atoms, -O-, -CO-, -S- or -SO ₂ - which may be substituted by a fluorine atom. Among them, the aliphatic hydrocarbon group is preferably an alkylene group. The aromatic hydrocarbon group (preferably a phenylene group) constituting Ar ⁰ may have an arbitrary substituent T (eg, a hydroxyl group) within the range in which the effects of the present invention are exhibited.

式（51）中，R⁵⁰ ～R⁵⁷ 分別獨立地為氫原子、氟原子或1價有機基，R⁵⁰ ～R⁵⁷ 中的至少1個為氟原子、甲基、氟甲基、二氟甲基或三氟甲基。 當R⁵⁰ ～R⁵⁷ 為1價有機基時，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。 式（61） [化學式10]

式（61）中，R⁵⁸ 及R⁵⁹ 分別獨立地為氟原子、氟甲基、二氟甲基或三氟甲基。 作為賦予式（51）或（61）的結構之二胺化合物，可舉出二甲基-4,4’-二胺基聯苯、2,2’-雙（三氟甲基）-4,4’-二胺基聯苯、2,2’-雙（氟）-4,4’-二胺基聯苯、4,4’-二胺基八氟聯苯等。可以使用該等中的一種，亦可以組合使用兩種以上。When imparting photosensitivity to the thermosetting resin composition, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or (61) from the viewpoint of i-ray transmittance. In particular, the divalent organic group represented by the formula (61) is more preferable from the viewpoints of i-ray transmittance and availability. Formula (51) [Chemical Formula 9]

In formula (51), R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group, a fluoromethyl group, or a difluoromethyl group group or trifluoromethyl. When R ⁵⁰ to R ⁵⁷ are monovalent organic groups, examples include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably carbon atoms of 1 to 6), carbon atoms of 1 to 10 (preferably carbon atoms of 1 to 6). 1-6) fluorinated alkyl groups, etc. Formula (61) [Chemical Formula 10]

In formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group. As the diamine compound giving the structure of 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 may be used in combination.

式（5）中，R¹¹² 可以是單鍵或可以經氟原子取代之碳數1～10的脂肪族烴基、選自-O-、-CO-、-S-、-SO₂ -、-NHCO-亦即該等的組合中之基團為較佳，單鍵、可以經氟原子取代之碳數1～3的伸烷基、選自-O-、-CO-、-S-及-SO₂ -中之基團為更佳，選自包括-CH₂ -、-C（CF₃ ）₂ -、-C（CH₃ ）₂ -、-O-、-CO-、-S-及-SO₂ -之群組中之2價基為進一步較佳。R ¹¹⁵ in formula (1) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable. In addition, the benzene ring in the formula may have a substituent T (eg, a hydroxyl group). Formula (5) [Chemical Formula 11]

In formula (5), R ¹¹² may be a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, selected from -O-, -CO-, -S-, -SO ₂ -, -NHCO -That is, the groups in these combinations are preferably, single bonds, alkylene groups with 1 to 3 carbon atoms that can be substituted by fluorine atoms, selected from -O-, -CO-, -S- and -SO The group in _2- is more preferably selected from the group consisting of -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S- and -SO The ₂ -valent base in the group of 2- is further preferred.

Formula (6) [Chemical Formula 12]

式（O）中，R¹¹⁵ 表示4價有機基。R¹¹⁵ 的定義與式（1）的R¹¹⁵ 相同。具體而言，可舉出式（5）或（6）的4價有機基。Specific examples of the tetravalent organic group represented by R ¹¹⁵ in the formula (1) include the tetracarboxylic acid residue remaining after removing the acid dianhydride group from the tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (O). Formula (O) [Chemical Formula 13]

In formula (O), R ¹¹⁵ represents a tetravalent organic group. The definition of R ¹¹⁵ is the same as that of R ¹¹⁵ of formula (1). Specifically, the tetravalent organic group of formula (5) or (6) is mentioned.

Specific examples of tetracarboxylic dianhydrides include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3 ',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane Ketonetetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3 ,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic 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 -Phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethanedianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethanedianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethanedianhydride At least one of 2,3,4-benzenetetracarboxylic dianhydride and these alkyl derivatives having 1 to 6 carbon atoms and/or alkoxy derivatives having 1 to 6 carbon atoms.

Moreover, the tetracarboxylic dianhydride (DAA-1) - (DAA-5) shown below are also mentioned as a preferable example. [Chemical formula 14]

R ¹¹³ and R ¹¹⁴ in formula (1) each independently represent a hydrogen atom or a monovalent organic group. In the case of imparting photosensitivity to the thermosetting resin composition as a photosensitive resin composition, it is preferable that at least one of R ¹¹³ and R ¹¹⁴ contains a radical polymerizable group, and it is more preferable that both of them contain a radical polymerizable group. . The radical polymerizable group is a group capable of performing a crosslinking reaction by the action of a radical, and a group having an ethylenically unsaturated bond is mentioned as a preferable example. As a group which has an ethylenically unsaturated bond, a vinyl group, an allyl group, a (meth)acryloyl group, the group represented by following formula (III), etc. are mentioned.

[Chemical formula 15]

In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, more preferably a methyl group. In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH(OH)CH ₂ - or a (poly)oxyalkylene group having 4 to 30 carbon atoms (as an alkylene group, carbon Numbers 1 to 12 are preferred, 1 to 6 are more preferred, and 1 to 3 are particularly preferred; the number of repetitions is preferably 1 to 12, more preferred is 1 to 6, and 1 to 3 is particularly preferred). In addition, the (poly)oxyalkylene group refers to an oxyalkylene group or a polyoxyalkylene group. Examples of preferable R ²⁰¹ include ethylidene, propylidene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, Hexamethylene, octamethylene, _dodecylene , -CH2CH ₍ OH)CH2-, ethylidene, propylidene, trimethylene, -CH2CH ₍ OH) _CH2- are better. Particularly preferred is that R ²⁰⁰ is a methyl group, and R ²⁰¹ is an ethyl group.

In another example of the embodiment of the polyimide precursor in the present invention, as the monovalent organic group of R ¹¹³ or R ¹¹⁴ , there may be 1, 2 or 3, preferably 1 acid aliphatic, aromatic, and aralkyl groups. 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, the phenyl group which has an acid group and the benzyl group which has an acid group are mentioned. The acid group is preferably a hydroxyl group. That is, R ¹¹³ or R ¹¹⁴ is preferably a group having a hydroxyl group. As the monovalent organic group represented by R ¹¹³ or R ¹¹⁴ , a substituent which increases the solubility of a developer can be preferably used. From the viewpoint of solubility in an aqueous developer, R ¹¹³ or R ¹¹⁴ is a hydrogen atom, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group, and a 4-hydroxybenzyl group, more preferably.

From the viewpoint of solubility in organic solvents, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. The monovalent organic group preferably includes a straight-chain or branched-chain alkyl group, a cyclic alkyl group, and an aromatic group, and more preferably an alkyl group substituted with an aromatic group. The carbon number of the alkyl group is preferably 1 to 30 (3 or more when it is cyclic). The alkyl group may be any one of straight chain, branched chain and cyclic. Examples of linear or branched alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl Alkyl, octadecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, 1-ethylpentyl and 2-ethylhexyl. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. As a monocyclic cyclic alkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group are mentioned, for example. Examples of the polycyclic cyclic alkyl group include adamantyl, norbornyl, camphenyl, camphenyl, decalinyl, tricyclodecyl, tetracyclodecyl, camphenyl Diacyl, dicyclohexyl and pinenyl. Among them, the cyclohexyl group is the most suitable from the viewpoint of achieving both high sensitivity. Further, as the alkyl group substituted with an aromatic group, a straight-chain alkyl group substituted with an aromatic group described later is preferable. Examples of the aromatic group include substituted or unsubstituted benzene rings, naphthalene rings, pentavinyl rings, indene rings, azulene rings, heptavine rings, indene rings, perylene rings, condensed pentaphenyl rings, acenaphthene rings Alkene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring, tetraphenyl ring, triphenylene ring, perylene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring , pyridine ring, pyrimidine ring, pyridyl ring, indole ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinoline ring, quinoline ring, phthalein ring, naphthalene pyridine ring, quinoline ring, quinazoline ring, isoquinoline ring, carbazole ring, phenanthrene ring, acridine ring, phenanthrene ring, thianthrene ring, chromene ring, mouth Yamaguchi star ring, phenothia ring, phenothia 𠯤 ring or fen 𠯤 ring. The benzene ring is the best.

In addition, in the polyimide precursor, it is also preferable to have a fluorine atom in the structural unit. The content of fluorine atoms 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.

Moreover, in order to improve the adhesiveness with a board|substrate, the aliphatic group which has a siloxane structure and the repeating unit represented by Formula (1) can be copolymerized. Specifically, as a diamine component, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. are mentioned.

式（1-A）中，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，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價有機基，R¹¹³ 及R¹¹⁴ 中的至少一者為包含自由基聚合性基之基團，自由基聚合性基為較佳。The repeating unit represented by the formula (1) is preferably the repeating unit represented by the formula (1-A). [Chemical formula 16]

In formula (1-A), A ¹¹ and A ¹² represent an oxygen atom or NH, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, At least one of R ¹¹³ and R ¹¹⁴ is a group containing a radical polymerizable group, and a radical polymerizable group is preferable.

The definitions of A ¹¹ , A ¹² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ are the same as those of A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (1), respectively, and their preferred ranges are also the same. The definition of R ¹¹² is the same as that of R ¹¹² in formula (5), and the preferred range is also the same.

In the polyimide precursor, the repeating unit represented by the formula (1) may be one kind or two or more kinds. Also, structural isomers of the repeating unit represented by the formula (1) may be included. Moreover, in addition to the repeating unit of the above-mentioned formula (1), the polyimide precursor may contain other kinds of repeating structural units.

As an embodiment of the polyimide precursor in the present invention, 50 mol % or more of the total repeating units, further 70 mol % or more, especially 90 mol % or more can be exemplified by the formula (1). Polyimide precursors of repeating units. The upper limit 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 even more preferably 10,000 to 50,000. Furthermore, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The degree of dispersion of the polyimide precursor is preferably 1.5 to 3.5, and more preferably 2 to 3.

The polyimide precursor can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. After halogenating a dicarboxylic acid or a dicarboxylic acid derivative using a halogenating agent, it is preferably obtained by 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 examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone.

When manufacturing the polyimide precursor, it is preferable to include a step of precipitating a solid. Specifically, solid precipitation can be performed by precipitating the polyimide precursor in the reaction liquid in water, and dissolving the polyimide precursor such as tetrahydrofuran in a soluble solvent.

式（2）中，R¹²¹ 表示2價有機基，R¹²² 表示4價有機基，R¹²³ 及R¹²⁴ 分別獨立地表示氫原子或1價有機基。<<Polybenzoxazole precursor>> It is preferable that the polybenzoxazole precursor used by this invention contains the repeating unit represented by following formula (2). [Chemical formula 17]

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

In formula (2), R ¹²¹ represents a divalent organic group. The divalent organic group includes aliphatic groups (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and particularly preferably 1 to 6) and aromatic groups (preferably having 6 to 22 carbon atoms, and 6 to 6). 14 is more preferable, and at least one of 6-12 is particularly preferable) is preferable. Examples of the group containing the aromatic group constituting R ¹²¹ include R ¹¹¹ in the above formula (1). As said aliphatic group, a straight-chain aliphatic group is preferable. R ¹²¹ is preferably derived from 4,4'-oxodibenzyl chloride. In formula (2), R ¹²² represents a tetravalent organic group. As a tetravalent organic group, the definition is the same as that of R ¹¹⁵ in the above formula (1), and the preferable range is also the same. R ¹²² is preferably derived from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane. R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group, and have the same definitions as R ¹¹³ and R ¹¹⁴ in the above formula (1), and their preferred ranges are also the same.

In addition to the repeating units of the above-mentioned formula (2), the polybenzoxazole precursor may also contain other kinds of repeating structural units. It is preferable that the precursor contains a diamine residue represented by the following formula (SL) as another kind of repeating structural unit from the viewpoint that the occurrence of warpage of the cured film accompanying ring closure can be suppressed.

式（SL）中，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1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，且可以分別相同亦可以不同。a結構及b結構的聚合可以是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 18]

In formula (SL), Z has a structure and b structure, R ^1s is a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms (preferably carbon number 1-6, more preferably carbon number 1-3), R ^2s is A hydrocarbon group having 1 to 10 carbon atoms (preferably having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and at least one of R ^3s , R ^4s , R ^5s and R ^6s is an aromatic group (preferably is carbon number 6-22, more preferably carbon number 6-18, particularly preferably carbon number 6-10), and the remainder is hydrogen atom or carbon number 1-30 (preferably carbon number 1-18, more preferably carbon number 1-30) The organic groups having 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms), 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 5-95 mol %, the b structure is 95-5 mol %, and a+b is 100 mol %.

In the formula (SL), as preferable Z, those in which R ^5s and R ^6s in the structure b are phenyl groups are exemplified. Moreover, the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. The molecular weight can be determined by a commonly used gel permeation chromatography method. By making the said molecular weight into the said range, the elastic modulus after the dehydration ring closure of a polybenzoxazole precursor is reduced, and the effect of suppressing warpage and the effect of improving solubility can be combined.

When the precursor contains the diamine residue represented by the formula (SL) as another type of repeating structural unit, the tetracarboxylic acid remaining after removing the acid dianhydride from the tetracarboxylic dianhydride is also included from the viewpoint of improving the alkali solubility. Acid residues are preferred as repeating structural units. As an example of such a tetracarboxylic-acid residue, 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 even more preferably 10,000 to 50,000. Furthermore, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The degree of dispersion of the polybenzoxazole precursor is preferably 1.5-3.5, more preferably 2-3.

The content of the polymer precursor in the thermosetting resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more with respect to the total solid content of the composition , 50 mass % or more is further preferable, 60 mass % or more is further preferable, and 70 mass % or more is further preferable. In addition, the content of the polymer precursor in the thermosetting resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, and further more preferably 98% by mass or less with respect to the total solid content of the composition. Preferably, 95 mass % or less is further preferable, 93 mass % or less is further preferable, and 90 mass % or more is further preferable. The thermosetting resin composition of the present invention may contain only one type of polymer precursor, or may contain two or more types. When two or more types are contained, it is preferable that the total amount falls within the above-mentioned range.

<Salt containing cation derived from amine compound and anion derived from acidic compound> The composition of the present invention contains a salt containing a cation derived from an amine compound and an anion derived from an acidic compound. In the present invention, the blending ratio of these compounds in the salt containing the cation derived from the amine compound and the anion derived from the acidic compound can be appropriately set according to the application or required properties, but the amount of the amine group in the amine compound is The amount of the acid group of the acidic compound is preferably in the range of 0.5 equivalent or more, more preferably in the range of 0.7 equivalent or more, and particularly preferably in the range of 0.9 equivalent or more. As an upper limit, the amount of the acid group of the acidic compound is preferably in the range of 5.0 equivalents or less, more preferably in the range of 4.0 equivalents or less, and particularly preferably in the range of 3.0 equivalents or less. By setting the amount of the acid group to 0.5 equivalent or more, the film thickness variation with time can be further effectively suppressed, and by setting the amount to 3.0 equivalent or less, imidization at the time of heat curing is accelerated, and the film strength is further improved. trend.

In the thermosetting resin composition of the present invention, the specific value (A-pKa) defined by the pKa of the conjugated acid of the amine compound and the pKa of the acidic compound contained therein satisfies the range of the following formula 1. A-pKa=(pKa of conjugate acid of amine compound+pKa of acidic compound)/2 Formula (1a) 3.5≤A-pKa≤7.1 (Formula 1) The lower limit of A-pKa is preferably 3.8 or more , 4.0 or higher is better, and 5.0 or higher is also possible. The upper limit is preferably 7.0 or less, and may be 6.9 or less, or 6.8 or less. In particular, A-pKa contributes to the suppression of the change of the film thickness over time below the above-mentioned upper limit value. On the other hand, the strength of the cured film can be improved by setting the above-mentioned lower limit value or more. The absolute value of the difference between the molecular weight of the amine compound and the molecular weight of the acidic compound is preferably 30 or more, more preferably 50 or more, more preferably 70 or more, and particularly preferably 80 or more. The upper limit is not particularly limited, but is actually 500 or less. By making the absolute value of the said difference 30 or more, the ratio of the amine compound with respect to the acidic compound remaining in a film at the time of heat hardening becomes large, and a hardening reaction is accelerated|stimulated more effectively. In addition, in the salt containing the cation derived from the amine compound and the anion derived from the acidic compound, the total amount added does not need to satisfy the above-mentioned conditions, and at least one of them may satisfy the above-mentioned conditions within the scope of exhibiting the effects of the present invention. Specifically, 70% by mass or more of the salt containing the cation derived from the amine compound and the anion derived from the acidic compound contained in the thermosetting resin composition preferably satisfies the above conditions, and more preferably 80% by mass or more, 90 mass % or more is particularly preferred. The upper limit is 100 mass % or less.

The content of the salt containing the cation derived from the amine compound and the anion derived from the acidic compound in the thermosetting resin composition of the present invention is preferably 0.1 part by mass or more, preferably 0.2 part by mass with respect to 100 parts by mass of the polymer precursor. The above is more preferable, and 0.4 mass part or more is further preferable. The content of the above-mentioned salt is more preferably 5 parts by mass or less, more preferably 3 parts by mass or less, more preferably less than 2 parts by mass, more preferably less than 1.8 parts by mass, and more preferably less than 1.8 parts by mass with respect to 100 parts by mass of the polymer precursor, and 1.5 Parts by mass or less are more preferable. In addition, in addition to the said salt, it is not excluded that a part of an acidic compound and an amine compound exists as an acidic compound or an amine compound without forming a salt in a thermosetting resin composition. Moreover, in addition to the said salt, a part of an acidic compound may form a salt with the quaternary ammonium cation of the hardening accelerator mentioned later.

