TW201908370A - Thermosetting resin composition, cured film thereof, laminated body, semiconductor device, and the like - Google Patents

Abstract

Provided are: a thermosetting resin composition which is excellent in terms of suppressing fluctuations over time in the thickness of a film formed from the thermosetting resin composition and which is excellent in terms of strength upon formation of a cured film; a cured film of the composition; a layered product; a semiconductor device; and methods for producing these. This thermosetting resin composition contains: a polymer precursor selected from between a polyimide precursor and a polybenzoxazole precursor; a salt containing a cation derived from an amine compound and an anion derived from an acidic compound; and a solvent. The pKa value of a conjugate acid of the amine compound and the pKa value of the acidic compound satisfy numerical formula 1. Numerical formula 1: 3.5 ≤ (pKa value of conjugate acid of amine compound + pKa value of the acidic compound) / 2 ≤ 7.1.

Description

Thermosetting resin composition and its cured film, laminated body, semiconductor device, and manufacturing method thereof

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

Polyimide resins and polybenzoxazole resins, such as cyclized resins, are excellent in heat resistance and insulation properties, and are therefore used in various applications (for example, see Non-Patent Document 1 and Non-Patent Document 2). This application is not particularly limited, and if an actual mounting semiconductor device is exemplified, it may be used as a material of an insulating film or a sealing member. It is also used as a base film or a cover film of a flexible substrate. The polyfluorene imine resin and the like generally have low solubility in a solvent. Therefore, as an example of applying a polyfluorene imide resin or the like to a substrate, a polymer precursor before the cyclization reaction may be mentioned, and specifically, a polyfluorine imide precursor resin or a polybenzofluorene may be mentioned. An example in which the state of the azole precursor resin is dissolved in a solvent, and this is applied to a substrate or the like. Then, the polymer precursor is cyclized by heating to form a cured resin layer (cured film).

Regarding specific blends related to the composition of the polymer precursor as described above, several research examples are cited. For example, Patent Document 1 discloses a compound containing an N-aromatic glycine derivative and a polymer precursor. Photosensitive resin composition. Patent Document 2 discloses a polyfluorene containing a polyfluorene imide precursor and a thermal base generator and a solvent composed of a second amine neutral compound by thermal decomposition caused by heating at a temperature of 200 ° C or lower. Imine precursor resin composition. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Publication No. 2006-282880 [Patent Document 2] Japanese Patent Application Publication No. 2007-056196 [Non-Patent Literature]

[Non-Patent Literature 1] Science & technology Co., Ltd. "High Functionality and Application Technology of Polyimide" April 2008 [Non-Patent Literature 2] Yamoto Kakimoto / Supervisor, CMC Technology Library "Juya Foundation and Development of Amine Materials "Issued in November 2011

As mentioned above, there have been several research examples regarding the component composition of the thermosetting resin composition. However, when considering these various uses or new uses, it is difficult to say that they have been sufficiently studied in relation to the characteristics 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 enrich the material. In particular, the object is to provide a thermosetting resin composition, which is excellent in suppressing changes with time in film thickness of a film formed of a thermosetting resin composition, and has excellent strength when used as a cured film, and its cured film, laminate, Semiconductor device and manufacturing method thereof.

Based on the above-mentioned problems, as a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by adding a predetermined salt to a thermosetting resin composition. Specifically, the above-mentioned problem is solved by the following mechanism <1>, preferably by <2> to <28>. <1> A thermosetting resin composition comprising: a polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor; a cation derived from an amine compound and an acid derived compound A salt of an anion; and a solvent, the pKa of the conjugate 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 conjugate acid of the amine compound + pKa of the acid 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 based on 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 1,000. <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 connected to each other to form a ring. However, 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 in} the formula (B1) are each independently a linear or branched alkyl group having 1 to 6 carbon atoms and cyclopentane. Or a cyclohexyl group, R ^B3 is 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 amine compound, a carbon atom having the farthest distance from the nitrogen atom to the nitrogen atom is bonded to the 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 molecular weight of the acidic compound is 60 to 500. <10> The thermosetting resin composition according to any one of <1> to <9>, wherein the polyfluorene imide precursor has a repeating unit represented by formula (1), [Chemical Formula 3] A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹¹ represents a divalent organic group. <11> The thermosetting resin composition according to <10>, wherein at least one of 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>, further comprising a radical 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 used for forming an interlayer insulating film for a redistribution layer. <19> A cured film formed of the thermosetting resin composition according to any one of <1> to <18>. <20> A laminated body comprising two or more layers of the cured film according to <19>. <21> The laminated body according to <20>, which has 3 to 7 layers of the cured film. <22> The laminated body according to <20> or <21>, wherein a metal layer is provided between the 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; and heating In the step, the layer of the thermosetting resin composition 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; Steps: exposing the thermosetting resin composition formed into a layer; exposing the thermosetting resin composition; exposing the exposing thermosetting resin composition; and heating, at a temperature of 50 to 500 ° C. The exposed thermosetting resin composition is heated. <25> A method for producing a laminated body, comprising forming a cured film according to the method for producing a cured film according to <23> or <24>, and further including producing a cured film according to <23> or <24> Method of forming a hardened film. <26> A semiconductor device comprising the cured film according to <19> or the multilayer body according to any one of <20> to <22>. <27> A method for manufacturing a semiconductor device, wherein the cured film according to <19> or the multilayer body according to any one of <20> to <22> is processed as a semiconductor device. <28> A method for producing a thermosetting resin composition, the method comprising: selecting a polyfluorene imide precursor such that the pKa of the conjugate acid of the amine compound and the pKa of the acidic compound fall within the range of Formula 1 below. And polybenzoxazole precursor polymer polymer precursor, amine compound, acidic compound and solvent mixing step, 3.5 ≤ (pKa of conjugate acid of amine compound + pKa of acidic compound) / 2 ≤ 7.1 (Numerical formula 1). [Inventive effect]