<<amine compound>> The amine compound in the present invention refers to a compound having an amine moiety (-N<) in the molecule (however, it is not ammonia (NH ₃ )). Regarding the amine compound in the present invention, specifically, a compound represented by the following formula (B1) is preferable.

[Chemical formula 19]

R ^B1 to R ^B3 each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms, and may be connected to each other to form a ring. As the organic group with 1 to 20 carbon atoms, straight or branched chain alkyl group with 1 to 20 carbon atoms, cycloalkyl group with 3 to 20 carbon atoms, aryl group with 6 to 20 carbon atoms, 1 to 20 carbon atoms (more Preferably, it is a heteroaryl group having 2 to 10 carbon atoms, and the special price is a heteroaryl group having a carbon number of 3 to 6). As a hetero atom contained in a heteroaryl group, an oxygen atom, a nitrogen atom, and a sulfur atom are mentioned. The heteroaryl group is preferably a 5- or 6-membered ring group, and examples thereof include a pyrrolyl group, a pyridyl group, a pyrazolyl group, an imidazolyl group, a benzimidazolyl group, a triazolyl group, a thiazolyl group, and an oxazolyl group. Heteroaryls are preferably substituted with hydrogen based on carbon positions. When R ^B1 to R ^B3 are organic groups having 1 to 20 carbon atoms, they may have the following substituent T within the range in which the effects of the present invention are exhibited. Examples of the optional substituent T include straight-chain or branched-chain alkyl groups (preferably with 1 to 24 carbon atoms, more preferably 1 to 12, and particularly preferably 1 to 6), cycloalkyl groups (with 3 to 3 carbon atoms). 24 is better, 3-12 is better, 3-6 is particularly good), straight-chain or branched alkenyl (carbon number 2-24 is better, 2-12 is better, 2-6 is particularly good ), cycloalkenyl (preferably carbon number 3-24, more preferably 3-12, especially 3-6), hydroxyl, hydroxyalkyl (preferably carbon number 1-24, more preferably 1-12 preferably, 1-6 is particularly preferred; the number of hydroxyl groups is preferably 1-6, more preferably 1-3, the alkyl group can be straight chain or branched chain, chain or cyclic), Hydroxyalkenyl (the number of carbons is 2-24 is better, 2-12 is better, 2-6 is particularly good; the number of hydroxyl groups is 1-6 is better, 1-3 is better, alkenyl can be straight The chain can also be branched, chain-like or cyclic), amino (preferably carbon number 0-24, more preferably 0-12, particularly preferred 0-6), aminoalkyl ( The number of carbon atoms is preferably 1-24, more preferably 1-12, and particularly preferably 1-6; the number of amine groups is preferably 1-6, more preferably 1-3, and the alkyl group can be straight chain or can be It is a branched chain, which can be chain or cyclic), amino alkenyl (carbon number 2-24 is preferred, 2-12 is more preferred, 2-6 is particularly preferred; the number of amino groups is 1- 6 is preferred, 1 to 3 are more preferred, alkenyl can be straight chain or branched chain, chain or cyclic), thiol group, thiol alkyl group (carbon number 1-24 is Preferably, 1 to 12 is more preferred, and 1 to 6 is particularly preferred; the number of thiol groups is preferably 1 to 6, and 1 to 3 is more preferred. The alkyl group can be straight chain or branched chain. It can be chain or cyclic), thiol alkenyl (the number of carbons is preferably 2-24, more preferably 2-12, and 2-6 is particularly preferred; the number of thiol groups is preferably 1-6 , 1-3 are better, alkenyl can be straight chain or branched chain, can be chain or cyclic), carboxyl, carboxyalkyl (carbon number 1-24 is preferred, 1-12 is More preferably, 1-6 is particularly preferred; the number of carboxyl groups is preferably 1-6, more preferably 1-3, the alkyl group can be straight chain or branched chain, chain or cyclic) , Carboxyl alkenyl (carbon number 2-24 is better, 2-12 is better, 2-6 is particularly good; the number of carboxyl groups is 1-6 is better, 1-3 is better, alkenyl can be Straight chain can also be branched, chain or cyclic), acyloxy (2-12 carbons are preferred, 2-6 are more preferred, 2-3 are particularly preferred), acyloxy ( Carbon number 2-12 is preferred, 2-6 is more preferred, 2-3 is particularly preferred), aryl group (carbon number 7-23 is preferred, 7-19 is more preferred, 7-11 is particularly preferred ), aryloxy (the number of carbons is preferably 7-23, more preferably 7-19, and particularly preferably 7-11), halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), oxygen group (=O), imino group (=NR ^N ), alkylene group (=C(R ^N ) ₂ ) and the like. Among them, as the substituent, a hydroxyl group, an amino group, a carboxyl group, a halogen atom and the like are preferable. R ^N is a hydrogen atom or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3), preferably a hydrogen atom. Further, when the substituent T is a group capable of forming a salt such as a carboxyl group, a salt may be formed with a counter ion (eg, ammonium ion).

Not all of R ^B1 to R ^B3 are hydrogen atoms, but among R ^B1 to R ^B3 , preferably one or less hydrogen atoms are used, and all are more preferably other than hydrogen atoms. In other words, the amine compound is preferably a secondary amine rather than a primary amine, and is preferably a tertiary amine rather than a secondary amine.

Preferably, R ^B1 and R ^B2 are each independently an alkyl group having 1 to 20 carbon atoms (may be linear or branched, and may be chain or cyclic). The alkyl group may have a substituent T. More preferably, it is a linear or branched alkyl group with 1 to 6 carbon atoms, a linear or branched hydroxyalkyl group with 1 to 6 carbon atoms (the number of hydroxyl groups is preferably 1 to 6, more preferably 1 to 3) , straight-chain or branched aminoalkyl with carbon number 1-6 (the number of amino groups is preferably 1-6, 1-3 is better), cycloalkyl with carbon number 3-8 (more preferably cyclic pentyl or cyclohexyl) are preferred. R ^B3 is a hydrogen atom, an alkyl group having 1 to 12 (preferably 1 to 6) carbon atoms (may be linear or branched, chain or cyclic), carbon number 1 to 6 Heteroaryl groups are preferred. More preferably, R ^B3 is a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms (preferably 1 to 6), or a linear or branched chain having 1 to 12 carbon atoms (preferably 1 to 6). Hydroxyalkyl (the number of hydroxyl groups is preferably 1-6, more preferably 1-3), straight-chain or branched aminoalkyl (the number of amino groups is 1-12) (preferably 1-6) The number is preferably 1-6, more preferably 1-3), cycloalkyl with 3-8 carbons (more preferably cyclopentyl or cyclohexyl) or heteroaryl with 3-6 carbons (more preferably is pyridyl) is preferred.

In the compound represented by the formula (B1), as described above, two or more of R ^B1 , R ^B2 and R ^B3 may be bonded to each other to form a ring, or may not be formed, but are preferably formed. It is preferable that the compound represented by the formula (B1) contains a cyclic structure. The cyclic structure may be an aromatic ring, an alicyclic ring, a heterocyclic ring, or a non-heterocyclic ring, but an alicyclic ring is preferred. The ring structure is preferably a 5- to 8-membered ring, more preferably a 6-membered ring. In addition, the cyclic structure may be a monocyclic ring or a condensed ring, but a monocyclic ring is preferable. The compound represented by the formula (B1) preferably contains 1 to 4 cyclic structures per molecule, and may be 2 to 4, or 2 or 3, or may be 2. Moreover, it may have an imine structure (>C=N-) in a ring structure, and it may not have. The compound represented by the formula (B1) preferably has one or two amine structures in one molecule, and more preferably has one. Furthermore, it is preferable that the amine compound does not have a carboxyl group and an ester chain (carbonyloxy group).

In the above-mentioned amine compound, it is preferable that the number of atoms connecting the carbon atom which is the farthest from the nitrogen atom and the number of atoms of the above-mentioned carbon atom is 2 or more. The upper limit of the number of atoms connected is preferably 20 or less, more preferably 12 or less, further preferably 8 or less, and particularly preferably 5 or less. The amine compound has a strong interaction with copper, and therefore tends to be biased on the surface of copper used for wiring in some cases. When the substituent of the amine compound is in this range, even if the amine is concentrated in the copper wiring, the polarity of the surface can be appropriately ensured, so that the decrease in the adhesion with the insulating film can be further effectively suppressed. Specifically, the number of atoms connecting the above-mentioned nitrogen atom and the farthest carbon atom refers to the carbon on the opposite side to the carbon (α carbon) substituted with the nitrogen atom of the 6-membered ring when R ^B1 is a cyclohexyl group Atom becomes the farthest carbon atom. It is the third carbon atom when considered from the above-mentioned α carbon. Therefore, the number of atoms connecting the third carbon atom and the α carbon is two.

The pKa of the conjugate acid of the amine compound is preferably 12.4 or less, more preferably 12.0 or less, further preferably 11.6 or less, and particularly preferably 11.4 or less. As a lower limit, 4.7 or more is preferable, 5.0 or more is more preferable, 6.0 or more is further preferable, and 7.0 or more is especially preferable.

The molecular weight of the amine compound is preferably 90 or more, more preferably 100 or more, more preferably 110 or more, and even more preferably 120 or more. As the upper limit, 1000 or less is preferable, 800 or less is more preferable, 600 or less is further preferable, 400 or less is further preferable, and 300 or less is still more preferable. By setting it as 90 or more, it becomes difficult to volatilize at the time of heat-hardening, it remains in a film, and it becomes easy to function as a hardening accelerator. On the other hand, by setting it as 1000 or less, it becomes easy to diffuse in a film, and it acts more effectively as a hardening accelerator.

As specific examples of the amine compound, the compounds described in paragraphs 0204 and 0205 of Japanese Unexamined Patent Application Publication No. 2011-221494 can be used in addition to the compounds described in the examples to be described later, and these contents are incorporated into the present specification. .

The compounding amount of the amine compound constituting the salt with respect to 100 parts by mass of the polymer precursor is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and further more preferably 3 parts by mass or less Preferably, 2 parts by mass or less is even more preferable. As a lower limit, 0.01 mass part or more is preferable, 0.05 mass part or more is more preferable, 0.1 mass part or more is further preferable, 0.3 mass part or more is further preferable, and 0.5 mass part or more is further preferable. The salt may have only one cation derived from an amine compound, or may have two or more cations derived from an amine compound. When two or more types are included, it is preferable that the total amount falls within the above-mentioned range. also. In addition to the salt containing the cation derived from the amine compound and the anion derived from the acidic compound used in the present invention, the salt containing the cation derived from ammonia may be contained. However, it is preferable that the salt containing the cation derived from ammonia is not substantially contained. Substantially not containing means that the content of the salt containing the cation derived from ammonia is 5 mass % or less, preferably 3 mass % or less, of the content of the salt containing the cation derived from the amine compound and the anion derived from the acidic compound, 1 mass % or less is more preferable.

<<acidic compound>> The acidic compound in this invention means the compound whose pH is less than 7 in an aqueous solution. A compound having an acid group is preferred, and as the acid group, a group that generates free hydrogen in an aqueous solution is preferred. For example, compounds having a sulfonic acid group, a carboxyl group, a phosphonic acid group, a phosphoric acid group, a boronic acid group, etc. are mentioned, and a compound having a sulfonic acid group or a carboxyl group is preferable. The acidic compound in the present invention preferably has one or two acid groups in one molecule. Among them, a compound represented by any one of the following formulae (AC1) to (AC5) is preferred.

[Chemical formula 20]

In the formula, R ^A1 represents a hydroxyl group or a monovalent organic group. Examples of the monovalent organic group include straight-chain or branched-chain alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and particularly preferably 1 to 3), and cycloalkyl groups (having 3 to 3 carbon atoms). 24 is preferred, 3-12 is more preferred, 3-6 is particularly preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-10 is particularly preferred), heteroaryl (The number of carbon atoms is preferably 1 to 12, and more preferably 1 to 6). Among them, straight-chain or branched-chain alkyl groups or aryl groups having the above-mentioned carbon numbers are preferred. These groups may or may not have the substituent T. For example, a group formed by combining an alkyl group and an aryl group (the number of carbon atoms is preferably 7 to 23, more preferably 7 to 19, and particularly preferably 7 to 11), and an aralkyl group (the carbon number is preferably 7 to 11). Number 7-23 is preferred, 7-19 is more preferred, 7-11 is particularly preferred) or alkylaryl (carbon number 7-23 is preferred, 7-19 is more preferred, 7-11 is particularly preferred ).

R ^A2 to R ^A6 each independently represent a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include the groups and carboxyl groups described in the above R ^A1 , and the same groups as the groups described in R ^A1 are more preferred. The monovalent organic group may or may not have the substituent T. R ^A7 to R ^A12 each independently represent a hydrogen atom or a monovalent organic group, preferably a hydrogen atom. As this monovalent organic group, the group with the same definition as the above-mentioned R ^A1 can be mentioned, and the preferable range is also the same. The monovalent organic group may or may not have the substituent T. R ^A13 has a hydrogen atom or a monovalent organic group, preferably a monovalent organic group. As this monovalent organic group, the group with the same definition as the above-mentioned R ^A1 can be mentioned, and the preferable range is also the same. The monovalent organic group may or may not have the substituent T.

The pKa of the acidic compound is preferably 5 or less, more preferably 4 or less, more preferably 3 or less, and may be 2 or less. The lower limit is preferably -5 or more, more preferably -4 or more, and particularly preferably -3 or more. By setting the pKa to 5 or less, the time-dependent decomposition reaction of the polyimide precursor and the polybenzoxazole precursor is further effectively suppressed by the acidic compound, and the time-dependent film thickness change can be further effectively suppressed.

The molecular weight of the acidic compound is preferably 50 or more, more preferably 60 or more, more preferably 70 or more, and even more preferably 80 or more. The upper limit is preferably 1000 or less, more preferably 700 or less, further preferably 500 or less, further preferably 300 or less, and particularly preferably 200 or less. Moreover, by making the molecular weight of an acidic compound into 1000 or less, it is hard to remain|survive in a film in a heat hardening process, a hardening reaction progresses efficiently, and there exists a tendency for film strength to improve. By setting the molecular weight to be 50 or more, the composition is less likely to volatilize during storage, and the change in film thickness with time can be further effectively suppressed.

The compounding amount of the acidic compound constituting the salt is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and may be 3 parts by mass with respect to 100 parts by mass of the polymer precursor. the following. As a lower limit, 0.01 mass part or more is preferable, 0.05 mass part or more is more preferable, 0.1 mass part or more is more preferable, 0.3 mass part or more is further preferable, and 0.5 mass part or more may be sufficient. The acidic compound may have only one anion derived from an acidic compound, or may have two or more anions derived from an acidic compound. When two or more types are included, it is preferable that the total amount falls within the above-mentioned range.

<Solvent> The thermosetting resin composition of the present invention contains a solvent. Any known solvent can be used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfites, and amides. As esters, for example, preferable ones include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate esters, butyl butyrate, methyl lactate, ethyl lactate, gamma-butyrolactone, epsilon-caprolactone, delta-valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, Ethoxyacetate, butyl alkoxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate etc.), alkyl 3-alkoxypropanoates (for example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropanoate, etc. (for example, methyl 3-methoxypropionate) , ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkoxypropionate alkyl esters (for example, 2- Methyl alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate , propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and 2- Ethyl alkoxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate ester, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc. As ethers, for example, preferable ones include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, and 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 ketones, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, etc. are mentioned, for example as preferable ones. As aromatic hydrocarbons, for example, preferable ones include toluene, xylene, anisole, limonene, and the like. As the sulfites, for example, dimethyl sulfite is mentioned as a preferable one. As the amides, preferred ones include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylmethane Amide, etc.

Regarding the solvent, it is also preferable to mix two or more types from the viewpoint of improvement of the coating surface shape and the like. 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 Ester, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, gamma-butyrolactone, dimethylsulfoxide, ethyl carbitol acetate, butyl carbitol One solvent or a mixed solvent consisting of two or more of alcohol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate is preferred. It is particularly preferred to use dimethyl sulfoxide and γ-butyrolactone together.

Regarding the content of the solvent, from the viewpoint of coatability, the total solid content concentration of the thermosetting resin composition of the present invention is preferably 5 to 80% by mass, and the thermosetting resin of the present invention is used as the content of the solvent. The total solid content concentration of the composition is more preferably an amount of 5 to 75 mass %, and the total solid content concentration of the thermosetting resin composition of the present invention is more preferably an amount of 10 to 70 mass %. More preferably, the total solid content concentration of the thermosetting resin composition of the present invention is 40 to 70% by mass. The content of the solvent may 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, it is preferable that the total is within the above-mentioned range.

<Radical Photopolymerization Initiator> The thermosetting resin composition of the present invention may contain a photoradical polymerization initiator to impart photosensitivity. The photoradical polymerization initiator that can be used in the present invention is not particularly limited, and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light from the ultraviolet region to the visible region is preferable. In addition, it may be an activator that has some effect on a photo-excited sensitizer to generate active radicals. Preferably, the photoradical polymerization initiator contains at least one compound having an absorption coefficient of at least about 50 molar in the range of about 300-800 nm (preferably 330-500 nm). The molar absorption coefficient of the compound can be measured by a known method. For example, it is preferable to measure at a concentration of 0.01 g/L with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent.

Since the thermosetting resin composition contains a photo-radical polymerization initiator, the thermosetting resin composition of the present invention is applied to a substrate such as a semiconductor wafer to form a thermosetting resin composition layer, and then the thermosetting resin composition is irradiated with light. The hardening by the generated radicals occurs, and the solubility in the light-irradiated portion can be reduced. Therefore, for example, there is an advantage that regions with different solubility can be easily produced according to the electrode pattern by exposing the thermosetting resin composition layer through a photomask having a pattern for shielding only the electrode portion.

As the photoradical polymerization initiator, any known compounds can be used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazole skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, and hexaarylbis Oxime compounds such as imidazoles 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 aromatic complexes, etc. For details of these, reference can be made to the descriptions in paragraphs 0165 to 0182 of JP 2016-027357 A, which are incorporated into the present specification.

As the ketone compound, for example, the compound described in paragraph 0087 of JP-A No. 2015-087611 can be exemplified, and the content is incorporated in the present specification. Among the 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 Japanese Patent Laid-Open No. 10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used. As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCURE 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (product names: all manufactured by BASF Corporation) can be used. As the aminoacetophenone-based initiator, commercially available IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF Corporation) can be used. As the aminoacetophenone-based initiator, compounds described in Japanese Patent Laid-Open No. 2009-191179 can also be used, the maximum absorption wavelength being matched to a light source with a wavelength of 365 nm or 405 nm. As an acylphosphine-based initiator, 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide etc. are mentioned. In addition, IRGACURE819 or IRGACURETPO (trade name: both are 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（常州強力電子新材料有限公司製）、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。作為該種肟化合物的具體例，可舉出日本特開2010-262028號公報中所記載之化合物、日本特表2014-500852號公報的0345段中所記載之化合物24、36～40、日本特開2013-164471號公報的0101段中所記載之化合物（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、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 a photoradical polymerization initiator, an oxime compound is mentioned more preferably. By using the oxime compound, the exposure latitude can be further effectively improved. Among the oxime compounds, the exposure latitude (exposure margin) is wide, and since it functions as a photohardening accelerator, it is particularly preferred. As specific examples of the oxime compound, the compounds described in JP 2001-233842 A, the compounds described in JP 2000-080068 A, and the compounds described in JP 2006-342166 A can be used . Examples of preferable oxime compounds include compounds having the following structures, 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-Propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1- Ketone, 2-Benzyloxyimino-1-phenylpropan-1-one, 3-(4-Tosyloxy)iminobutan-2-one, and 2-ethoxycarbonyl Oxyimino-1-phenylpropan-1-one, etc. In the thermosetting 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 21]

Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are manufactured by BASF Corporation), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, Japanese Patent Laid-Open No. 2012-014052) can also be preferably used. Photo-radical polymerization initiator 2) described in Gazette No. In addition, TR-PBG-304 (manufactured by Changzhou Qiangqi Electronic New Material 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 such oxime compounds include compounds described in JP 2010-262028 A, compounds 24, 36 to 40 described in paragraph 0345 of JP 2014-500852 A, and JP 24-500852 A. Compound (C-3) and the like described in paragraph 0101 of Unexamined Publication No. 2013-164471. As the optimum oxime compound, the oxime compound having a specific substituent disclosed in JP-A No. 2007-269779, and the oxime having a thioaryl group disclosed in JP-A No. 2009-191061 can be mentioned. compounds, etc.

式（I）中，R^I00 係碳數1～20的烷基、因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、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1個取代之苯基或聯苯基，R^I01 係由式（II）表示之基團，或者係與R^I00 相同的基團，R^I02 ～R^I04 各自獨立地係碳數1～12的烷基、碳數1～12的烷氧基或鹵素。 [化學式23]

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 trihalomethyltrisium compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acyl groups Phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl - Compounds in the group of benzene-iron complexes and salts thereof, halomethyl oxadiazole compounds, 3-aryl substituted coumarin compounds. More preferable photo-radical polymerization initiators are trihalomethyltrisium compound, α-amino ketone compound, acylphosphine compound, phosphine oxide compound, metallocene compound, oxime compound, triarylimidazole dimer, onium Salt compounds, benzophenone compounds, and acetophenone compounds, selected from the group consisting of trihalomethyltriazole compounds, α-amino ketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds It is further preferable to use at least one compound, it is even more preferable to use a metallocene compound or an oxime compound, and it is even more preferable to use an oxime compound. In addition, as the photo-radical polymerization initiator, N such as benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), etc. can be used. N'-Tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-merolinylphenyl)-butanone-1 , 2-methyl-1-[4-(methylthio)phenyl]-2-endorolinyl-acetone-1 and other aromatic ketones, alkyl anthraquinones, etc., and quinones formed by condensation of aromatic rings benzoin, benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, and the like. Moreover, the compound represented by following formula (I) can also be used. [Chemical formula 22]

In formula (I), R ^I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, Alkyl having 1 to 20 carbon atoms, alkoxy group having 1 to 12 carbon atoms, halogen atom, cyclopentyl group, cyclohexyl group, alkenyl group having 2 to 12 carbon atoms, carbon interrupted by one or more oxygen atoms A phenyl or biphenyl group substituted with at least one of an alkyl group having 2 to 18 carbon atoms and an alkyl group having 1 to 4 carbon atoms, and R ^I01 is a group represented by formula (II), or the same as R ^I00 The groups, 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 a halogen. [Chemical formula 23]

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

In addition, the compounds described in paragraphs 0048 to 0055 of International Publication WO2015/125469 can also be used as the photoradical polymerization initiator.

When a photoradical polymerization initiator is contained, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.1 to 30% by mass relative to the total solid content of the thermosetting resin composition of the present invention. It is 0.5-15 mass %, More preferably, it is 1.0-10 mass %. The photoradical polymerization initiator may contain only one type, or may contain two or more types. When two or more kinds of photo-radical polymerization initiators are contained, it is preferable that the sum of them is within the above-mentioned range.

<Thermal radical polymerization initiator> The thermosetting resin composition of this invention may contain a thermal radical polymerization initiator in the range which does not deviate from the meaning of this invention. The thermal radical polymerization initiator is a compound that generates 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. Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A No. 2008-063554.

When a thermal radical polymerization initiator is contained, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.1 to 30% by mass relative to the total solid content of the thermosetting resin composition of the present invention. It is 5-15 mass %. Only one type of thermal radical polymerization initiator may be contained, or two or more types may be contained. When two or more kinds of thermal radical polymerization initiators are contained, it is preferable that the sum of them falls within the above-mentioned range.

<Polymerizable compound> <<Radically polymerizable compound>> When providing photosensitivity to the thermosetting resin composition of the present invention, it is preferable to contain a radically polymerizable compound.

As the radically polymerizable compound, a compound having a radically polymerizable group can be used. As a radical polymerizable group, the group which has an ethylenically unsaturated bond, such as a vinylphenyl group, a vinyl group, a (meth)acryloyl group, and an allyl group, is mentioned. The radically polymerizable group is preferably a (meth)acryloyl group.

The number of radically polymerizable groups possessed by the radically polymerizable compound may be one or two or more, but the radically polymerizable compound preferably has two or more radically polymerizable groups, and has three The above 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 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radically polymerizable compound is preferably 100 or more.

From the viewpoint of developability, the thermosetting resin composition of the present invention preferably contains at least one difunctional or more radical polymerizable compound containing two or more polymerizable groups, and contains at least one trifunctional or more radical radical A polymerizable compound is more preferable. Moreover, it may be a mixture of a bifunctional radically polymerizable compound and a trifunctional or more radically polymerizable compound. In addition, the number of functional groups of a radically polymerizable compound means the number of radically polymerizable groups in 1 molecule.

Specific examples of the radically polymerizable compound include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters and amides thereof. , preferably esters of unsaturated carboxylic acids and polyol compounds and amides of unsaturated carboxylic acids and polyamine compounds. In addition, the addition reaction products of unsaturated carboxylic acid esters or amides with affinity substituents such as hydroxyl groups or amine groups and monofunctional or polyfunctional isocyanates or epoxy groups, and monofunctional or polyfunctional isocyanates or epoxides can also be preferably used. Dehydration condensation reaction products of polyfunctional carboxylic acids, etc. In addition, the addition reaction products of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols, and halogen groups or toluene Substitution reaction products of unsaturated carboxylic acid esters or amides having a releasable substituent such as sulfonyloxy and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. In addition, as another example, instead of the above-mentioned unsaturated carboxylic acid, a group of compounds substituted with unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, allyl ether, and the like can be used. As a specific example, the description of paragraphs 0113 to 0122 of JP 2016-027357 A can be referred to, and these contents are incorporated into the present specification.

In addition, the radically polymerizable compound is also preferably a compound having a boiling point of 100° C. or higher under normal pressure. Examples thereof include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, and neopentaerythritol tri(meth)acrylate. (Meth)acrylate, Neotaerythritol Tetra (meth)acrylate, Dipivalerythritol Penta (meth)acrylate, Dipivalerythritol Hexa (meth)acrylate, Hexylene Glycol (Methyl) In polyfunctional alcohol Compounds which are (meth)acrylated after adding ethylene oxide or propylene oxide, Japanese Patent Publication No. Sho 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Patent Publication No. Sho 51-037193 (Meth)acrylate urethanes described in the gazettes, polyester acrylates described in Japanese Patent Laid-Open No. 48-064183, Japanese Patent Laid-Open No. 49-043191, and Japanese Patent Laid-Open No. 52-030490 These 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, compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Moreover, the polyfunctional (meth)acrylate etc. obtained by making a polyfunctional carboxylic acid react with a compound which has a cyclic ether group and an ethylenically unsaturated bond, such as glycidyl (meth)acrylate, are mentioned. Moreover, as preferable radically polymerizable compounds other than the above, those having a pyrene ring described in Japanese Patent Laid-Open No. 2010-160418, Japanese Patent Laid-Open No. 2010-129825, Japanese Patent No. 4364216, etc. can also be used , A compound or cardo resin with two or more groups with ethylenically unsaturated bonds. Furthermore, as other examples, the specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 1-040337, and Japanese Patent Publication No. 1-040336, and Japanese Patent Publication No. Hei 2 can also be cited. - Vinylphosphonic acid-based compounds and the like described in Gazette No. 025493. Moreover, the compound containing a perfluoroalkyl group described in Unexamined-Japanese-Patent No. 61-022048 can also be used. Furthermore, those described as photocurable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pp. 300 to 308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP-A No. 2015-034964 can be preferably used, and these contents are incorporated into the present specification.

In addition, the following compounds described in Japanese Patent Laid-Open No. 10-062986 as formulas (1) and (2) together with specific examples can also be used as radically polymerizable compounds, which are added to polyfunctional alcohols. A compound obtained by (meth)acrylate esterification of 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 into the present specification.

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

Commercially available products of the radical polymerizable compound include, for example, SR-494 produced by Sartomer Company, Inc. as a tetrafunctional acrylate having four ethoxy-extending chains, and SR-494 as a tetrafunctional acrylate having four vinyloxy chains Functional methyl acrylate SR-209, 231, 239 manufactured by Sartomer Company, Inc, DPCA-60 manufactured by Nippon Kayaku Co., Ltd. as a hexafunctional acrylate having 6 pentyloxy chains, as DPCA-60 having 3 Isobutoxy chain trifunctional acrylate TPA-330, urethane oligomer UAS-10, urethane oligomer 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 the radically polymerizable compound, as described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 2-032293, and Japanese Patent Publication No. 2-016765 Urethane acrylates, those described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 Urethane compounds with oxyethane-based skeletons are also preferred. Furthermore, as the radically polymerizable compound, those having an amino group in the molecule described in Japanese Patent Laid-Open No. 63-277653, Japanese Patent Laid-Open No. 63-260909, and Japanese Patent Laid-Open No. Hei 1-105238 can also be used. Compounds of structure or sulfide structure.

The radically polymerizable compound may be a radically 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 preferable, and the unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to give an acid. The radically polymerizable compound of the base is more preferable. Among the radically polymerizable compounds having an acid group by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride, the aliphatic polyhydroxy compound is used as neotaerythritol and/or two new compounds. Compounds of pentaerythritol. As a commercial item, M-510, M-520 etc. are mentioned as a polybasic acid-modified acrylic oligomer by TOAGOSEI CO., Ltd., for example. The preferable acid value of the radically polymerizable compound having an acid group is 0.1 to 40 mgKOH/g, particularly preferably 5 to 30 mgKOH/g. As long as the acid value of the radically polymerizable compound is within the above-mentioned range, the production and workability are excellent, and furthermore, the developability is excellent. In addition, the polymerizability was good.

The thermosetting resin composition of the present invention can preferably use a monofunctional radically polymerizable compound as the radically polymerizable compound from the viewpoint of suppressing warpage accompanying the control of the elastic modulus of the cured film. As the monofunctional radically 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, (Meth)acrylic acid such as N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono (meth)acrylate, polypropylene glycol mono (meth)acrylate, etc. Derivatives, N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, etc. Allyl compounds, etc. As the monofunctional radically 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-mentioned radically polymerizable compounds>> The thermosetting resin composition of the present invention can further contain polymerizable compounds other than the above-mentioned radically polymerizable compounds. Examples of polymerizable compounds other than the above-mentioned radically polymerizable compounds include compounds having a methylol group, an alkoxymethyl group, or an acyloxymethyl group; an epoxy compound; an oxetane compound; compound.

(Compound with hydroxymethyl, alkoxymethyl or acyloxymethyl) As a compound with hydroxymethyl, alkoxymethyl or acyloxymethyl, it is represented by the following formula (AM1), (AM4) or (AM5 ) is the preferred compound.

（式中，t表示1～20的整數，R⁴ 表示碳數1～200的t價有機基，R⁵ 表示由-OR⁶ 或-OCO-R⁷ 表示之基團，R⁶ 表示氫原子或碳數1～10的有機基，R⁷ 表示碳數1～10的有機基。）[Chemical formula 24]

(in the formula, t represents an integer of 1 to 20, R ⁴ represents a t-valent organic group with a carbon number of 1 to 200, R ⁵ represents a group represented by -OR ⁶ or -OCO-R ⁷ , R ⁶ represents a hydrogen atom or An organic group having 1 to 10 carbon atoms, and R ⁷ represents an organic group having 1 to 10 carbon atoms.)

（式中，R⁴⁰⁴ 表示碳數1～200的2價有機基，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，R⁴⁰⁷ 表示碳數1～10的有機基。）[Chemical formula 25]

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

（式中，u表示3～8的整數，R⁵⁰⁴ 表示碳數1～200的u價有機基，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，R⁵⁰⁷ 表示碳數1～10的有機基。）[Chemical formula 26]

(In the formula, u represents an integer of 3 to 8, R ⁵⁰⁴ represents a u-valent organic group having 1 to 200 carbon atoms, R ⁵⁰⁵ represents a group represented by -OR ⁵⁰⁶ or -OCO-R ⁵⁰⁷ , and R ⁵⁰⁶ represents a hydrogen atom Or an organic group with 1 to 10 carbon atoms, and 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 (the above are trade names, 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 (trade names above, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (trade name above, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-buthylphenol (2,6-dimethoxymethyl-4-tert-butylphenol) , 2,6-dimethoxymethyl-p-cresol (2,6-dimethoxymethyl-p-cresol), 2,6-diacethoxymethyl-p-cresol (2,6-diacetoxymethyl-p-cresol) cresol), etc.

Moreover, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML- TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade names, manufactured by ASAHI YUKIZAI CORPORATION), NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW-100LM (the above are trade names, manufactured by Sanwa Chemical Co., Ltd.).

(Epoxy compound (compound which has an epoxy group)) As an epoxy compound, the compound which has two or more epoxy groups in one molecule is preferable. The epoxy base undergoes a cross-linking reaction at 200° C. or lower, and hardly causes film shrinkage since it does not cause a dehydration reaction derived from the cross-linking. Therefore, by containing an epoxy compound, the low-temperature hardening and warpage of a composition can be suppressed effectively.

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

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

(Oxetane compound (compound having an oxetanyl group)) Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl 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, 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 two or more.

(Benzophthalic compounds (compounds with polybenzoxazolyl groups)) Benzosic compounds do not produce outgassing during curing due to the cross-linking reaction derived from the ring-opening addition reaction, thereby reducing thermal shrinkage and inhibiting Since warpage occurs, it is preferable.

Preferable examples of benzodiazepine compounds include B-a-type benzodiazepines, B-m-type benzodiazepines (the above are trade names, manufactured by Shikoku Chemicals Corporation), and benzodiazepines of polyhydroxystyrene resins. Adducts, novolac-type dihydrobenzos 㗁𠯤 compounds. These may be used alone, or two or more may be mixed.

When a polymerizable compound is contained, its content is preferably more than 0 mass % and 60 mass % or less with respect to the total solid content of the thermosetting resin composition of the present invention. The lower limit is more preferably 5 mass % or more. The upper limit is more preferably 50% by mass, and more preferably 30% by mass or less. A polymerizable compound may be used individually by 1 type, and may be used in mixture of 2 or more types. When two or more types are used at the same time, it is preferable that the total amount thereof falls within the above-mentioned range.

<Migration inhibitor> It is preferable that the thermosetting resin composition of this invention further contains a migration inhibitor. By including the migration inhibitor, the transfer of metal ions from the metal layer (metal wiring) into the thermosetting resin composition layer can be effectively suppressed. The migration inhibitor is not particularly limited, and examples include heterocycles (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetra azole ring, pyridine ring, pyridoxine ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, endoxoline ring, 2H-pyran ring and 6H-pyran ring, tripyran ring) compounds, with Thiourea and mercapto compounds, hindered phenolic compounds, salicylic acid derivatives, and hydrazine derivatives. 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, an ion scavenger that captures 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 A, and JP 2011 A can be used. - The compound described in paragraph 0052 of Gazette No. 059656, the compound described in paragraphs 0114, 0116 and 0118 of JP-A No. 2012-194520, and the like.

Specific examples of the migration inhibitor include the following compounds. [Chemical formula 27]

When the thermosetting resin composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass % relative to the total solid content of the thermosetting resin composition, more preferably 0.05 to 2.0 mass %, and 0.1 -1.0 mass % is more preferable. Only one type of migration inhibitor may be used, or two or more types may be used. When there are two or more kinds of migration inhibitors, it is preferable that the sum of them falls within the above-mentioned range.