According to the present invention, it is possible to provide a new thermosetting resin composition and enrich the material. In particular, it is possible to provide a thermosetting resin composition, a cured film thereof, a laminated body, and a semiconductor having excellent film thickness variation suppression properties over time and excellent strength when used as a cured film. Device, and manufacturing method thereof.

The content of the present invention will be described below. In addition, in this specification, "~" means the meaning which uses the numerical value described before and after that as a lower limit and an upper limit.

The description of the constituent elements in the present invention described below may be made based on the representative embodiments of the present invention, but the present invention is not limited to these embodiments. Regarding the label of a group (atomic group) in this specification, the descriptions of the substituted and unsubstituted labels include both those having no substituent and those having a substituent. For example, "alkyl" includes not only alkyl groups (unsubstituted alkyl groups) having no substituents, but also alkyl groups (substituted alkyl groups) having substituents. As long as "exposure" is not specifically limited in this specification, in addition to exposure using light, drawing using a particle beam such as an electron beam and an ion beam is also included in the exposure. In addition, as the light used for exposure, active light rays such as bright line spectrum of a mercury lamp and excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams, or radiation are generally mentioned. In this specification, "(meth) acrylate" means either or both of "acrylate" and "methacrylate", and "(meth) acrylic" means "acrylic" and "methacrylic" Either or any one of them, and "(meth) acrylfluorenyl" means either or both of "acrylfluorenyl" and "methacrylfluorenyl". In this specification, the term "step" is not only an independent step, but even if it cannot be clearly distinguished from other steps, if the desired effect on the step can be achieved, it is also included in this term. In the present specification, the solid content refers to the mass percentage of components other than the solvent with respect to the total mass of the composition. In addition, unless otherwise stated, the solid content concentration means 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 based on gel permeation chromatography (GPC measurement), and are defined as styrene conversion values. In this specification, for example, HLC-8220 (manufactured by TOSOH CORPORATION) can be used as the weight average molecular weight (Mw) and the number average molecular weight (Mn), and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION). Unless otherwise stated, the eluent was measured by THF (tetrahydrofuran). In addition, unless otherwise stated, the detection is performed using a UV ray (ultraviolet) wavelength 254 nm detector. Unless otherwise stated, the physical property value in the present invention is a value at 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") includes a precursor selected from a polyimide precursor and a polybenzoxazole precursor. A polymer precursor including a amine compound-derived cation and an acid compound-derived anion salt and a solvent, and a thermosetting resin composition, characterized in that the pKa of the conjugate acid of the amine compound and the acid compound pKa is in the range of the following formula 1. 3.5 ≤ (pKa of conjugate acid of amine compound + pKa of acidic compound) / 2 ≤ 7.1 (Equation 1) With these configurations, it is possible to provide a film thickness change over time of a film formed of a thermosetting resin composition. It is a thermosetting resin composition that is small and has excellent strength when cured. That is, as a result of studies conducted by the present inventors, it was confirmed that an acidic compound contributes to the suppression of the change in the thickness of a film mainly composed of a composition with time, and an amine compound contributes to the strength of the cured film. However, there are unexpected aspects in the blending equilibrium. The above effects were observed by confirming and analyzing various experiments, based on the pKa of the two compounds, and by specifying the blending equilibrium.

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

<<< Polyimine precursor> It is preferable that the polyfluorene imide precursor contains 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.

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

It is preferred that R ¹¹¹ is derived from a diamine. Examples of the diamine used in the production of the polyfluorene imide precursor include a linear or branched aliphatic, cyclic aliphatic, or aromatic diamine. The diamine may be used alone or in combination of two or more. Specifically, the diamine includes 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 more preferable, and a diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable. Examples of the aromatic group include the following aromatic groups.