當本發明的熱硬化性樹脂組成物具有聚合抑制劑時，聚合抑制劑的含量相對於本發明的熱硬化性樹脂組成物的總固體成分係0.01～5質量%為較佳，0.02～3質量%為更佳，0.05～2.5質量%為特佳。 聚合抑制劑可以僅為一種，亦可以為兩種以上。當聚合抑制劑為兩種以上時，其合計為上述範圍為較佳。<Polymerization inhibitor> It is preferable that the thermosetting resin composition of this invention contains a polymerization inhibitor. As the polymerization inhibitor, for example, hydroquinone, 4-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butyl catechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4- Methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylidene diphenylamine Aminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyl Quinoline, 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-tert-butyl)phenylmethane, etc. In addition, the polymerization inhibitors described in paragraph 0060 of JP-A 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication WO 2015/125469 can also be used. Moreover, the following compound (Me is a methyl group) can also be used. [Chemical formula 28]

When the thermosetting resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5 mass %, preferably 0.02 to 3 mass %, based on the total solid content of the thermosetting resin composition of the present invention % is more preferable, and 0.05 to 2.5 mass % is particularly preferable. Only one type of polymerization inhibitor may be used, or two or more types may be used. When there are two or more kinds of polymerization inhibitors, it is preferable that the sum of them falls within the above-mentioned range.

<Metal Adhesion Improver> It is preferable that the thermosetting resin composition of the present invention contains a metal adhesion improver for improving the adhesion to metal materials used for electrodes, wiring, and the like. As a metal adhesion improver, a silane coupling agent etc. are mentioned.

Examples of the silane coupling agent include compounds described in paragraphs 0062 to 0073 of JP 2014-191002 A, compounds described in paragraphs 0063 to 0071 of International Publication WO 2011/080992A1, and Japanese Patent Laid-Open Publication No. 0063 to 0071. The compounds described in paragraphs 0060 to 0061 of JP 2014-191252 A, the compounds described in paragraphs 0045 to 0052 of JP 2014-041264 A, and the compounds described in paragraph 0055 of International Publication WO 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-A-2011-128358. Moreover, it is also preferable to use the following compounds as a silane coupling agent. In the following formula, Et represents an ethyl group. [Chemical formula 29]

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

The content of the metal adhesion improver is preferably in the range of 0.1 to 30 parts by mass, more preferably in the range of 0.5 to 15 parts by mass, and particularly preferably in the range of 0.5 to 5 parts by mass, relative to 100 parts by mass of the polymer precursor. By setting it as the said 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 value, the heat resistance and mechanical properties of the cured film after a curing process become favorable. Only one type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, it is preferable that the sum of them falls within the above-mentioned range.

<Curing Accelerator> The thermosetting resin composition of the present invention may contain a curing accelerator. The hardening accelerator may be a thermal hardening accelerator or a photohardening accelerator. <<Thermosetting accelerator>> The thermosetting accelerator is preferably a salt of a quaternary ammonium cation and a carboxylate anion. The quaternary ammonium cation is preferably represented by the following formula (Y1-1). [Chemical formula 30]

In formula (Y1-1), R ^N1 represents an Nn-valent (Nn is an integer of 1 to 12) organic group, preferably an Nn-valent hydrocarbon group. Examples of the hydrocarbon group include Nn-valent groups containing alkanes (preferably having 1 to 12 carbon atoms, more preferably 1-6, and particularly preferably 1-3), and Nn-valent groups containing alkenes (having 2 to 2 carbon atoms) 12 is preferred, 2-6 is more preferred, 2-3 is particularly preferred), an Nn-valent group containing aromatic hydrocarbons (carbon number 6-22 is preferred, 6-18 is more preferred, 6-10 is Excellent) or a combination of these. Among them, the aromatic hydrocarbon group of R ^N1 is preferable. R ^N1 may have the aforementioned substituent T within a range not impairing the effects of the present invention. R ^N2 to R ^N5 independently represent a hydrogen atom or a hydrocarbon group (preferably carbon number 1-36, more preferably 1-24, especially 1-12), alkyl (preferably carbon number 1-36, 1-24 is more preferred, 1-23 is particularly preferred), alkenyl (carbon number 2-36 is preferred, 2-24 is more preferred, 2-23 is particularly preferred), alkynyl (carbon number 1-36 1-24 is more preferred, 1-23 is particularly preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-10 is particularly preferred) is preferred. The alkyl group, alkenyl group, and alkynyl group may be linear or branched, and may be cyclic or chain. R ^N6 is alkyl (preferably carbon number 1-36, more preferably 2-24, especially 4-18), alkenyl (preferably carbon number 2-36, more preferably 2-24, 4 ~18 is particularly preferred), alkynyl (preferably carbon number 2-36, 2-24 is more preferred, 4-18 is particularly preferred), aryl (carbon number 6-22 is preferred, 6-18 is preferred) Better, 6 to 10 is particularly good). The alkyl group, the alkenyl group, and the alkynyl group may be linear or branched, and may be cyclic or chain. In this case, in the alkyl group, the alkenyl group, the alkynyl group, and the aryl group, a linking group Lh containing a heteroatom may be interposed in the middle of the chain or in the connection with the parent nucleus. Examples of the linking group Lh containing a hetero atom include -O-, -S-, -CO-, ^-NRN- , or a linking group consisting of a combination of these. The number of atoms constituting the linking group Lh containing the heteroatom is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3. The number of atoms in the specific group of the linking group Lh containing the heteroatom is preferably 1-12, more preferably 1-6, and particularly preferably 1-3. The definition of R ^N is the same as above. R ^N6 may further have the aforementioned substituent T within a range not impairing the effects of the present invention. Nn represents an integer of 1 or more and 12 or less, an integer of 1 to 6 is more preferred, and an integer of 1 to 3 is particularly preferred. No is preferably an integer of 1 to 12, more preferably an integer of 1 to 6, and particularly preferably an integer of 1 to 3. Two of R ^N2 to R ^N6 may be bonded to each other to form a ring.

In this embodiment, as a specific example of the carboxylate anion paired with the above-mentioned quaternary ammonium cation, an anion derived from a compound represented by any one of the formulae AC2 to AC5 exemplified by the above-mentioned acidic compound can be mentioned. The molecular weight of the thermosetting accelerator in the present invention is preferably 100 or more and less than 2000, more preferably 200 to 1000. As an example of the thermosetting accelerator in the present invention, there are exemplified acidic compounds that generate bases when heated to 40°C or higher, and ammonium salts having anions and ammonium cations with pKa1 of 0 to 4, which are described in WO2015/199219. These contents are incorporated into this manual.

When a thermosetting accelerator is used, the content of the thermosetting accelerator in the composition is preferably 0.01 to 50 mass % with respect to the total solid content of the composition. The lower limit is more preferably 0.05 mass % or more, and still more preferably 0.1 mass % or more. The upper limit is more preferably 10 mass % or less, and even more preferably 5 mass % or less. One type or two or more types of thermosetting accelerators can be used. When two or more kinds are used, the total amount is preferably within the above range. Moreover, the composition of this invention can also be comprised so that a thermosetting accelerator may not be contained substantially. Not substantially contained means less than 0.01 mass %, more preferably less than 0.005 mass % with respect to the total solid content of the composition.

<<Photocuring accelerator>> The thermosetting resin composition used in the present invention may contain a photocuring accelerator. The photohardening accelerator in the present invention refers to one that generates alkali by exposure, and does not show activity under normal conditions of normal temperature and pressure, but if it is irradiated with electromagnetic waves and heated as external stimuli, as long as it generates alkali ( Alkaline substances) are not particularly limited. The alkali generated by exposure acts as a catalyst when the polymer precursor is hardened by heating, and thus can be preferably used. In this invention, a well-known thing can be used as a photohardening accelerator. For example, transition metal complexes, those having structures such as ammonium salts, and those in which an amidine moiety and a carboxylic acid are latentized by formation of a salt include ionic compounds in which an alkali component is neutralized by formation of a salt, and amines. Carbamate derivatives, oxime ester derivatives, acyl compounds, etc. are nonionic compounds that are latentized by alkali components such as amine ester bonds, oxime bonds, and the like.

As the photohardening accelerator according to the present invention, for example, as disclosed in Japanese Patent Laid-Open No. 2009-080452 and International Publication No. 2009/123122, the photohardening accelerator having a cinnamate structure, such as Japanese Photohardening accelerators having a urethane structure as disclosed in Japanese Patent Laid-Open No. 2006-189591 and Japanese Patent Laid-Open No. 2008-247747, such as Japanese Patent Laid-Open No. 2007-249013 and Japanese Patent Laid-Open No. 2008-003581 Although the photohardening accelerator etc. which have an oxime structure and an aminoformoxime structure are disclosed, it is not limited to these, In addition, the structure of a well-known hardening accelerator can be used.

In addition, as the photohardening accelerator, the compounds described in paragraphs 0185 to 0188, 0199 to 0200, and 0202 of JP 2012-093746 A, and 0022 to 0069 of JP 2013-194205 A can be mentioned as examples. The compounds described in the paragraphs, the compounds described in paragraphs 0026 to 0074 of JP 2013-204019 A, and the compounds described in paragraph 0052 of International Publication WO 2010/064631 A.

As a commercial product of a photohardening accelerator, WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, PBG-018, WPGB-015, WPBG-041, WPGB can also be used -172, WPGB-174, WPBG-166, WPGB-158, WPGB-025, WPGB-168, WPGB-167 and WPBG-082 (manufactured by Wako Pure Chemical Industries, Ltd.).

When a photohardening accelerator is used, the content of the photohardening accelerator in the composition is preferably 0.1 to 50 mass % with respect to the total solid content of the composition. The lower limit is more preferably 0.5 mass % or more, and even more preferably 1 mass % or more. The upper limit is more preferably 30 mass % or less, and even more preferably 20 mass % or less. One type or two or more types of photohardening accelerators can be used. When two or more kinds are used, the total amount is preferably within the above range.

<Organic Compound Containing Group 4 Element> It is preferable that the composition of the present invention contains an organic compound containing a Group 4 element (hereinafter, sometimes referred to as "organo-titanium compound and the like"). As the organic compound containing the Group 4 element, an organic compound containing at least one selected from a titanium atom, a zirconium atom and a hafnium atom is preferable, and an organic compound containing at least one selected from a titanium atom and a zirconium atom is more preferable . In addition, the organic compound containing at least one selected from a titanium atom and a zirconium atom is preferably a compound containing an organic group and a titanium atom or a zirconium atom, and the total number of the titanium atom and the zirconium atom in one molecule is preferably one . Although it does not specifically limit as an organic group, The group which consists of a combination of a hydrocarbon group, a hydrocarbon group, and a hetero atom is preferable. As a hetero atom, an oxygen atom, a sulfur atom, and a nitrogen atom are preferable. In the present invention, at least one cyclic group in the organic group is preferable, and at least two cyclic groups are more preferable. The aforementioned cyclic group is preferably selected from a 5-membered ring cyclic group and a 6-membered ring cyclic group, and more preferably is selected from a 5-membered ring cyclic group. As the 5-membered ring cyclic group, a cyclopentadienyl group is preferable. Moreover, it is preferable that the organotitanium compound etc. used for this invention contain 2-4 cyclic groups in 1 molecule. In the present invention, the organic titanium compound and the like are preferably represented by the following formulae (P-1) to (P-3), and the compound represented by the formula (P-1) is more preferable. [Chemical formula 31]

In the formula, M is a Group 4 element. As the Group 4 element represented by M, a titanium atom, a zirconium atom, and a hafnium atom are preferable, and a titanium atom and a zirconium atom are more preferable.

R is each independently a substituent. R is preferably selected from an aryl group, an alkyl group, a halogen atom, an alkylsulfonyloxy group and an arylsulfonyloxy group, and more preferably is selected from an alkyl group, a halogen atom and an alkylsulfonyloxy group. The aryl group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. Specifically, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and the like can be mentioned. As the alkyl group, the number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3. Specifically, methyl, ethyl, propyl, octyl, and isopropyl may be mentioned. , tert-butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl, etc. As a halogen atom, F, Cl, Br, and I are mentioned. As the alkyl group constituting the alkylsulfonyloxy group, the number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3. Specifically, methyl, ethyl, propyl base, octyl, isopropyl, tert-butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl and the like. The above-mentioned substituent may have a substituent. Examples of the substituent include substituent T and the like, and specifically, halogen atoms (F, Cl, Br, I), hydroxyl, carboxyl, amino, cyano, aryl, alkoxy, aryl Oxy group, aryl group, alkoxycarbonyl group, aryloxycarbonyl group, aryloxy group, monoalkylamine group, dialkylamine group, monoarylamine group and diarylamine group, etc.

R^P11 係定義與R^P1 相同之基團。 R^P12 ～R^P14 係氫原子或取代基T。取代基T中，尤其烷基（碳數1～12為較佳，1～6為更佳，1～3為進一步較佳）或烷氧基（碳數1～12為較佳，1～6為更佳，1～3為進一步較佳）為較佳。 px係1～4的整數。py係0～4的整數。py+px=4R ^P1 to R ^P4 are halogen atoms, hydroxyl groups or organic groups (except cyclopentadienyl groups). Examples of the organic group include alkyl (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3), and alkenyl (preferably having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms). more preferably, 2-3 are further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-10 is further preferred), alkoxy (carbon number 1-12 is preferred, 1-6 is more preferred, 1-3 is further preferred), aryloxy (carbon number 6-22 is preferred, 6-18 is more preferred, 6-10 is further preferred), alkane Sulfonyloxy (preferably with 1-12 carbon atoms, more preferably 1-6, and further preferably 1-3), arylsulfonyloxy (preferably with 1-12 carbon atoms, 1-6 is more preferable, 1-3 are further preferable), acyloxy (2-12 carbons are preferable, 2-6 are more preferable, 2-3 are further preferable), aryloxy (7 carbons) ~23 is better, 7~19 is better, 7~11 is further better). R ^P0 is an organic linking group that constitutes the ligand in the formula (the number of carbons is preferably 2-12, more preferably 2-6, and further preferably 2-4, and it may not be through the hetero linking group Lh), for example β-diketone ligands can be mentioned. As the β-diketone, acetone acetone, ethyl acetoacetate, and the like can be mentioned. As R ^P0 , the structure of the following formula (P-3(a)) can be mentioned. * is a bond with an oxygen atom. [Chemical formula 32]

R ^P11 defines the same group as R ^P1 . R ^P12 to R ^P14 are hydrogen atoms or substituents T. Among the substituents T, especially alkyl (preferably with carbon number 1-12, more preferably with 1-6, more preferably with 1-3) or alkoxy (preferably with carbon number of 1-12, with 1-6 More preferably, 1 to 3 are more preferable) is more preferable. px is an integer from 1 to 4. py is an integer from 0 to 4. py+px=4

When R, R ^P1 to R ^P4 , and R ^P11 to R ^P14 contain an alkyl group, an alkenyl group, an aryl group, or a linking group containing these groups, they may also have any substituent T within the scope of the effect of the present invention. (eg hydroxyl group, carboxyl group, halogen atom, etc.). R ^P1 to R ^P4 when there are plural, and R ^P11 and R ^P12 to R ^P14 when there are plural may be the same or different from each other. In addition, two or more adjacent groups may be bonded to form a ring with or without the following linking group L. The linking group L is an alkylene group (the carbon number of 1-12 is preferable, 1-6 is more preferable, and 1-3 is particularly preferable), alkenyl (the carbon number of 2-12 is preferable, and 2-6 is more preferable) preferably), O, CO, NR ^N , S, or a group of this combination is preferred. In addition to hydrogen atoms, the number of atoms constituting the linking group L is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3. The number of linking atoms of the linking group L is preferably 10 or less, more preferably 8 or less. The lower limit is 1 or more. The above-mentioned number of linking atoms means the minimum number of atoms which are located on the route between the predetermined structural parts and which are related to the linking. For example, in the case of -CH ₂ -C(=O)-O-, the number of atoms constituting the linking group is 6, but the number of linking atoms is 3.

The organic compound containing Group 4 elements used in the present invention is preferably selected from titanocene compounds, tetraalkoxytitanium compounds, titanocene compounds, titanium chelates, zirconocene compounds and hafnocene compounds, and is preferably selected from Titanocene compounds, zirconocene compounds and hafnocene compounds are more preferred, and it is further preferred to be selected from titanocene compounds and zirconocene compounds.

The molecular weight of the organic titanium compound or the like is preferably 50 to 2000, more preferably 100 to 1000.

Specific examples of the organic titanium compound and the like include tetraethylpropoxytitanium, tetrakis(2-ethylhexyloxy)titanium, diisopropoxybis(ethylacetate)titanium, and diisopropoxybis Titanium (acetylpyruvate), the following compounds or compounds exemplified in the following examples. [Chemical formula 33]

In addition, as an organic compound containing a titanium atom among the organic titanium compounds and the like, di-cyclopentadienyl-Ti-dichloride (bis(cyclopentadienyl) titanium dichloride), bi-cyclopentadienyl-Ti-dichloride can also be used Pentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, di-cyclopentadienyl -Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl-1-yl, di- -Cyclopentadienyl-Ti-2,6-difluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,4-difluorophenyl-1-yl, di-methyl ylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, bis-methylcyclopentadienyl-Ti-bis-2,3,5, 6-Tetrafluorophenyl-1-yl, bis-methylcyclopentadienyl-Ti-bis-2,4-difluorophenyl-1-yl, bis(cyclopentadienyl)-bis(2 ,6-Difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(methylsulfonamide)phenyl ] titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butylbiaroyl-amino)phenyl]titanium, bis(cyclopentadienyl) ) bis[2,6-difluoro-3-(N-ethylacetamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N- Methylacetamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-ethylpropionamido)phenyl]titanium, bis( Cyclopentadienyl)bis[2,6-difluoro-3-(N-ethyl-(2,2-dimethylbutyryl)amino)phenyl]titanium, bis(cyclopentadienyl)bis [2,6-Difluoro-3-(N-butyl-(2,2-dimethylbutyryl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro -3-(N-pentyl-(2,2-dimethylbutyryl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl) )-(2,2-dimethylbutyrylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-methylbutyrylamino)phenyl]titanium, Bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-methylpentylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-di Fluoro-3-(N-ethylcyclohexylcarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-ethylisobutyrylamino)benzene base] titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-ethylacetamido)phenyl]titanium,

Bis(cyclopentadienyl)bis[2,6-difluoro-3-(2,2,5,5-tetramethyl-1,2,5-azadipropyl-1-yl)phenyl ] titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(octylsulfonamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-di Fluoro-3-(4-Tolylsulfonamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(4-dodecylbenzenesulfonamido) ) phenyl] titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(4-(1-pentylheptyl)phenylsulfonamido)phenyl]titanium, bis( Cyclopentadienyl)bis[2,6-difluoro-3-(ethylsulfonamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-( (4-Bromophenyl)-sulfonamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2-naphthylsulfonamido)phenyl] Titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(hexadecylsulfonamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6- Difluoro-3-(N-methyl-(4-dodecylphenyl)sulfonamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3- (N-methyl-4-(1-pentylheptyl)phenyl)sulfonamido)]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl) -(4-Toluyl)-sulfonamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(pyrrolidine-2,5-dione- 1-yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3,4-dimethyl-3-pyrrolidine-2,5-dione-1) -yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(phthalimide)phenyl]titanium, bis(cyclopentadienyl)bis [2,6-Difluoro-3-(isobutoxycarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(ethoxycarbonylamino) ) phenyl] titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-((2-chloroethoxy)-carbonylamino)phenyl]titanium, bis(cyclopentadiene) base) bis[2,6-difluoro-3-(phenoxycarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3-phenyl) thiourea)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3-butylthiourea)phenyl]titanium, bis(cyclopentadienyl)bis[ 2,6-Difluoro-3-(3-phenylurea)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3-butylurea)phenyl] Titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N,N-diacetylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2, 6-Difluoro-3-(3,3-dimethylurea)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(acetylamino)phenyl ] titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(butyrylamino)phenyl]titanium, bis(cyclopentadienyl) ) bis[2,6-difluoro-3-(decanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(octadecanoylamine) base) phenyl] titanium,

Bis(cyclopentadienyl)bis[2,6-difluoro-3-(isobutyrylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-( 2-Ethylhexylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2-methylbutyrylamino)phenyl]titanium, bis( Cyclopentadienyl)bis[2,6-difluoro-3-(neopentylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-( 2,2-Dimethylbutanylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2-ethyl-2-methylheptanylamino) ) phenyl] titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(cyclohexylcarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6 -Difluoro-3-(2,2-dimethyl-3-chloropropionylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3 -Phenylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2-chloromethyl-2-methyl-3-chloropropionyl) Amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3,4-xylosylamino)phenyl]titanium, bis(cyclopentadienyl) ) bis[2,6-difluoro-3-(4-ethylbenzylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2 ,4,6-Mesitylcarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(benzylamino)phenyl]titanium, Bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-phenylpropyl)benzylamino)phenyl]titanium, bis(cyclopentadienyl) Bis[2,6-difluoro-3-(N-(3-ethylheptyl)-2,2-dimethylpentanoylamino]phenyl titanium, bis(cyclopentadienyl)bis[ 2,6-Difluoro-3-(N-isobutyl-(4-toluyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro- 3-(N-Isobutylbenzylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexylmethylneopentyl) Amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(oxolan-2-ylmethyl)benzylamino) Phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-ethylheptyl)-2,2-dimethylbutyrylamino)phenyl] Titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-phenylpropyl-(4-tolylyl)amino)phenyl]titanium, bis( Cyclopentadienyl)bis[2,6-difluoro-3-(N-(oxolan-2-ylmethyl)-(4-tolylyl)amino)phenyl]titanium, Bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(4-tolylmethyl)benzylamino)phenyl]titanium, bis(cyclopentadienyl) ) bis[2,6-difluoro-3-(N-(4-tolylmethyl)-(4 -Toluyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butylbenzylamino)phenyl]titanium,

Bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(4-toluyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis [2,6-Difluoro-3-(N-hexyl-(4-tolylyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3- (N-(2,4-Dimethylpentyl)-2,2-dimethylbutanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3- (2,4-Dimethylpentyl)-2,2-dimethylpentanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-( (4-Toluyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2,2-dimethylpentanoylamino)benzene base] titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2,2-dimethyl-3-ethoxypropionylamino)phenyl]titanium, bis( Cyclopentadienyl)bis[2,6-difluoro-3-(2,2-dimethyl-3-allyloxypropionylamino)phenyl]titanium, bis(cyclopentadienyl) ) bis[2,6-difluoro-3-(N-allylacetylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2 -Ethylbutylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexylmethylbenzylamino)phenyl]titanium, Bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexylmethyl-(4-tolylyl)amino)phenyl]titanium, bis(cyclopentadienyl) ) bis[2,6-difluoro-3-(N-(2-ethylhexyl)benzylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro -3-(N-isopropylbenzylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-phenylpropyl) )-2,2-dimethylpentyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexylbenzylamino) ) phenyl] titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexylmethyl-2,2-dimethylpentanoyl)amino)phenyl] Titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butylbenzylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2, 6-Difluoro-3-(N-(2-ethylhexyl)-2,2-dimethylpentanoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6 -Difluoro-3-(N-hexyl-2,2-dimethylpentanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N -Isopropyl-2,2-dimethylpentanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-phenyl) propyl) neopentylamino) phenyl] titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-2,2-dimethylpentyl) Amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(2-methyl) oxyethyl)benzylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-benzylbenzylamino)phenyl ] titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-benzyl-(4-tolylyl)amino)phenyl]titanium,

Bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(2-methoxyethyl)-(4-tolyl)amino)phenyl]titanium, bis(cyclopentyl) Dienyl)bis[2,6-difluoro-3-(N-(4-methylphenylmethyl)-2,2-dimethylpentanoylamino)phenyl]titanium, bis(cyclohexyl) pentadienyl) bis[2,6-difluoro-3-(N-(2-methoxyethyl)-2,2-dimethylpentanoylamino)phenyl]titanium, bis(cyclohexyl) Pentadienyl)bis[2,6-difluoro-3-(N-cyclohexylmethyl-(2-ethyl-2-methylheptanoyl)amino)phenyl]titanium, bis(cyclopentyl) Dienyl)bis[2,6-difluoro-3-(N-butyl-(4-chlorobenzyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2, 6-Difluoro-3-(N-hexyl-(2-ethyl-2-methylbutanoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3 -(N-Cyclohexyl-2,2-dimethylpentanoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(oxygen pentcyclo-2-ylmethyl)-2,2-dimethylpentanoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N -Cyclohexyl-(4-chlorobenzyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexyl-(2-chloro) Benzyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3,3-dimethyl-2-azetidinone)- 1-yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-isocyanatophenyl)titanium, bis(cyclopentadienyl)bis[2,6-di Fluoro-3-(N-ethyl-(4-tolylsulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl) -(4-Tolylsulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(4-tolylsulfonyl) (yl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-isobutyl-(4-tolylsulfonyl)amino)phenyl ] titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(2,2-dimethyl-3-chloropropanoyl)amino)phenyl] Titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-phenylpropionyl)-2,2-dimethyl-3-chloropropionyl)amine base)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexylmethyl-(2,2-dimethyl-3-chloropropionyl)) Amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-isobutyl-(2,2-dimethyl-3-chloropropionyl)) Phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(2-chloromethyl-2-methyl-3-chloropropionyl)amine base)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro -3-(Butylthiocarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(phenylthiocarbonylamino)phenyl]titanium, Bis(cyclopentadienyl)bis[2,6-difluoro-3-isocyanatophenyl)titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-ethyl) -(4-Tolylsulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl-(4-tolylsulfonyl) )amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(4-tolylsulfonyl)amino)phenyl]titanium , bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-isobutyl-(4-tolylsulfonyl)amino)phenyl]titanium, bis(cyclopentadiene) base) bis[2,6-difluoro-3-(N-butyl-(2,2-dimethyl-3-chloropropionyl)amino)phenyl]titanium,

Bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-phenylpropionyl)-2,2-dimethyl-3-chloropropionyl)amino)benzene base] titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexylmethyl-(2,2-dimethyl-3-chloropropionyl)amino) Phenyl] titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-isobutyl-(2,2-dimethyl-3-chloropropionyl)phenyl] Titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(2-chloromethyl-2-methyl-3-chloropropionyl)amino)benzene base] titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(butylthiocarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6 -Difluoro-3-(phenylthiocarbonylamino)phenyl]titanium, bis(methylcyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl-2,2- Dimethylbutyryl)amino)phenyl]titanium, bis(methylcyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl-2,2-dimethylpentadienylamine) yl)phenyl]titanium, bis(methylcyclopentadienyl)bis[2,6-difluoro-3-(N-ethylacetamido)phenyl]titanium, bis(methylcyclopentadienyl) Dienyl)bis[2,6-difluoro-3-(N-ethylpropionylamino)phenyl]titanium, bis(trimethylsilylcyclopentadienyl)bis[2,6 -Difluoro-3-(N-butyl-2,2-dimethylpropionylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-( N-(2-Methoxyethyl)-trimethylsilylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl) Hexyldimethylsilylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-ethyl-(1,1,2-trimethyl) propyl)dimethylsilylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3-ethoxymethyl-3-methyl- 2-Azaquinone-1-yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3-allyloxymethyl-3-methyl-2 -Azaquinone-1-yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3-chloromethyl-3-methyl-2-azaquinone) -1-yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-benzyl-2,2-dimethylpropionylamino)phenyl ] titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(5,5-dimethyl-2-pyrrolidin-1-yl)phenyl]titanium, bis(cyclopentadiene) base) bis[2,6-difluoro-3-(6,6-diphenyl-2-piperidin-1-yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6 -Difluoro-3-(N-(2,3-dihydro-1,2-benzisothiazol-3-one(1,1-dioxide)-2-yl)phenyl]titanium, bis( Cyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl-(4-chlorobenzyl)amine base) phenyl] titanium,

Bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl-(2-chlorobenzyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis [2,6-Difluoro-3-(N-isopropyl-(4-chlorobenzyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro -3-(N-(4-Methylphenylmethyl)-(4-chlorobenzyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro -3-(N-(4-Methylphenylmethyl)-(2-chlorobenzyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro -3-(N-butyl-(4-chlorobenzyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-benzyl) -2,2-Dimethylpentylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(2-ethylhexyl)-4 -Tolyl-sulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-oxeptyl)benzyl) Amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3,6-dioxadecyl)benzylamino)phenyl ] titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(trifluoromethylsulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2 ,6-Difluoro-3-(trifluoroacetamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2-chlorobenzyl) Amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(4-chlorobenzyl)amino)phenyl]titanium, bis(cyclopentadiene) base) bis[2,6-difluoro-3-(N-(3,6-dioxadecyl)-2,2-dimethylpentanoylamino)phenyl]titanium, bis(cyclopentyl) Dienyl)bis[2,6-difluoro-3-(N-(3,7-dimethyl-7-methoxyoctyl)benzylamino)phenyl]titanium, bis(cyclohexyl) pentadienyl)bis[2,6-difluoro-3-(N-cyclohexylbenzylamino)phenyl]titanium, etc.

In addition, among the organic titanium compounds and the like, examples of organic compounds containing zirconium atoms or compounds containing hafnium atoms include (cyclopentadienyl)trimethylzirconium, (cyclopentadienyl)triphenylzirconium, (cyclopentadienyl)triphenylzirconium, and (cyclopentadienyl)triphenylzirconium Cyclopentadienyl)tribenzylzirconium, (cyclopentadienyl)zirconium trichloride, (cyclopentadienyl)trimethoxyzirconium, (cyclopentadienyl)dimethyl(methoxy)zirconium , cyclopentadienyl methyl zirconium dichloride, (methyl cyclopentadienyl) trimethyl zirconium, (methyl cyclopentadienyl) triphenyl zirconium, (methyl cyclopentadienyl) triphenyl zirconium Benzyl zirconium, (methylcyclopentadienyl) zirconium trichloride, (methyl cyclopentadienyl) dimethyl (methoxy) zirconium, (dimethyl cyclopentadienyl) trimethyl zirconium , (trimethylcyclopentadienyl)trimethylzirconium, (trimethylsilylcyclopentadienyl)trimethylzirconium, (tetramethylcyclopentadienyl)trimethylzirconium, ( Pentamethylcyclopentadienyl)trimethylzirconium, (pentamethylcyclopentadienyl)triphenylzirconium, (pentamethylcyclopentadienyl)tribenzylzirconium, (pentamethylcyclopentadienyl)zirconium Dienyl) zirconium trichloride, (pentamethylcyclopentadienyl) zirconium trimethoxy, (pentamethyl cyclopentadienyl) dimethyl (methoxy) zirconium, (cyclopentadienyl) Triethylzirconium, (cyclopentadienyl)tripropylzirconium, (cyclopentadienyl)trineopentylzirconium, (cyclopentadienyl)tris(diphenylmethyl)zirconium, (cyclopentadienyl)zirconium Dienyl) dimethyl zirconium hydride, (cyclopentadienyl) triethoxy zirconium, (cyclopentadienyl) triisopropoxy zirconium, (cyclopentadienyl) triphenoxy zirconium, (cyclopentadienyl) dimethyl isopropoxy zirconium, (cyclopentadienyl) diphenyl isopropoxy zirconium, (cyclopentadienyl) dimethoxy zirconium chloride, (cyclopentadienyl) Dienyl) methoxy zirconium chloride, (cyclopentadienyl) diphenoxy zirconium chloride, (cyclopentadienyl) phenoxy zirconium dichloride, (cyclopentadienyl) tris ( Phenyldimethylsilyl)zirconium, (n-butylcyclopentadienyl)dimethyl-n-butoxyzirconium, (benzylcyclopentadienyl)di-m-tolylmethylzirconium, ( Trifluoromethylcyclopentadienyl)tribenzylzirconium, (diphenylcyclopentadienyl)dinorbornylmethylzirconium, (tetraethylcyclopentadienyl)tribenzylzirconium, (five -Trimethylsilylcyclopentadienyl)tribenzylzirconium, (pentamethylcyclopentadienyl)trineopentylzirconium, (pentamethylcyclopentadienyl)methylzirconium dichloride , (pentamethylcyclopentadienyl) triethoxy zirconium, (pentamethyl cyclopentadienyl) triphenoxy zirconium, (pentamethyl cyclopentadienyl) methoxy zirconium dichloride , (pentamethylcyclopentadienyl)diphenoxyzirconium chloride, (pentamethylcyclopentadienyl)phenoxyzirconium dichloride, (indenyl)trimethylzirconium, (indenyl) Tribenzyl zirconium, (indenyl) zirconium trichloride, (indenyl) trimethoxy zirconium,

(Indenyl)triethoxyzirconium, bis(cyclopentadienyl)dimethylzirconium, bis(cyclopentadienyl)diphenylzirconium, bis(cyclopentadienyl)diethylzirconium, bis(cyclopentadienyl)zirconium (cyclopentadienyl) zirconium dibenzyl, bis (cyclopentadienyl) zirconium dimethoxy, bis (cyclopentadienyl) zirconium dichloride (bis (cyclopentadienyl) dichloride zirconium), bis(cyclopentadienyl) zirconium dihydride, bis(cyclopentadienyl) zirconium hydrochloride, bis(methylcyclopentadienyl) dimethyl zirconium, bis(methylcyclopentadiene) base) dibenzyl zirconium, bis(methylcyclopentadienyl) zirconium dichloride, bis(pentamethylcyclopentadienyl) dimethyl zirconium, bis(pentamethylcyclopentadienyl) dibenzyl base zirconium, bis(pentamethylcyclopentadienyl) zirconium dichloride, bis(pentamethylcyclopentadienyl) chloromethyl zirconium, bis(pentamethylcyclopentadienyl) methyl zirconium hydride, (Cyclopentadienyl)(pentamethylcyclopentadienyl) dimethyl zirconium, bis(cyclopentadienyl) di-neopentyl zirconium, bis(cyclopentadienyl) bis-m-tolyl zirconium , bis(cyclopentadienyl) bis(p-tolyl) zirconium, bis(cyclopentadienyl) bis(diphenylmethyl) zirconium, bis(cyclopentadienyl) dibromo zirconium, bis(cyclopentadienyl) Alkenyl) methyl zirconium chloride, bis (cyclopentadienyl) ethyl zirconium chloride, bis (cyclopentadienyl) cyclohexyl zirconium chloride, bis (cyclopentadienyl) phenyl zirconium chloride, bis (cyclopentadienyl) zirconium chloride pentadienyl) benzyl zirconium chloride, bis(cyclopentadienyl) hydride methyl zirconium, bis(cyclopentadienyl) methoxy zirconium chloride,