[Chemical Formula 5]

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

Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminocyclohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diamino Cyclohexane or 1,4-diaminocyclohexane, 1,2-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane or 1,4-bis (Aminomethyl) cyclohexane, bis- (4-aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethyl Cyclohexylmethane and isophorone diamine; m-phenylenediamine and p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl and 3,3'-diaminobiphenyl, 4 , 4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4 , 4'-diaminodiphenylphosphonium and 3,3-diaminodiphenylphosphonium, 4,4'-diaminodiphenylsulfide and 3,3'-diaminodiphenylsulfide, 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-hydroxy Phenyl) fluorene, bis (4-amino-3-hydroxyphenyl) fluorene, 4,4'-diamino p-terphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, Bis [4- (4-aminophenoxy) phenyl] fluorene, bis [4- (3-aminophenoxy) phenyl] fluorene, bis [4- (2-aminophenoxy) benzene Yl] pyrene, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis (4-aminophenyl) anthracene, 3,3'-dimethyl-4,4'-di Amino diphenylphosphonium, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenylbenzene) Group) benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4, 4'-diamino octafluorobiphenyl, 2,2-bis [4- (4-aminophenoxy) Phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 3, 3 ', 4,4'-tetraaminobiphenyl, 3,3', 4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone , 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis (4-aminophenyl) fluorene, 4,4'-dimethyl-3,3'-di Aminodiphenylphosphonium, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4-diaminocumene and 2,5-diamine Cumene, 2,5-dimethyl-p-phenylenediamine, ethidium guanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m- Phenylenediamine, bis (3-aminopropyl) tetramethyldisilaxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-aminobenzene Group) ethane, diaminobenzidine aniline, 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-amine Phenyl) tetradecafluoroheptane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane 2,2-bis [4- (2-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylbenzene [Yl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-bis (trifluoromethyl) phenyl] hexafluoropropane, p-bis (4-amino- 2-trifluoromethylphenoxy) benzene, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3 -Trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenylphosphonium, 4,4'-bis (3-amino -5-trifluoromethylphenoxy) diphenylphosphonium, 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' At least one diamine among 5,5 ', 6,6'-hexafluorobenzidine and 4,4'-diaminotetraphenyl.

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

[Chemical Formula 6]

[Chemical Formula 7]

In addition, as a preferable example, a diamine having at least two or more alkylene glycol units in the main chain may be mentioned. A diamine containing two or more of ethylene glycol chains and propylene glycol chains in one molecule is preferably combined, and a diamine containing no aromatic ring is more preferred. Specific examples include JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR- 148, JEFFAMINE (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (the above are the product names, manufactured by HUNTSMAN), 1- (2- (2- (2-amino group) Propoxy) ethoxy) propoxy) propane-2-amine, 1- (1- (1- (2-aminopropoxy) propane-2-yl) oxy) propane-2-amine, etc. , But not limited to these. 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 structure.

[Chemical Formula 8]

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

From the viewpoint of the flexibility of the obtained cured film, R ¹¹¹ is preferably represented by -Ar ⁰ -L-Ar ^0- . Among them, Ar ^{0 is} each independently an aromatic hydrocarbon group (carbon number 6 to 22 is preferred, 6 to 18 is more preferred, and 6 to 10 is particularly preferred), and L is a carbon number 1 to 10 including fluorine atoms which may be substituted. Aliphatic hydrocarbon group, -O-, -CO-, -S-, -SO ₂ -or -NHCO-, and a group containing 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, which may be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO ₂ -is more preferable. Among them, an aliphatic hydrocarbon-based alkylene group is preferred. The aromatic hydrocarbon group (preferably phenylene group) constituting Ar ⁰ may have an arbitrary substituent T (for example, a hydroxyl group) within the range in which the effects of the present invention are exhibited.

When imparting photosensitivity to a thermosetting resin composition, from the viewpoint of i-ray transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, the divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-ray transmittance and ease of 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 difluoromethane. Or trifluoromethyl. When R ⁵⁰ to R ⁵⁷ are a monovalent organic group, an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a carbon group having 1 to 10 carbon atoms (preferably carbon atoms) are mentioned. 1 to 6) fluorinated alkyl and the like. 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. Examples of the diamine compound imparting a structure of the formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4, 4'-diaminobiphenyl, 2,2'-bis (fluoro) -4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like. One of these may be used, or two or more of them may be used in combination.

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. The benzene ring in the formula may have a substituent T (for example, 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 with a fluorine atom, and is selected from the group consisting of -O-, -CO-, -S-, -SO _2- , and -NHCO. -That is, the group in the combination of these is preferred, a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted by a fluorine atom, selected from the group consisting of -O-, -CO-, -S-, and -SO ₂ -is more preferably a group selected from the group consisting of -CH _2- , -C (CF ₃ ) _2- , -C (CH ₃ ) _2- , -O-, -CO-, -S-, and -SO _{The 2} -valent group in the 2-group is further preferred.

Formula (6) [Chemical Formula 12]

Specific examples of the tetravalent organic group represented by R ¹¹⁵ in formula (1) include a tetracarboxylic acid residue remaining after removing an acid dianhydride group from a tetracarboxylic dianhydride. Tetracarboxylic dianhydride may be used alone, or two or more of them may be used. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (O). Formula (O) [Chemical Formula 13] In the formula (O), R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ is the same as defined in formula (1) is R ^115. Specifically, a tetravalent organic group of Formula (5) or (6) is mentioned.