Bis(cyclopentadienyl)ethoxyzirconium chloride, bis(cyclopentadienyl)(trimethylsilyl)methyl zirconium, bis(cyclopentadienyl)bis(trimethylsilyl) ) zirconium, bis (cyclopentadienyl) (triphenylsilyl) methyl zirconium, bis (cyclopentadienyl) (tris (dimethylsilyl) silyl) methyl zirconium, bis ( Cyclopentadienyl)(trimethylsilyl)(trimethylsilylmethyl)zirconium, bis(methylcyclopentadienyl)diphenylzirconium, bis(ethylcyclopentadienyl) ) dimethyl zirconium, bis(ethylcyclopentadienyl) zirconium dichloride, bis(propylcyclopentadienyl) dimethyl zirconium, bis(propylcyclopentadienyl) zirconium dichloride, bis(propylcyclopentadienyl) zirconium dichloride, (n-butylcyclopentadienyl) zirconium dichloride, bis(tert-butylcyclopentadienyl) bis(trimethylsilyl) zirconium, bis(hexylcyclopentadienyl) zirconium dichloride, Bis(cyclohexylcyclopentadienyl) dimethyl zirconium, bis(dimethylcyclopentadienyl) dimethyl zirconium, bis(dimethylcyclopentadienyl) zirconium dichloride, bis(dimethyl cyclopentadienyl) zirconium Cyclopentadienyl) ethoxy zirconium chloride, bis(ethylmethylcyclopentadienyl) zirconium dichloride, bis(propylmethylcyclopentadienyl) zirconium dichloride, bis(butylmethyl cyclopentadienyl) zirconium chloride pentadienyl) zirconium dichloride, bis(trimethylcyclopentadienyl) zirconium dichloride, bis(tetramethylcyclopentadienyl) zirconium dichloride, bis(cyclohexylmethylcyclopentadienyl) ) Dibenzyl zirconium, bis(trimethylsilylcyclopentadienyl) dimethyl zirconium, bis(trimethylsilyl cyclopentadienyl) zirconium dichloride, bis(trimethylgermanyl cyclopentadiene) base) dimethyl zirconium, bis (trimethylgermanyl cyclopentadienyl) diphenyl zirconium, bis (trimethylstannyl cyclopentadienyl) dimethyl zirconium, bis (trimethyl stannyl cyclopentadienyl) dimethyl zirconium Methylstannylcyclopentadienyl)dibenzylzirconium, bis(trifluoromethylcyclopentadienyl)dimethylzirconium, bis(trifluoromethylcyclopentadienyl)norbornylzirconium , bis (indenyl) dibenzyl zirconium, bis (indenyl) zirconium dichloride, bis (indenyl) zirconium dibromide, bis (tetrahydroindenyl) zirconium dichloride, bis (indenyl) zirconium dichloride, ( propylcyclopentadienyl) (cyclopentadienyl) dimethyl zirconium, (cyclohexylmethyl cyclopentadienyl) (cyclopentadienyl) dibenzyl zirconium, (pentatrisilyl ring pentadienyl) (cyclopentadienyl) dimethyl zirconium, (trifluoromethylcyclopentadienyl) (cyclopentadienyl) dimethyl zirconium, ethylidene bis(indenyl) dimethyl Ethyl zirconium, ethylidene bis(indenyl) zirconium dichloride, ethylidene bis(tetrahydroindenyl) zirconium dimethyl, ethylene bis(tetrahydroindenyl) zirconium dichloride, dimethylsilyl bis(cyclopentadienyl) dimethyl zirconium, dimethylsilylidene bis(cyclopentadienyl) zirconium dichloride, isopropyl(cyclopentadienyl) (9-intenyl) Dimethyl zirconium, isopropyl (cyclopentadienyl) (9-phenylene) zirconium dichloride, [phenyl (methyl) propylidene] (9-phenylene) (cyclopentadienyl) Dimethyl zirconium, diphenylpropylidene (cyclopentadienyl) (9-phenylene) dimethyl zirconium, ethylidene (9-phenylene) (cyclopentadienyl) dimethyl zirconium, Cyclohexyl (9-phenylene) (cyclopentadienyl) dimethyl zirconium, cyclopentylene (9-phenylene) (cyclopentadienyl) dimethyl zirconium, cyclobutyl (9-phenylene) base) (cyclopentadienyl) dimethyl zirconium, dimethylsilylidene (9-phenylene) (cyclopentyl Dienyl) dimethyl zirconium, dimethylsilylidene bis(2,3,5-trimethylcyclopentadienyl) dimethyl zirconium, dimethylsilylidene bis(2,3 ,5-trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylidene bis (indenyl) zirconium dichloride, propylidene bis (cyclopentadienyl) dimethyl zirconium, propylene bis(cyclopentadienyl)bis(trimethylsilyl)zirconium,

Propylidene (cyclopentadienyl) (tetramethylcyclopentadienyl) dimethyl zirconium, propylidene (cyclopentadienyl) (phenylene) dimethyl zirconium, ethylidene bis (cyclopentane) pentadienyl) dimethyl zirconium, ethylidene bis (cyclopentadienyl) dibenzyl zirconium, ethylidene bis (cyclopentadienyl) zirconium dihydride, ethylidene bis (indenyl) bis Phenyl zirconium, ethylidenebis(indenyl)methyl zirconium chloride, ethylidenebis(tetrahydroindenyl)dibenzylzirconium, isopropylidene(cyclopentadienyl)(methylcyclopentadiene) base) zirconium dichloride, isopropyl (cyclopentadienyl) (octahydrointenyl) zirconium dihydride, dimethylsilylidene bis (cyclopentadienyl) bis-neopentyl zirconium, dimethyl Dimethylsilylidenebis(cyclopentadienyl)zirconium dihydride, dimethylsilylidenebis(methylcyclopentadienyl)zirconium dichloride, dimethylsilylidenebis(dimethylsilylidene) cyclopentadienyl) zirconium dichloride, dimethylsilylidene bis(tetrahydroindenyl) zirconium dichloride, dimethylsilylidene (cyclopentadienyl) (indenyl) zirconium dichloride, Dimethylsilylidene(cyclopentadienyl)(phenylene) zirconium dihydride, dimethylsilylene(methylcyclopentadienyl)(phenylene) zirconium dihydride, dimethylidene Silylbis(3-trimethylsilylcyclopentadienyl)zirconium dihydride, dimethylsilylidenebis(indenyl)dimethylzirconium, diphenylsilylidenebis(indenyl)di Zirconium chloride, phenylmethylsilylidene bis(indenyl) zirconium dichloride. Moreover, the compound etc. which replaced the zirconium atom of these compounds with a hafnium atom can also be used.

The content of the organic titanium compound or the like is preferably 0.1 to 30 mass % with respect to the total solid content of the composition of the present invention. The lower limit is more preferably 1.0 mass % or more, more preferably 1.5 mass % or more, and particularly preferably 2.0 mass % or more. The upper limit is more preferably 25 mass % or less, more preferably 15 mass % or less, still more preferably 10 mass % or less, and particularly preferably 5 mass % or less. One kind or two or more kinds of organic titanium compounds and the like can be used. When two or more kinds are used, the total amount is preferably within the above range. In addition, in the composition of the present invention, the mass ratio of the content of the organic titanium compound and the like to the content of the thermal alkali generator is preferably 100:1 to 1:100, more preferably 90:10 to 10:90, and 40:1. 60～20:80 is better. By setting it as such a range, a higher ring-closure rate and a higher glass transition temperature of the polymer precursor at low temperature can be achieved.

By blending an organotitanium compound or the like with the composition of the present invention, it is possible to achieve a higher ring opening rate and a higher glass transition temperature of the heterocyclic ring-containing polymer precursor at low temperature. Especially high effect can be acquired by making this compounding quantity into the said range.

<Other additives> The thermosetting resin composition of the present invention can add various additives, such as thermal acid generators, sensitizing dyes, chain transfer agents, and surfactants, as necessary, within the range that does not impair the effects of the present invention. , higher fatty acid derivatives, inorganic particles, hardeners, hardening catalysts, fillers, antioxidants, ultraviolet absorbers, aggregation inhibitors, etc. are blended. When these additives are blended, the total blending amount is preferably 3 mass % or less of the solid content of the composition.

<<Thermal acid generator>> The thermosetting resin composition of the present invention may contain a thermal acid generator. The thermal acid generator generates an acid by heating, and promotes the cyclization of the polymer precursor to further improve the mechanical properties of the cured film. As a thermal acid generator, the compound etc. which are described in the 0059 paragraph of Unexamined-Japanese-Patent No. 2013-167742 are mentioned.

The content of the thermal acid generator is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, relative to 100 parts by mass of the polymer precursor. By containing a thermal acid generator in an amount of 0.01 parts by mass or more, the crosslinking reaction and the cyclization of the polymer precursor are accelerated, so that the mechanical properties and chemical resistance of the cured film can be further improved. Moreover, from the viewpoint of the electrical insulating properties 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 particularly 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-mentioned range.

<<Sensitizing Dye>> The thermosetting 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 dyes in the electronically excited state come into contact with thermosetting accelerators, thermal radical polymerization initiators, photoradical polymerization initiators, etc., to produce electron transfer, energy transfer, and heat generation. Thereby, the thermal hardening accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator are chemically changed and decomposed to generate radicals, acids, or bases. For details of the sensitizing dye, the descriptions in paragraphs 0161 to 0163 of JP 2016-027357 A can be referred to, and the contents are incorporated in the present specification.

When the thermosetting resin composition of the present invention contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01 to 20 mass % relative to the total solid content of the thermosetting resin composition of the present invention, and 0.1 to 15 mass % % is more preferable, and 0.5-10 mass % is more preferable. One of the sensitizing dyes may be used alone, or two or more of them may be used simultaneously.

<<Chain Transfer Agent>> The thermosetting resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in Polymer Dictionary 3rd Edition (edited by The Society of Polymer Science, Japan, 2005) pp. 683-684. As a chain transfer agent, for example, it is used for the compound group which has SH, PH, SiH and GeH in a molecule|numerator. These can generate free radicals by supplying hydrogen to low-activity free radicals, or by deprotonation after oxidation, and generating free radicals. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptopolybenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.) can be preferably used. azoles, etc.).

When the thermosetting resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the total solid content of the thermosetting resin composition of the present invention, 1 -10 mass parts is more preferable, and 1-5 mass parts is more preferable. Only one type of chain transfer agent may be used, or two or more types may be used. When there are two or more kinds of chain transfer agents, the total range thereof is preferably the above-mentioned range.

<<surfactant>> From the viewpoint of further improving coatability, various surfactants can be added to the thermosetting resin composition of the present invention. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. Moreover, the following surfactant is also preferable. mixture [chemical formula 34]

When the thermosetting resin composition of the present invention has a surfactant, the content of the surfactant is preferably 0.001 to 2.0 mass % with respect to the total solid content of the thermosetting resin composition of the present invention, more preferably 0.005 ~1.0 mass %. Only one type of surfactant may be used, or two or more types may be used. When there are two or more surfactants, it is preferable that the sum of the surfactants falls within the above-mentioned range.

<<Higher fatty acid derivatives>> In order to prevent polymerization inhibition by oxygen, a higher fatty acid derivative such as behenic acid or behenamide may be added to the thermosetting resin composition of the present invention to make it. It is locally present on the surface of the composition during the drying process after coating. When the thermosetting resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the thermosetting resin composition of the present invention. Only one type of higher fatty acid derivatives may be used, or two or more types may be used. When there are two or more kinds of higher fatty acid derivatives, it is preferable that the sum of them falls within the above-mentioned range.

<Restrictions on other substances contained> From the viewpoint of the properties of the coated surface, the moisture content of the thermosetting 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. Excellent.

In addition to the above-mentioned Group 4 metals, the metal content of the thermosetting resin composition of the present invention is preferably less than 5 parts per million (parts per million), preferably less than 1 ppm by mass, from the viewpoint of insulating properties More preferably, less than 0.5 mass ppm is particularly preferable. Examples of the metal to be suppressed include sodium, potassium, magnesium, calcium, iron, chromium, nickel, and the like. When a plurality of metals are contained, it is preferable that the sum of these metals is in the above-mentioned range. In addition, as a method of reducing metal impurities unintentionally contained in the thermosetting resin composition of the present invention, it is possible to select a raw material with a small metal content as a raw material constituting the thermosetting resin composition of the present invention. The raw material of the thermosetting resin composition of the invention is filtered by a filter, and the inside of the apparatus is lined with polytetrafluoroethylene, etc., and distillation is performed under conditions such as contamination suppressed as much as possible.

Regarding the thermosetting resin composition of the present invention, considering the use as a semiconductor material, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and less than 200 mass ppm from the viewpoint of wiring corrosion. Mass ppm is particularly good. Among them, it is preferable that it is less than 5 mass ppm in the state of a halogen ion, and it is more preferable that it is less than 1 mass ppm, and it is more preferable that it is less than 0.5 mass ppm. As a halogen atom, a chlorine atom and a bromine atom are mentioned. The total of chlorine atoms and bromine atoms or chlorine ions and bromine ions is preferably within the above ranges, respectively.

As the storage container of the thermosetting resin composition of the present invention, a conventionally known storage container can be used. In addition, as a container, it is also preferable to use a multilayer bottle in which the inner wall of the container is constituted by 6 kinds of 6-layer resins, or a bottle in which 6 kinds of resins are formed into a 7-layer structure for the purpose of suppressing the contamination of impurities into the raw material or the composition. As such a container, the container described in Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

<Preparation of composition> The thermosetting resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and can be performed by a conventionally known method. The thermosetting resin composition of the present invention includes a compound selected from a polyimide precursor and a polybenzoxazole such that the pKa of the conjugated acid of the amine compound and the pKa of the acidic compound fall within the range of Formula 1. The case of the step of mixing the polymer precursor, the amine compound, the acidic compound and the solvent in the precursor. In addition, the thermoplastic resin of the present invention includes a compound selected from a polyimide precursor and a polybenzoxazole precursor such that the pKa of the conjugated acid of the amine compound and the pKa of the acidic compound fall within the range of Formula 1. In the case of the step of mixing a polymer precursor, a salt comprising a cation derived from an amine compound and an anion derived from an acidic compound, and a solvent. In addition, it is preferable to perform filtration using a filter for the purpose of removing foreign matter such as garbage and particles in the composition. The filter pore diameter is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. Filters can be pre-cleaned with organic solvents. In the filtering step of the filter, a plurality of filters can be used in parallel or in series. When multiple filters are used, filters with different pore sizes and/or materials can be used in combination. Also, various materials can be filtered multiple times. When filtering multiple times, it can be circular filtering. Moreover, you may filter after pressurization. When filtration is performed after pressurization, the pressure for pressurization is preferably 0.05 MPa or more and 0.3 MPa or less. In addition to filtration using a filter, impurity removal treatment using an adsorbent can also be performed. It is also possible to combine 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 mentioned.

<The manufacturing method of a cured film, a laminated body, a semiconductor device, and these> Next, a cured film, a laminated body, a semiconductor device, and the manufacturing method of these are demonstrated. The cured film of the present invention is formed by curing the thermosetting 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 cured film of this invention can be laminated|stacked in two or more layers as a laminated body. It is preferable that the laminated system which has two or more layers of the cured film of this invention has a metal layer between the cured films. These metal layers can be preferably used as metal wiring such as rewiring layers.

As an applicable field of the cured film of this invention, the insulating film of a semiconductor device, the interlayer insulating film for rewiring layers, a stress buffer film, etc. are mentioned. In addition, the case where a sealing film, a substrate material (base film or cover film of a flexible printed circuit board, an interlayer insulating film), or an insulating film for practical mounting as described above are patterned by etching, and the like. For such applications, see, for example, Science & technology Co., Ltd. "High Functionalization and Application Technology of Polyimide" April 2008, Masaki Kakimoto/Supervisor, CMC Technology Library "Basics of Polyimide Materials" and development", November 2001 et al.

Moreover, the cured film in this invention can also be used for manufacture of layouts, such as an offset printing plate surface and a screen plate surface, the use of the etching of a molded part, the manufacture of a protective lacquer in electronics, especially microelectronics, and a dielectric layer, and the like.

The manufacturing method of the cured film of this invention includes using the thermosetting resin composition of this invention. Specifically, it includes: a layer forming step of applying the thermosetting resin composition of the present invention to a substrate to form a layer; and a heating step of forming a layered thermosetting resin composition at 50 to 500° C. things are heated. In the case of imparting photosensitivity to the thermosetting resin composition, it is preferable to include an exposure step of exposing the above-mentioned layer formation step and an exposure step of exposing the above-mentioned exposed thermosetting resin composition layer (resin layer). The manufacturing method of the developing processing step of developing processing. After this development, it is preferable to further harden the exposed resin layer by heating at 50-500 degreeC (more preferably 150-400 degreeC). In addition, as described above, when a thermosetting resin composition imparted with photosensitivity is used, the composition can be cured by exposure in advance, and then desired processing (for example, lamination described below) can be performed as necessary, and further by heating to harden it further.

The manufacturing method of the laminated body of this invention includes the manufacturing method of the cured film of this invention. In the manufacturing method of the laminated body of this invention, after forming a cured film, the layer forming step and the heating step of the thermosetting resin composition are sequentially performed again in this order according to the manufacturing method of the cured film described above, or when photosensitivity is imparted, again Preferably, the layer forming step, the exposure step, and the developing treatment step (and further the heating step as needed) are performed in sequence. In particular, it is preferable to perform each of the above steps in sequence 2 to 5 times (that is, 3 to 6 times in total). It can be set as a laminated body by laminating|stacking a cured film in this way. In the present invention, it is particularly preferable to provide a metal layer on the part where the cured film is provided. The details of these will be described below.

<<Layer Formation Step>> The manufacturing method of a preferred embodiment of the present invention includes a layer formation step in which a thermosetting resin composition is applied to a substrate to form a layer. The type of substrate can be appropriately set according to the application, but is not particularly limited, and examples include semiconductor production substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, and vapor-deposited films. , Magnetic film, reflective film, Ni, Cu, Cr, Fe and other metal substrates, paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, electrode plates of plasma display panels (PDP), etc. In the present invention, the semiconductor fabrication substrate is particularly preferred, and the silicon substrate is even more preferred. Moreover, when a thermosetting resin composition layer is formed on the surface of a resin layer or the surface of a metal layer, a resin layer or a metal layer becomes a board|substrate. As a method of applying the thermosetting resin composition to a substrate, coating is preferable. Specifically, as a method of application, a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, and a spin coating method can be exemplified. , slit coating method and inkjet method, etc. From the viewpoint of the uniformity of the thickness of the thermosetting resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an ink jet method are more preferred. A resin layer of a desired thickness can be obtained by adjusting an appropriate solid content concentration and coating conditions according to the method. In addition, the coating method can be appropriately selected according to the shape of the substrate. As long as it is a circular substrate such as a wafer, a spin coating method, a spray coating method, an inkjet method, etc. are preferred, and as long as a rectangular substrate is used, slit coating is used. Method, spray method, ink jet method, etc. are preferred. In the case of a spin coating method, it can be applied, for example, at a rotational speed of 500 to 2000 rpm for about 10 seconds to 1 minute.

<<Drying step>> In the production method of the present invention, after forming the thermosetting resin composition layer and after the layer forming step, a step of drying to remove the solvent may be included. The preferred drying temperature is 50-150°C, more preferably 70-130°C, and even more preferably 90-110°C. As a drying time, 30 seconds - 20 minutes are illustrated, Preferably it is 1 minute - 10 minutes, More preferably, it is 3 minutes - 7 minutes.

<<Exposure Step>> The production method of the present invention may include an exposure step in which the above-mentioned thermosetting resin composition layer is exposed to light. The exposure amount is not particularly limited within the range that can cure the thermosetting resin composition. For example, it is preferably 100 to 10,000 mJ/cm ² in terms of exposure energy at a wavelength of 365 nm, and more preferably 200 to 8,000 mJ/cm ² . good. The exposure wavelength can be appropriately set within the range of 190 to 1000 nm, and is preferably 240 to 550 nm. Regarding the exposure wavelength, 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), broad (3 wavelengths of g, h, i-ray), (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. With regard to the thermosetting resin composition of the present invention, exposure by a high-pressure mercury lamp is particularly preferable, and among them, exposure by i-ray is preferable. Thereby, especially high exposure sensitivity can be obtained.

<<Development Treatment Step>> The production method of the present invention may include a development treatment step of subjecting the exposed thermosetting resin composition layer to development treatment. By performing development, when it is a negative type, an unexposed part (non-exposed part) is removed, and when it is a positive type, an exposed part (exposed part) is removed. The development method is not particularly limited as long as a desired pattern can be formed, and for example, development methods such as spin-on immersion, spray, immersion, and ultrasonic waves can be employed. Development is performed using a developer. The developer can be used without particular limitation as long as the unexposed part (non-exposed part) can be removed. The developer preferably contains an organic solvent. In the present invention, the developer preferably contains an organic solvent with ClogP of -1 to 5, and more preferably contains an organic solvent with ClogP of 0 to 3. ClogP can be obtained as a calculated value by inputting a structural formula in ChemBioDraw (Chemical Biograph). As the organic solvent, the esters include, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyric acid. Ethyl ester, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxy acetate (example: methyl alkoxy acetate , ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate esters, etc.)), 3-alkoxypropionic acid alkyl esters (for example: methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate) ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkoxypropionate alkyl esters (Example: 2 -Methyl alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate ester, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.)), methyl 2-alkoxy-2-methylpropionate and Ethyl 2-alkoxy-2-methylpropanoate (eg, methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropanoate), pyruvic acid Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, such as Preferable examples include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, and 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 Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and aromatic hydrocarbons For example, toluene, xylene, anisole, limonene, etc. are suitably mentioned, and dimethyl sulfite is suitably mentioned as a sulfite. In the present invention, especially cyclopentanone and γ-butyrolactone are preferable, and cyclopentanone is even more preferable. 50 mass % or more of the developer is preferably an organic solvent, 70 mass % or more is an organic solvent, and 90 mass % or more is an organic solvent. Moreover, 100 mass % of the developer may be an organic solvent.

The development time is preferably 10 seconds to 5 minutes. The temperature at the time of image development is not specifically limited, Usually, it can carry out at 20-40 degreeC. After the treatment with the developer, further rinsing can be performed. Rinse is preferably performed with a solvent different from that of the developer. For example, rinsing can be performed using a solvent contained in the thermosetting resin composition. The flushing time is preferably 5 seconds to 1 minute.

<<Heating step>> In the production method of the present invention, it is preferable to include a step of heating after the layer forming step, the drying step, or the developing step. In the heating step, a cyclization reaction of the polymer precursor is carried out. In addition, the composition of the present invention may contain a radically polymerizable compound other than the polymer precursor, and in this step, curing and the like of the radically polymerizable compound other than the unreacted polymer precursor can be performed. The heating temperature (maximum heating temperature) in the heating step is 50 to 500°C, preferably 50 to 450°C, more preferably 140 to 400°C, and even more preferably 160 to 350°C. The heating is preferably performed at a temperature increase rate of 1 to 12°C/min, more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min from the temperature at the start of heating to the maximum heating temperature. By setting the temperature increase rate to be 2° C./min or more, excessive volatilization of the amine can be prevented while ensuring productivity, and by setting the temperature increase rate to 12° C./min or less, the residual stress of the cured film can be relieved. The temperature at the start of heating is preferably 20 to 150°C, more preferably 20 to 130°C, and even more preferably 25 to 120°C. The temperature at the start of heating means the temperature at the time of starting the step of heating up to the maximum heating temperature. For example, when the thermosetting resin composition is applied to the substrate and then dried, the temperature after drying is, for example, 30 to 200°C lower than the boiling point of the solvent contained in the thermosetting resin composition. It is better to raise the temperature gradually. The heating time (heating time at the highest heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and particularly preferably 30 to 240 minutes. Especially when forming a multilayer laminated body, it is preferable to heat at the heating temperature of 180-320 degreeC from the viewpoint of the adhesiveness between layers of a cured film, and it is more preferable to heat at 180-260 degreeC. Although the reason for this is uncertain, the reason is considered to be as follows. That is, by setting this temperature, the acetylene groups of the polymer precursors between the layers undergo a cross-linking reaction with each other.

Heating can be done in stages. As an example, the previous treatment steps can be carried out from 25°C to 180°C at 3°C/min and held at 180°C for 60 minutes, 2°C/min from 180°C to 200°C and held at 200°C for 120 minutes . The heating temperature of the pretreatment step is preferably 100-200°C, more preferably 110-190°C, and even more preferably 120-185°C. In this pretreatment process, as described in US Patent No. 9159547, it is also preferable to perform treatment while irradiating ultraviolet rays. The properties of the film can be improved by these pretreatment steps. The pretreatment step may be performed in a short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be two or more steps, for example, the pretreatment step 1 may be performed in the range of 100 to 150°C, and then the pretreatment step 2 may be performed in the range of 150 to 200°C. Furthermore, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5°C/min.

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

<<Metal layer forming step>> It is preferable that the production method of the present invention includes a metal layer forming process of forming a metal layer on the surface of the thermosetting resin composition layer after the development treatment. The metal layer is not particularly limited, and conventional metals can be used, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper and aluminum are more preferred, and copper is further preferred. The formation method of a metal layer is not specifically limited, Existing methods can be applied. For example, the methods described in Japanese Patent Laid-Open No. 2007-157879, Japanese Patent Publication No. 2001-521288, Japanese Patent Laid-Open No. 2004-214501, and Japanese Patent Laid-Open No. 2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and methods of combining these can be considered. More specifically, a patterning method in which sputtering, photolithography and etching are combined, and a patterning method in which photolithography and electrolytic plating are combined can be mentioned. The thickness of the metal layer is preferably 0.1 to 50 μm, and more preferably 1 to 10 μm, in the thickest portion.

<<Lamination step>> It is preferable that the production method of the present invention further includes a lamination step. The lamination step includes performing the layer forming step and the heating step in this order again, or when the thermosetting resin composition is given photosensitivity, performing one of the layer forming step, the exposing step, and the developing treatment step in this order. series of steps. Of course, the layering step may also include the above drying step or heating step, and the like. When the layering step is further performed after the layering step, the surface activation treatment step may be further performed after the above-mentioned heating step, after the above-mentioned exposure step, or after the above-mentioned metal layer forming step. As the surface activation treatment, plasma treatment is exemplified. Preferably, the above-mentioned layering step is performed 2 to 5 times, more preferably 3 to 5 times. For example, resin layers such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer are preferably 3 or more and 7 or less layers, and more preferably 3 or more and 5 or less layers. Specifically, in the present invention, after the metal layer is provided, the layer forming step and the heating step of the above-mentioned thermosetting resin composition are sequentially performed, or when photosensitivity is imparted to the thermosetting resin composition, the step is sequentially performed. The above-mentioned layer forming step, the above-mentioned exposing step and the above-mentioned developing treatment step (and further heating step as needed) are preferably used to cover the above-mentioned metal layer. The thermosetting resin composition layer (resin layer) and the metal layer can be alternately laminated by alternately performing the lamination process of laminating the thermosetting resin composition layer (resin) and the metal layer forming process.

This invention also discloses the semiconductor device which has the cured film or laminated body of this invention. As a specific example of a semiconductor device in which the thermosetting resin composition of the present invention is used in the formation of the interlayer insulating film for rewiring layers, the description and the drawings in paragraphs 0213 to 0218 of Japanese Patent Laid-Open No. 2016-027357 can be referred to. 1, and these contents are incorporated into this manual. [Example]

Hereinafter, the present invention will be described in further detail with reference to Examples. Materials, usage amounts, ratios, processing contents, and processing steps shown in the following examples are within the scope of not departing from the spirit of the present invention, and can be appropriately changed. Therefore, the scope of the present invention is not limited to the specific examples shown below.

(Synthesis example 1) [Synthesis of polyimide precursor resin A-1 derived from pyromellitic dianhydride, 4,4'-diaminodiphenyl ether and 3-hydroxybenzyl alcohol] 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140°C for 12 hours) and 16.33 g (131.58 mmol) of 3-hydroxybenzyl alcohol were suspended in 50 mL of N-methylpyrrolidone, and dried over molecular sieves. The suspension was heated at 100°C for 3 hours. A clear solution was obtained after a few minutes after heating. The reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) of pyridine and 90 mL of N-methylpyrrolidone were added. Next, the reaction mixture was cooled to -10°C, and 16.12 g (135.5 mmol) of thionite chloride was added over 10 minutes while maintaining the temperature at -10±4°C. During the addition of thionite chloride, the viscosity increased. The reaction mixture was stirred at room temperature for 2 hours after dilution with 50 mL of N-methylpyrrolidone. Next, N-methylpyrrolidone in which 11.08 g (58.7 mmol) of 4,4'-diaminodiphenyl ether was dissolved in 100 mL was added dropwise to the reaction mixture at 20 to 23° C. over 20 minutes. solution. Next, the reaction mixture was stirred at room temperature for 1 night. Next, the polyimide precursor resin was precipitated in 5 liters of water, and the water-polyimide precursor resin mixture was stirred at 5000 rpm for 15 minutes. The polyimide precursor resin was removed by filtration, and the mixture was stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor resin was dried at 45° C. for 3 days under reduced pressure. In the polyimide precursor, Mw=22800 and Mn=8100.

(Synthesis example 2) [Polyimide precursor resin A-2 derived from oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate and 4,4'-diaminodiphenyl ether Synthesis] 20.0 g (64.5 mmol) of oxodiphthalic dianhydride was suspended in diethylene glycol diethylene glycol while removing water in a drying reactor equipped with a stirrer, a capacitor, and a flat bottom applicator equipped with an internal thermometer. Methyl ether 140mL. 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, and 10.7 g (135 mmol) of pyridine were continuously added, and the mixture was stirred at a temperature of 60° C. for 18 hours. Next, after cooling the mixture to -20°C, 16.1 g (135.5 mmol) of thionium chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. Next, after warming the mixture to room temperature and stirring for 2 hours, 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added. Thus, a clear solution was obtained. Next, to the obtained transparent liquid, 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added by dropwise addition over 1 hour. During the addition of 4,4'-diaminodiphenyl ether, the viscosity increased. Next, 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added, and the mixture was stirred for 2 hours. Next, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was removed by filtration, and the mixture was stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor resin was dried at 45° C. for 3 days under reduced pressure. In the polyimide precursor, Mw=23500 and Mn=8800.

(Synthesis example 3) [derived from oxodiphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2-hydroxyethyl methacrylate and 4,4'- Synthesis of Polyimide Precursor Resin A-3 of Diaminodiphenyl Ether] While removing moisture in a drying reactor equipped with a stirrer, a capacitor, and a flat-bottom applicator equipped with an internal thermometer 10.0 g (32.2 mmol) of dicarboxylic dianhydride and 9.47 g (32.3 mmol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride were suspended in 140 mL of diglyme. 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, and 10.7 g (135 mmol) of pyridine were continuously added, and the mixture was stirred at a temperature of 60° C. for 18 hours. Next, after cooling the mixture to -20°C, 16.1 g (135.5 mmol) of thionium chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. Next, after warming the mixture to room temperature and stirring for 2 hours, 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added. Thus, a clear solution was obtained. Next, to the obtained transparent liquid, 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added by dropwise addition over 1 hour. During the addition of 4,4'-diaminodiphenyl ether, the viscosity increased. Next, 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added, and the mixture was stirred for 2 hours. Next, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was removed by filtration, and the mixture was stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor resin was dried at 45° C. for 3 days under reduced pressure. In the polyimide precursor, Mw=24300 and Mn=9500.

(Synthesis Example 4) [Polybenzoxazole precursor A derived from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 4,4'-oxydibenzoyl chloride -4 Synthesis] 28.0 g (76.4 mmol) of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was dissolved in 200 g of N-methylpyrrolidone with stirring. Next, 12.1 g (153 mmol) of pyridine was added, and 20.7 g (70.1 mmol) of 4,4'-oxodibenzyl chloride was added dropwise over 1 hour while maintaining the temperature at -10 to 0°C. ear) was dissolved in a solution of 75 g of N-methylpyrrolidone. After stirring for 30 minutes, 1.00 g (12.7 mmol) of acetyl chloride was added, and the mixture was further stirred for 60 minutes. Next, the polybenzoxazole precursor resin was precipitated in 6 liters of water, and the water-polybenzoxazole precursor resin mixture was stirred at 500 rpm for 15 minutes. The polybenzoxazole precursor resin was removed by filtration, and the mixture was further stirred in 6 liters of water for 30 minutes and filtered again. Next, the polybenzoxazole precursor resin was dried at 45° C. for 3 days under reduced pressure. In the polybenzoxazole precursor, Mw=21500 and Mn=7500.

(Synthesis Example 5) 1.16 g (10.0 mmol) of maleic acid was dissolved in 20.0 g of methanol, and 1.95 g (10.0 mmol) of N,N-dicyclohexylmethyl was added dropwise over 10 minutes. amine group. The resulting solution was concentrated at 35° C. under reduced price to obtain a salt of N,N-dicyclohexylmethylamine and maleic acid.

(Synthesis Example 6) The salts other than the salt of N,N-dicyclohexylmethylamino group and maleic acid were synthesized in the same manner as in Synthesis Example 5.

<Method for Measuring Molecular Weight> The molecular weight (weight-average molecular weight, number-average molecular weight) of the polymer precursor was defined as a polystyrene-equivalent value in accordance with gel permeation chromatography (GPC measurement). Specifically, HLC-8220 (trade name: manufactured by Tosoh Corporation) was used, and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (trade name: Tosoh Corporation) were used as columns. system) to obtain. The eluent was measured using THF (tetrahydrofuran).

<Method for determining pKa> <<Acid compound> As for the pKa of the acidic compound, 50 mg of the acidic compound was added to 50 mL of water, and AT-420 manufactured by KYOTO ELECTRONICS MANUFACTURING CO., LTD. was used as a titrant with a 0.01N aqueous sodium hydroxide solution. (trade name) Potentiometric difference automatic titrator, measured at 25°C. The pH at which half of the amount of the aqueous sodium hydroxide solution required to neutralize the acid group was added was taken as the pKa of the acidic compound. <<Amine compound>> Regarding the pKa of the conjugate acid of the amine compound, 50 mg of the amine compound was added to 50 mL of water, and 0.01N hydrochloric acid was used as a titrant, and AT-420 (trade name) manufactured by KYOTO ELECTRONICS MANUFACTURING CO., LTD. was used. The potentiometric difference automatic titrator measured at 25 degreeC. The pH at which half of the amount of hydrochloric acid required to neutralize the amine group was added was taken as pKb. The pKa of the amine-valent conjugated acid is subtracted from 14 to the numerical value of pK[b]. <<Sulfonic acid compound etc.>> Basically, it is measured by the above-mentioned method, but the pKa of sulfonic acid, which is a strong acid, may not be obtained by this method. In these cases, literature values measured in water are used (Angew. Chem. Int. Ed. 2016, 55, 350-354).

The relationship (A-pKa) between the pKa of the amine compound and the acidic compound evaluated in the present invention is represented by the following formula (1a). A-pKa=(pKa of conjugate acid of amine compound+pKa of acidic compound)/2 Formula (1a)

<Preparation of thermosetting resin composition> Each component described in the following table was blended, passed through a filter with a pore width of 0.8 μm, and subjected to pressure filtration at a pressure of 3.0 MPa to obtain a thermosetting resin. Curable resin composition. also. In Examples 1 to 62, 70 to 85, and Comparative Examples 4, 5, 9 and 10, the synthesized salts were added according to the above synthesis examples. In Examples 63 to 69, amine compounds and acidic compounds were added. In 7 and 8, an amine compound or an acidic compound is added.