Specific examples of the tetracarboxylic dianhydride include those selected from pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, and 3,3 ', 4,4'-Diphenylsulfide tetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfonium tetracarboxylic dianhydride, 3,3 ', 4,4'-dibenzoyl Ketotetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2', 3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3 , 3 ', 4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxodiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2 2,2-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-fluorenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10 -Phenanthrene tetracarboxylic dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-di Phenyl) ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and alkyl derivatives of 1 to 6 carbon and / or alkoxy derivatives of 1 to 6 carbon At least one of them.

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

R ¹¹³ and R ¹¹⁴ in the formula (1) each independently represent a hydrogen atom or a monovalent organic group. When photosensitivity is imparted to the thermosetting resin composition as the 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 cross-linking reaction by the action of a radical, and a preferable example includes a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth) acrylfluorenyl group, and a group represented by the following formula (III).

[Chemical Formula 15]

In the formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and a methyl group is more preferred. In formula (III), R ²⁰¹ represents an alkylene 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; repeating numbers 1 to 12 are preferred, 1 to 6 are more preferred, and 1 to 3 are particularly preferred). In addition, (poly) oxyalkylene means oxyalkylene or polyoxyalkylene. Examples of preferred R ²⁰¹ include ethylene, propyl, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, Hexamethylene, octamethylene, dodecyl methylene, -CH ₂ CH (OH) CH _2- , ethylene, propyl, trimethylene, -CH ₂ CH (OH) CH ₂ -is Better. Particularly preferred are R ^200- based methyl groups and R ^201- based ethylene groups.

In another example of the embodiment of the polyfluorene imide precursor in the present invention, examples of the monovalent organic group of R ¹¹³ or R ¹¹⁴ include one, two, or three, preferably one acid. Examples of the group include aliphatic groups, aromatic groups, and aralkyl groups. Specific examples include an aromatic group having 6 to 20 carbon atoms in the acid group and an aralkyl group having 7 to 25 carbon atoms in the acid group. More specific examples include a phenyl group having an acid group and a benzyl group having an acid group. An acidic hydroxyl group is preferred. That is, R ¹¹³ or R ¹¹⁴ is preferably a group having a hydroxyl group. As the monovalent organic group represented by R ¹¹³ or R ¹¹⁴ , a substituent that improves the solubility of the developing solution can be preferably used. From the viewpoint of solubility in an aqueous developer, R ¹¹³ or R ¹¹⁴ is more preferably a hydrogen atom, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group, and a 4-hydroxybenzyl group.

From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. As the monovalent organic group, a linear or branched alkyl group, a cyclic alkyl group, and an aromatic group are more preferable, and an alkyl group substituted with an aromatic group is more preferable. The carbon number of the alkyl group is preferably 1 to 30 (in the case of a cyclic group, it is 3 or more). The alkyl group may be any of linear, branched, and cyclic. Examples of the linear or branched alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and tetradecyl Alkyl, octadecyl, isopropyl, isobutyl, second butyl, third butyl, 1-ethylpentyl and 2-ethylhexyl. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of the polycyclic cyclic alkyl group include adamantyl, norbornyl, fluorenyl, camphenyl, decalinyl, tricyclodecyl, tetracyclodecyl, and fluorene. Difluorenyl, dicyclohexyl and pinenyl. Among them, cyclohexyl is the most preferable from the viewpoints of both the balance and high sensitivity. The alkyl group substituted with an aromatic group is preferably a linear alkyl group substituted with an aromatic group described later. Examples of the aromatic group include a substituted or unsubstituted benzene ring, a naphthalene ring, a pentenene ring, an indene ring, a fluorene ring, a heptene ring, an indenene ring, a fluorene ring, a fused pentaphenyl ring, and fluorene. Olefin ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring, fluorene ring, triphenylene ring, fluorene 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, quino ring, quinoline ring, phthalocyclic ring, naphthyridine ring, quinoxaline Porphyrin ring, quinazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thiathracene ring, chromene ring, star mouth ring, morphine ring Or brown ring. The benzene ring is the best.

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

In addition, for the purpose of improving adhesion to a substrate, an aliphatic group having a siloxane structure and a repeating unit represented by the formula (1) can be copolymerized. Specific examples of the diamine component include bis (3-aminopropyl) tetramethyldisilazane and bis (p-aminophenyl) octamethylpentasiloxane.

The repeating unit represented by the formula (1) is preferably a 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 preferred.

The definitions of A ¹¹ , A ¹² , R ¹¹¹ , R ^113, and R ¹¹⁴ are independently the same as A ¹ , A ² , R ¹¹¹ , R ^113, and R ^{114 in} Formula (1), and the preferred ranges are also the same. The same as R (5) R ¹¹² is as defined in Formula ^112, the preferred range is also the same.