<Change in Film Thickness> <<Film Thickness Before Elapsed Time>> Each thermosetting resin composition described in the following table was applied to a silicon wafer by spin coating to form a thermosetting resin composition layer. The obtained silicon wafer to which the thermosetting resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes, thereby obtaining a uniform thermosetting resin composition layer with a thickness of about 15 μm on the silicon wafer. This value was taken as the film thickness before elapsed time. <<Film thickness after elapse of time>> Put each thermosetting resin composition described in the table below into a glass container, seal it, and leave it to stand at 25°C for 14 days, then apply and determine the pre-elapsed film. A thermosetting resin composition layer was formed on a silicon wafer by spin coating at the same rotational speed when thick. The obtained silicon wafer to which the thermosetting resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes, thereby obtaining a uniform thermosetting resin composition layer on the silicon wafer. The film thickness of the obtained thermosetting resin composition layer was measured by the same method as the above, and this value was made into the film thickness after time. <<Film thickness change rate>> The film thickness change rate was calculated by the following formula. Film thickness change rate [%] = | film thickness before time - film thickness after time | / film thickness before time × 100 Film thickness change rate A: less than 10% B: 10% or more and less than 15% C: 15 % or more and less than 20% D: 20% or more

<Film strength> Thermosetting resin composition layers were formed by applying each thermosetting resin composition described in the following table to a silicon wafer by spin coating. The obtained silicon wafer to which the thermosetting resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes, thereby obtaining a uniform thermosetting resin composition layer with a thickness of about 15 μm on the silicon wafer. The obtained thermosetting resin composition layer (resin layer) was heated at a temperature increase rate of 10° C./min in a nitrogen atmosphere, and after reaching 250° C., it was heated for 3 hours. The cured resin layer (cured film) was immersed in a 4.9% hydrofluoric acid solution to peel off the cured film from the silicon wafer. Using a punching machine, the peeled cured film was produced into a test piece having a width of 3 mm and a sample length of 30 mm. Using a tensile tester (Tensilon), at a crosshead speed of 300 mm/min, along the longitudinal direction of the film, in an environment of 25°C and 65% RH (relative humidity), the obtained test pieces were subjected to JIS-K6251. measured. The evaluation was carried out five times each, and the average value was used for the elongation at the time of film breaking (elongation at break). A: 60% or more B: 55% or more and less than 60% C: 50% or more and less than 55% D: less than 50%

<Adhesion> Thermosetting resin composition layers were formed by applying each thermosetting resin composition described in the following table to a copper wafer by spin coating. The obtained copper wafer to which the thermosetting resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes to obtain a uniform thermosetting resin composition layer with a thickness of about 15 μm on the copper wafer. The resulting thermosetting resin composition layer (resin layer) was heated at a temperature increase rate of 10°C/min in a nitrogen atmosphere, and after reaching 250°C, heated for 3 hours, thereby forming a copper wafer on the copper wafer. Hardened film. From this board|substrate, it cut|disconnected by 1 mm space|interval according to JIS K5600-5-6:1999, and the cross-cut test was performed, and the adhesive force of a cured film and a copper wafer was evaluated. A The total area of the cured film from the copper wafer glass is less than 2% B The total area of the cured film from the copper wafer glass is more than 2% and less than 5% C The total area of the cured film from the copper wafer glass is 5% More than 10% D is more than 10% from the total area of the cured film of the copper wafer glass

<Corrosion (Cu Corrosion)> Thermosetting resin composition layers were formed by applying each thermosetting resin composition described in the following table to a copper wafer by spin coating. The obtained copper wafer to which the thermosetting resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes to obtain a uniform thermosetting resin composition layer with a thickness of about 15 μm on the copper wafer. The obtained thermosetting resin composition layer was heated at a temperature increase rate of 10° C./min in a nitrogen atmosphere, and after reaching 250° C., the cured film was formed on the copper wafer by heating for 3 hours. The substrate was put into a constant temperature and humidity layer with a temperature of 85°C and a humidity of 85% for 24 hours, and the corrosion-producing part was observed with an optical microscope, and the corrosion-producing part was measured with respect to the area of the surface on the side where the cured film of the copper wafer was provided. The area is a few percent. A: Less than 5% B: More than 5% and less than 10% C: More than 10% and less than 20% D: More than 20%

<Analysis> Thermosetting resin compositions containing photo-radical polymerization initiators (photosensitive resin compositions) among the thermosetting resin compositions described in the following table were applied to a copper wafer by spin coating to form thermal Curable resin composition layer. The obtained silicon wafer to which the thermosetting resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes to obtain a uniform thermosetting resin composition layer with a thickness of about 15 μm on the silicon wafer. Using an exposure device (Karl-Suss MA150 [trade name]), the thermosetting resin composition layer was exposed through a mask having a pattern of lines and spaces (step: 5 to 20 μm). The exposure was performed by a high-pressure mercury lamp, and 500 mJ/cm ² was irradiated in terms of exposure energy at a wavelength of 365 nm. The exposed thermosetting resin composition layer was dissolved in cyclopentanone for 75 seconds, and spin-on immersion development was performed. The line width of the developed site was evaluated on the following criteria. When the exposed width of the developed base substrate is within ±10% of the mask size, it is determined that the line width has been analyzed, indicating that the analyzed line width is smaller than the light irradiated portion and the light non-irradiated portion. The higher the solubility of the developer, the better the result. A The analyzed line width is more than 5 μm and less than 10 μm B The analyzed line width is more than 10 μm and less than 15 μm C The analyzed line width is more than 15 μm, or no image is displayed

<Glass transition temperature (Tg)> After passing each thermosetting resin composition through a filter with a pore width of 0.8 μm and performing pressure filtration at a pressure of 0.3 MPa, it was spin-coated on a silicon wafer . The silicon wafer to which the thermosetting resin composition was applied was dried on a hot plate at 100° C. for 5 minutes to form a thermosetting resin composition layer with a uniform thickness of 10 μm on the silicon wafer. The resin layer was obtained by completely exposing the thermosetting resin composition layer on the silicon wafer with an exposure energy of 400 mJ/cm ² using a stepper (Nikon NSR 2005 i9C). However, when the thermosetting resin composition which does not contain a photoradical polymerization initiator is used, exposure is not performed. Furthermore, after heating the resin layer at 200 degreeC for 3 hours, it was immersed in the hydrofluoric acid aqueous solution, and the resin layer was peeled from the silicon wafer. The Tg of the peeled resin layer was measured using a viscoelasticity measuring apparatus Rhosol-E4000 (manufactured by UBM Co Ltd). Specifically, the Tg of the resin layer was measured as the temperature at which the loss tangent (tan δ) measured with a viscoelasticity measuring apparatus became the maximum under a constant temperature rise condition. The temperature of the resin layer was increased from 0°C to 350°C at a temperature increase rate of 5°C/min, and a strain of 0.1 degree was applied to the resin layer at a cycle of 100 Hz, and Tg was measured and evaluated based on the following criteria. A: Above 270°C B: Above 260°C and below 270°C C: Above 250°C and below 260°C D: Above 240°C and below 250°C E: Above 230°C and below 240°C F: Above 220°C and below 230°C G: less than 220℃

表中的“添加量”的單位為質量份。Mw是指各化合物的分子量，ΔMw是指“酸性化合物的分子量-鹼性化合物的分子量”。表2以後均相同。 [表2]

[Table 1]

The unit of "addition amount" in the table is parts by mass. Mw means the molecular weight of each compound, and ΔMw means "the molecular weight of the acidic compound - the molecular weight of the basic compound". Table 2 and later are the same. [Table 2]

[table 3]

[表5]

[表6]

[Table 4]

[table 5]

[Table 6]

[Table 7]

[Table 8]

[Table 9]

[Table 10]

[Table 11]

[Table 12]

[Table 13]

(A) Polymer Precursors A-1 to A-4: Polymer Precursors Produced in Synthesis Examples 1 to 4

(B) Amine compound Each of the amine compounds listed in the table was used

(C) Acidic compound Each acid compound described in the table was used

(D) Solvent DMSO: dimethyl sulfoxide GBL: γ-butyrolactone The mixing ratio of DMSO and GBL was 20:80 in terms of mass ratio.

(E) Photoradical polymerization initiators (all trade names) OXE-1: IRGACURE OXE 01 (manufactured by BASF) OXE-2: IRGACURE OXE 02 (manufactured by BASF) NCI-831: NCI-831 (ADEKA CORPORATION system)

(F) Radically polymerizable compounds (all trade names) SR-209: SR-209 (manufactured by Sartomer Company, Inc.) SR-231: SR-231 (manufactured by Sartomer Company, Inc.) SR-239: SR- 239 (manufactured by Sartomer Company, Inc.)

(G) Polymerization inhibitor G-1: 1,4-p-benzoquinone G-2: 4-methoxyphenol G-3: 1,4-dihydroxybenzene

(H) Metal adhesion modifier H-1: The following compound H-2: The following compound H-3: The following compound

Et表示乙基。[Chemical formula 35]

Et represents ethyl.

(I) Migration inhibitor I-1: 1H-tetrazole I-2: 1,2,4-triazole I-3: 5-phenyltetrazole

(J) Hardening accelerator J-1: The following compound J-2: The following compound J-3: The following compound

[Chemical formula 36]

(K) Orgatix TC-100, an organic compound containing a Group 4 element, diisopropoxybis(acetylacetone)titanium manufactured by Matsumoto Fine Chemical Co. Ltd. [Chemical formula 37]

Orgatix TC-401, titanium tetraacetylacetone manufactured by Matsumoto Fine Chemical Co. Ltd. [Chemical formula 38]

Orgatix TC-710, Diisopropoxybis(ethylacetate)titanium manufactured by Matsumoto Fine Chemical Co. Ltd. [Chemical formula 39]

Orgatix TC-201, titanium bis-2-ethylhexyloxybis(2-ethyl-3-hydroxyhexanol) manufactured by Matsumoto Fine Chemical Co. Ltd. [Chemical formula 40]

Orgatix TC-245, manufactured by Matsumoto Fine Chemical Co. Ltd. Titanium octane glycol glycol ester

Orgatix TC-150, zirconium tetraacetylacetonate manufactured by Matsumoto Fine Chemical Co. Ltd.

Bis(cyclopentadienyl)titanium dichloride [Chemical formula 41]

Bis(cyclopentadienyl)dimethyltitanium [Chemical formula 42]

Bis(cyclopentadienyl)zirconium dichloride [Chemical formula 43]

Bis(cyclopentadienyl)hafnium dichloride [Chemical formula 44]

IRGACURE 784 [Chemical Formula 45]

As is clear from the results in the above table, using an amine compound and an acidic compound, it was found that one-half (A-pKa) of the sum of the pKa of the conjugate acid of the amine compound and the pKa of the acidic compound is in the range of 3.5 to 7.1. In the curable resin composition, the suppression of the film thickness change was excellent, and the strength of the cured film was high (Examples 1 to 85). In addition, regarding the analytical properties when adhesion, copper corrosion resistance, and photosensitivity are imparted, the samples of the examples all satisfy the requirements for use. On the other hand, for those that did not contain an amine compound or an acidic compound (Comparative Examples 1 to 3, 6 to 8), even if both were contained, the A-pKa was less than 3.5 (Comparative Examples 4 and 9) and greater than 7.1 (Comparative Examples 5 and 10). ), the inhibition of film thickness variation or the film strength is poor.

<Example 100> Using the thermosetting resin composition of Example 48, it was coated on a silicon wafer by a spin coating method. The silicon wafer coated with the thermosetting resin composition layer was dried on a hot plate at 100° C. for 5 minutes to form a uniform thermosetting resin composition layer with a thickness of 15 μm on the silicon wafer. Using a stepper (NSR 2005 i9C [trade name] manufactured by NIKON CORPORATION), the thermosetting resin composition layer on the silicon wafer was subjected to an exposure energy of 500 mJ/cm ² through a mask having a hole of 10 μm in diameter. exposure. The resin layer was developed with cyclopentanone for 60 seconds, thereby forming pores having a diameter of 10 μm. Next, it heated up at the temperature increase rate of 10 degreeC/min under nitrogen atmosphere, and after reaching 250 degreeC, it heated for 3 hours, and obtained the cured film (final cured film). After cooling to room temperature, a copper foil layer (metal layer) with a thickness of 2 μm was formed on the surface of the cured film by vapor deposition in the direction of covering the above-mentioned holes, and the excess part of the copper foil layer was removed by dry etching. . Furthermore, the same kind of thermosetting resin composition was used again on the surface of the metal layer and the cured film, and the step of filtration of the thermosetting resin composition until the patterned film was heated for 3 hours was performed again in the same manner as above, As shown in FIG. 1, the laminated body which consists of cured film/metal layer/cured film was produced. It turns out that this cured film is excellent in insulation, and can be utilized suitably as an interlayer insulating film for rewiring layers. In FIG. 1, 201-204 show a cured film, 301-303 show a metal layer, 401-403 show the groove|channel formed between a cured film and a cured film, 500 shows a laminated body. Moreover, as a result of manufacturing a semiconductor device using the interlayer insulating film for rewiring layers, it was confirmed that the operation was normal.

201～204‧‧‧Curing film 301～303‧‧‧Metal layer 401～403‧‧‧Slot 500‧‧‧Laminated body

FIG. 1 shows a schematic diagram of the laminate produced in this example.

Claims (29)

A kind of thermosetting resin composition, it comprises: is selected from polyimide precursor and polybenzyl

A polymer precursor in an azole precursor; a salt comprising a cation derived from an amine compound and an anion derived from an acidic compound; and a solvent, the pKa of the conjugated acid of the amine compound and the pKa of the acidic compound are in the following formula 1 range, 3.5

(pKa of conjugate acid of amine compound + pKa of acidic compound)/2

6.8 (Formula 1), and the molecular weight of the amine compound is 120 or more. The thermosetting resin composition according to claim 1, wherein the amount of the acid group of the acidic compound is 0.9 to 3.0 equivalents relative to the amount of the amine group of the amine compound. The thermosetting resin composition according to claim 1 or claim 2, wherein the molecular weight of the amine compound is 120-1000. The thermosetting resin composition as described in claim 1 or claim 2, wherein the amine compound is represented by the following formula (B1),

R ^B1 to R ^B3 each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms, and may be linked to each other to form a ring, but not all of R ^B1 to R ^B3 are hydrogen atoms. The thermosetting resin composition according to claim 4, wherein R ^B1 and R ^B2 of the formula (B1) are independently a linear or branched alkyl group having 1 to 6 carbon atoms, a cyclopentane or cyclohexyl, R ^B3 represents a hydrogen atom, a straight or branched alkyl group having 1 to 6 carbon atoms, a cyclopentyl group, a cyclohexyl group or a pyridyl group. The thermosetting resin composition according to claim 1 or claim 2, wherein in the amine compound, the number of connecting nitrogen atoms to the carbon atom farthest from the nitrogen atom and the number of atoms of the carbon atom are 2~5. The thermosetting resin composition according to claim 1 or claim 2, wherein the acidic compound has a pKa of 2 or less. The thermosetting resin composition as described in claim 1 or claim 2, wherein the acidic compound is represented by any one of the following formulae (AC1) to (AC5),

In the formula, R ^A1 represents a hydroxyl group or a monovalent organic group, and R ^A2 to R ^A13 each independently represent a hydrogen atom or a monovalent organic group. The thermosetting resin composition according to claim 1 or claim 2, wherein the molecular weight of the acidic compound is 60-500. The thermosetting resin composition according to claim 1 or claim 2, wherein the polyimide precursor has a repeating unit represented by formula (1),

A1 and A2 each independently represent ^an oxygen atom or NH, ^R113 and ^R114 each independently represent a ^hydrogen atom or a monovalent organic group, ^R115 represents a tetravalent organic group, and ^R111 represents a divalent organic group. The thermosetting resin composition according to claim 10, wherein at least one of R ¹¹³ and R ¹¹⁴ is a group having an ethylenically unsaturated bond. The thermosetting resin composition according to claim 1 or claim 2, further comprising a photoradical polymerization initiator. The thermosetting resin composition according to claim 12, wherein the photo-radical polymerization initiator is an oxime compound. The thermosetting resin composition according to claim 1 or claim 2, further comprising a radical polymerizable compound. The thermosetting resin composition according to claim 1 or claim 2, further comprising an organic compound containing a Group 4 element. The thermosetting resin composition according to claim 15, wherein the Group 4 element is at least one element selected from the group consisting of titanium, zirconium and hafnium. The thermosetting resin composition according to claim 15, wherein the Group 4 element is at least one element selected from the group consisting of titanium and zirconium. The thermosetting resin composition according to claim 1 or claim 2, which is for forming an interlayer insulating film for a rewiring layer. A cured film formed from the thermosetting resin composition described in any one of the first to eighteenth claims. A laminate having two or more layers of the cured film described in claim 19. The laminated body according to claim 20 of the scope of application has 3 to 7 layers of the cured film. The laminate according to claim 20, wherein a metal layer is provided between the cured films. A method for manufacturing a cured film, comprising: a layer forming step of applying the thermosetting resin composition described in any one of the claims 1 to 18 to a substrate to form a layer; heating In the step, the layered thermosetting resin composition is heated at a temperature of 50 to 500°C. A method for producing a cured film, comprising: a layer forming step of applying the thermosetting resin composition described in any one of the claims 1 to 18 to a substrate to form a layer; exposing a step of exposing the thermosetting resin composition formed in a layered shape; a developing treatment step, developing treatment of the exposed thermosetting resin composition; and a heating step, at a temperature of 50-500° C. The exposed thermosetting resin composition is heated. A method for manufacturing a layered product, which further includes the method for producing a cured film described in Item 23 or 24 of the scope of application after forming a cured film according to the method for manufacturing a cured film described in claim 23 The step of forming a hardened film. A method for manufacturing a layered product, which further includes the method for producing a cured film according to the claim 23 or 24 after forming a cured film according to the method for manufacturing a cured film described in claim 24. The step of forming a hardened film. A semiconductor device having the cured film described in claim 19 of the patent application scope. A method of manufacturing a semiconductor device, wherein the cured film described in claim 19 is processed as a semiconductor device. A method for producing a thermosetting resin composition, comprising: making the pKa of the conjugated acid of the amine compound and the pKa of the acidic compound into the range of the following formula 1 to be selected from a polyimide precursor and a polybenzoyl

The step of mixing the polymer precursor, the amine compound, the acidic compound and the solvent in the azole precursor, 3.5

(pKa of conjugate acid of amine compound + pKa of acidic compound)/2

6.8 (Formula 1), and the molecular weight of the amine compound is 120 or more.

Images