In the polyimide precursor, the repeating unit represented by the formula (1) may be one type, or may be two or more types. Further, it may contain a structural isomer of a repeating unit represented by formula (1). In addition to the repeating unit of the formula (1), the polyfluorene imide 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 unit may be exemplified, and furthermore, 70 mol% or more, and particularly 90 mol% or more may be represented by formula (1). Polyimide precursors of repeating units. The upper limit is actually 100 mol% or less.

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

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

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

<< Polybenzoxazole precursor> The polybenzoxazole precursor used in the present invention preferably includes a repeating unit represented by the following formula (2). [Chemical Formula 17] In the 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 the formula (2), R ¹²¹ represents a divalent organic group. The divalent organic group includes an aliphatic group (carbon number 1 to 24 is preferred, 1 to 12 is more preferred, and 1 to 6 is particularly preferred) and an aromatic group (carbon number 6 to 22 is preferred, 6 to 6) 14 is more preferred, and 6-12 are particularly preferred. Examples of the group containing an aromatic group constituting R ¹²¹ include R ¹¹¹ of the formula (1). As the aliphatic group, a linear aliphatic group is preferred. More preferably, R ^{121 is} derived from 4,4'-oxodibenzoyl 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 formula (1), and the preferred range is also the same. R ¹²² is preferably derived from 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane. R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group, and their definitions are the same as those of R ¹¹³ and R ¹¹⁴ in the formula (1), and preferred ranges are also the same.

In addition to the repeating unit of formula (2) described above, the polybenzoxazole precursor may also contain other kinds of repeating structural units. From the viewpoint of suppressing the occurrence of warping of the cured film accompanying the ring closure, it is preferable that the precursor contains a diamine residue represented by the following formula (SL) as another kind of repeating structural unit.

[Chemical Formula 18] In the formula (SL), Z has an a structure and a b structure, R ^1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and R ^2s is A hydrocarbon group having 1 to 10 carbons (preferably 1 to 6 carbons, more preferably 1 to 3 carbons), and at least one of R ^3s , R ^4s , R ^5s , and R ^6s is an aromatic group (preferably Is 6 to 22 carbons, more preferably 6 to 18 carbons, particularly preferably 6 to 10 carbons, and the remainder is a hydrogen atom or 1 to 30 carbons (preferably 1 to 18 carbons, more preferably 1 to 18 carbons) 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 portion, the a structure is preferably 5 to 95 mole%, the b structure is 95 to 5 mole%, and a + b is 100 mole%.

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

When the precursor contains other diamine residues represented by the formula (SL) as another kind of repeating structural unit, from the viewpoint of improving alkali solubility, it also includes the residual tetracarboxylic acid after removing the acid dianhydride from the tetracarboxylic dianhydride. Acid residues are preferred as repeating structural units. Examples of such a tetracarboxylic acid residue include an example of R ¹¹⁵ in formula (1).

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

The content of the polymer precursor in the thermosetting resin composition of the present invention is preferably 20% by mass or more with respect to the total solid content of the composition, more preferably 30% by mass or more, and more preferably 40% by mass or more. 50% by mass or more is further preferred, 60% by mass or more is further preferred, and 70% by mass or more is further preferred. 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 more preferably 98% by mass or less based on the total solid content of the composition. Preferably, 95% by mass or less is further preferred, 93% by mass or less is further preferred, and 90% by mass or more is further preferred. The thermosetting resin composition of the present invention may contain only one kind of polymer precursor, or may contain two or more kinds. When two or more kinds are contained, the total amount is preferably in the above range.

<Salt containing a cation derived from an amine compound and an anion derived from an 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 the cations derived from the amine compound and the salt derived from the anion derived from the acidic compound can be appropriately set depending on the use or required characteristics, but relative to the amount of the amine group of the amine compound, The amount of the acid group of the acidic compound is preferably in a range of 0.5 equivalent or more, more preferably in a range of 0.7 equivalent or more, and particularly preferably in a range of 0.9 equivalent or more. As the upper limit, the range of the acid group of the acidic compound is preferably in a range of 5.0 equivalents or less, more preferably in a range of 4.0 equivalents or less, and particularly preferably in a range of 3.0 equivalents or less. By setting the amount of acid groups to 0.5 equivalent or more, it is possible to further effectively suppress the variation in film thickness over time, and by setting the amount to 3.0 equivalents or less, the fluorene imidization during heat curing is promoted and the film strength is further improved. The trend.

In the thermosetting resin composition of this invention, the specific value (A-pKa) prescribed | regulated by the pKa of the conjugate acid of the amine compound and the pKa of an acidic compound contained in the thermosetting resin composition 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 value of A-pKa is preferably 3.8 or more It is more preferably 4.0 or more, and may be 5.0 or more. The upper limit value is preferably 7.0 or less, and may be 6.9 or less, or 6.8 or less. A-pKa contributes particularly to the suppression of changes in film thickness over time as the value is below the upper limit value. On the other hand, the strength of the cured film can be increased by setting the value above the lower limit value. 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 it is actually 500 or less. By setting the absolute value of the difference to 30 or more, the ratio of the amine compound to the acidic compound remaining in the film during heat curing becomes larger, and the curing reaction is further effectively promoted. In addition, in a salt including a cation derived from an amine compound and an anion derived from an acidic compound, the total amount added need not satisfy the above-mentioned conditions, and as long as the effects of the present invention are exhibited, at least one of them may satisfy the above-mentioned conditions. Specifically, it is preferable that 70% by mass or more of a salt containing a cation derived from an amine compound and an anion derived from an acidic compound contained in the thermosetting resin composition satisfies the above conditions, and more preferably 80% by mass or more. Above 90% by mass is particularly preferred. The upper limit is 100% by mass or less.

The content of the salt containing a cation derived from an amine compound and an anion derived from an acidic compound in the thermosetting resin composition of the present invention is preferably 0.1 part by mass or more with respect to 100 parts by mass of the polymer precursor, and 0.2 part by mass The above is more preferable, and 0.4 mass part or more is more preferable. The content of the salt is more preferably 5 parts by mass or less, more preferably 3 parts by mass or less, more preferably 2 parts by mass or less, and 1.8 parts by mass or less, more preferably 1.5 parts by weight, based on 100 parts by mass of the polymer precursor. It is more preferable to be less than the mass part. In addition to the above salts, it is not excluded that in the thermosetting resin composition, a part of the acidic compound and the amine compound does not form a salt and exists as an acidic compound or as an amine compound. In addition to the above salts, a part of the acidic compound may form a salt with a quaternary ammonium cation of a hardening accelerator described later.

<< Amine Compound >> The amine compound in the present invention refers to a compound having an amine site (-N <) in the molecule (not ammonia (NH ₃ )). The amine compound in the present invention is preferably a compound represented by the following formula (B1).

[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 having 1 to 20 carbon atoms, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 1 to 20 carbon atoms (more Heteroaryl groups having 2 to 10 carbon atoms are preferred, and 3 to 6 carbon atoms are particularly preferred. Examples of the hetero atom contained in the heteroaryl group include an oxygen atom, a nitrogen atom, and a sulfur atom. The heteroaryl group is preferably a 5- or 6-membered ring group, and examples thereof include pyrrolyl, pyridyl, pyrazolyl, imidazolyl, benzimidazolyl, triazolyl, thiazolyl, and oxazolyl. Heteroaryl is more preferably substituted by hydrogen at the carbon atom position. When R ^B1 to R ^B3 are an organic group having 1 to 20 carbon atoms, the following substituents T may be included 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 (carbon numbers 1 to 24 are preferred, 1 to 12 are more preferred, and 1 to 6 are particularly preferred), and cycloalkyl groups (carbon numbers 3 to 3) 24 is preferred, 3 to 12 is more preferred, 3 to 6 is particularly preferred), linear or branched alkenyl (carbon number of 2 to 24 is preferred, 2 to 12 is more preferred, 2 to 6 is particularly preferred ), Cycloalkenyl (3 to 24 carbons is preferred, 3 to 12 is more preferred, 3 to 6 is particularly preferred), hydroxy and hydroxyalkyl (1 to 24 carbons are preferred, 1 to 12 are more preferred) 1 to 6 are particularly preferred; the number of hydroxyl groups is preferably 1 to 6, and 1 to 3 is more preferred. The alkyl group may be linear or branched, and may be chain or cyclic), Hydroxy alkenyl (carbon number 2 to 24 is preferred, 2 to 12 is more preferred, 2 to 6 is particularly preferred; the number of hydroxyl groups is preferably 1 to 6, 1 to 3 is more preferred, alkenyl can be straight The chain may also be branched, or it may be chain or cyclic), amine group (carbon number 0 to 24 is preferred, 0 to 12 is more preferred, 0 to 6 is particularly preferred), and amino alkyl group ( The carbon number is 1 to 24, 1 to 12 is more preferable, and 1 to 6 is particularly preferable. The number of amine groups is preferably 1 to 6, 1 to 3 is more preferable, and the alkyl group may be linear. May be branched, chain or cyclic), amino alkenyl (carbon number 2-24 is preferred, 2-12 is more preferred, 2-6 is particularly preferred; the number of amine groups is 1 ～ 6 is preferred, and 1-3 is more preferred. The alkenyl group may be straight or branched, and may be chain or cyclic), thiol group, and thiol alkyl group (carbon number 1 to 24). For the sake of preference, 1 to 12 is more preferable, and 1 to 6 is particularly preferable. The number of thiol groups is preferably 1 to 6, and 1 to 3 is more preferable. The alkyl group may be linear or branched. It can be chain or cyclic), thiol alkenyl (carbon number 2 to 24 is preferred, 2 to 12 is more preferred, 2 to 6 is particularly preferred; the number of thiol groups is 1 to 6 for comparison 1 to 3 are more preferred. The alkenyl group may be straight or branched, and may be chain or cyclic. A carboxyl group or a carboxyalkyl group is preferred. More preferably, 1 to 6 are particularly preferred; the number of carboxyl groups is preferably 1 to 6, and 1 to 3 is more preferred. The alkyl group may be straight or branched, and may be chained or cyclic. ), Carboxy alkenyl (carbon number 2-24 is preferred, 2-12 is more preferred, 2-6 is particularly preferred; the number of carboxyl groups Systems 1 to 6 are preferred, and 1 to 3 are more preferred. The alkenyl group can be straight or branched, can be chain or cyclic), fluorenyl (carbon number 2 to 12 is preferred, 2 to 6 are more preferred, 2 to 3 are particularly preferred), oxo (carbon number 2 to 12 is preferred, 2 to 6 is more preferred, 2 to 3 is particularly preferred), arylfluorenyl (carbon number 7 23 to 23 are preferred, 7 to 19 are more preferred, 7 to 11 are particularly preferred), arylfluorenyl (7 to 23 carbons are preferred, 7 to 19 are more preferred, 7 to 11 are particularly preferred), A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an oxygen group (= O), an imino group (= NR ^N ), an 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 (carbon number 1 to 12 is more preferable, 1 to 6 is more preferable, and 1 to 3 is more preferable), and a hydrogen atom is more preferable. When the substituent T is a group capable of forming a salt such as a carboxyl group, a salt may be formed along with a counter ion (for example, an ammonium ion).

R ^B1 to R ^B3 are not all hydrogen atoms. Among R ^B1 to R ^B3 , one or less hydrogen atoms are preferred, and all other hydrogen atoms are more preferred. In other words, it is preferable that the amine compound is a secondary amine instead of a primary amine, and a tertiary amine is not a secondary amine.

R ^B1 and R ^B2 are each independently an alkyl group having 1 to 20 carbon atoms (which may be a straight chain, a branched chain, or a chain or a ring). The alkyl group may have a substituent T. More preferably, it is a linear or branched alkyl group having 1 to 6 carbon atoms, and a linear or branched chain hydroxyalkyl group having 1 to 6 carbon atoms (the number of hydroxyl groups is preferably 1 to 6, and 1 to 3 is more preferable). Straight-chain or branched amine alkyl groups having 1 to 6 carbon atoms (the number of amine groups is preferably 1 to 6, more preferably 1 to 3), 3 to 8 carbon alkyl groups (more preferably a cyclic group) (Pentyl or cyclohexyl) is preferred. R ^B3 is a hydrogen atom, an alkyl group having a carbon number of 1 to 12 (preferably 1 to 6) (which may be a straight chain or a branched chain, and may be a chain or a ring), and a carbon number of 1 to 6 Heteroaryl is preferred. More preferably, it is a R ^B3 series hydrogen atom, a straight or branched alkyl group having 1 to 12 carbon atoms (preferably 1 to 6), and a straight or branched chain having 1 to 12 carbon atoms (preferably 1 to 6) Hydroxyalkyl (the number of hydroxyl groups is preferably 1 to 6, more preferably 1 to 3), straight or branched chain amino groups (amino groups) having 1 to 12 carbon atoms (preferably 1 to 6) The number is preferably from 1 to 6, more preferably from 1 to 3), cycloalkyl (more preferably cyclopentyl or cyclohexyl) having 3 to 8 carbons or heteroaryl (more preferably 3 to 6 carbons) (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 they are preferably formed. It is preferred 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 member ring, and a 6 member ring is more preferable. The cyclic structure may be a single ring or a condensed ring, but a single ring is preferred. The compound represented by the formula (B1) preferably contains 1 to 4 cyclic structures in each molecule, and may be 2 to 4, or 2 or 3, or 2 may be used. Moreover, it may or may not have an imine structure (> C = N-) in a ring structure. 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 said amine compound, it is preferable that the number of the connected nitrogen atom and the said carbon atom of the carbon atom which has the farthest distance from a nitrogen atom is 2 or more. The upper limit of the number of linked atoms is preferably 20 or less, more preferably 12 or less, even more preferably 8 or less, and particularly preferably 5 or less. The amine compound has a strong interaction with copper, and therefore it is easy to be biased on the surface of copper used in wiring. When the substituent of the amine compound is within this range, the polarity of the surface can be appropriately secured even if the amine is biased in the copper wiring, and thus it is possible to further effectively suppress a decrease in adhesion with the insulating film. Specifically, the number of atoms connecting the above-mentioned nitrogen atom and the farthest carbon atom means that when R ^B1 is a cyclohexyl group, the carbon on the opposite side to the carbon (α carbon) substituted by the nitrogen atom of the 6-membered ring The atom becomes the furthest carbon atom. This is the third carbon atom in consideration of the α carbon. Therefore, the number of the third carbon atom and the α carbon atom is two.

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

The molecular weight of the amine compound is preferably 90 or more, more preferably 100 or more, more preferably 110 or more, and more preferably 120 or more. As the upper limit, 1,000 or less is preferred, 800 or less is more preferred, 600 or less is further preferred, 400 or less is further preferred, and 300 or less is further preferred. By setting it as 90 or more, it hardly volatilizes at the time of heat hardening, it remains in a film, and it becomes easier to function as a hardening accelerator. On the other hand, when it is 1000 or less, it is easy to diffuse in a film, and it functions more effectively as a hardening accelerator.

As specific examples of the amine compound, in addition to the compounds described in the examples described later, the compounds described in paragraphs 0204 and 0205 of Japanese Patent Application Laid-Open No. 2011-221494 can be used and incorporated into this specification. .

The blending 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, 5 parts by mass or less is more preferable, and 3 parts by mass or less is further Preferably, 2 parts by mass or less is more preferable. As the lower limit value, 0.01 parts by mass or more is preferable, 0.05 parts by mass or more is more preferable, 0.1 parts by mass or more is still more preferable, 0.3 parts by mass or more is still more preferable, and 0.5 parts by mass or more is more preferable. The salt may have only one type of cation derived from an amine compound, or may have two or more types of cation derived from amine compound. When two or more kinds are included, the total amount is preferably in the above range. Also. In addition to salts containing cations derived from amine compounds and anions derived from acidic compounds used in the present invention, salts containing cations derived from ammonia may also be contained. However, it is preferable not to substantially contain a salt containing a cation derived from ammonia. By not substantially containing, it means that the content of the salt containing the cation derived from ammonia is 5 mass% or less, and the content of the salt containing the cation derived from the amine compound and the anion derived from the acidic compound is preferably 3 mass% or less. 1 mass% or less is more preferable.

<<< Acidic compound> The acidic compound in the present invention refers to a compound which is less than pH 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 more preferred. For example, a compound having a sulfonic acid group, a carboxyl group, a phosphonic acid group, a phosphate group, a boric acid group, or the like is 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 a linear or branched alkyl group (carbon number 1 to 12 is preferred, 1 to 6 is more preferred, and 1 to 3 are particularly preferred), and a cycloalkyl group (carbon number 3 to 3) 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 carbons is preferably 1 to 12, and more preferably 1 to 6). Among them, a linear or branched alkyl group or an aryl group having the above carbon number is preferable. These groups may or may not have a substituent T. For example, a combination of an alkyl group and an aryl group (7 to 23 carbon atoms is preferred, 7 to 19 is more preferred, and 7 to 11 is particularly preferred), and an aralkyl group (carbon Numbers 7 to 23 are preferred, 7 to 19 are more preferred, 7 to 11 are particularly preferred) or alkylaryl groups (carbon number 7 to 23 are preferred, 7 to 19 are more preferred, 7 to 11 are 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 a group described by R ^A1 and a carboxyl group, and a group similar to the group described by R ^A1 is more preferable. The monovalent organic group may or may not have a substituent T. R ^A7 to R ^A12 each independently represent a hydrogen atom or a monovalent organic group, and a hydrogen atom is preferred. Examples of the monovalent organic group include a group having the same definition as the above-mentioned R ^A1 , and a preferable range is also the same. The monovalent organic group may or may not have a substituent T. R ^A13 has a hydrogen atom or a monovalent organic group, and a monovalent organic group is preferred. Examples of the monovalent organic group include a group having the same definition as the above-mentioned R ^A1 , and a preferable range is also the same. The monovalent organic group may or may not have a substituent T.

The pKa of the acidic compound is preferably 5 or less, more preferably 4 or less, even more preferably 3 or less, and may be 2 or less. As the lower limit, -5 or more is preferable, -4 or more is more preferable, and -3 or more is particularly preferable. By setting pKa to 5 or less, the decomposition reaction of the polyimide precursor and the polybenzoxazole precursor with time is further effectively suppressed by the acidic compound, so that the change in film thickness with time 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 more preferably 80 or more. The upper limit value is preferably 1000 or less, more preferably 700 or less, further preferably 500 or less, more preferably 300 or less, and particularly preferably 200 or less. In addition, by setting the molecular weight of the acidic compound to 1,000 or less, it is difficult to remain in the film during the heat-hardening step, and the curing reaction proceeds effectively, so that the strength of the film tends to increase. By setting the molecular weight to 50 or more, the composition is less likely to volatilize during storage, and the change in film thickness over time can be more effectively suppressed.

The blending amount of the acidic 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, 5 parts by mass or less is more preferable, and 3 parts by mass may also be used. the following. The lower limit value is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.1 parts by mass or more, 0.3 parts by mass or more is more preferable, and may be 0.5 parts by mass or more. The acidic compound may have only one type of anion derived from an acidic compound, or may have two or more types of anion derived from an acidic compound. When two or more kinds are included, the total amount is preferably in the above range.

<Solvent> The thermosetting resin composition of the present invention contains a solvent. The solvent can be any known one. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, fluorenes, and amidines. Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, and ethyl butyrate. Ester, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (for example, methyl alkoxyacetate, Ethyl alkoxyacetate, butyl ethoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate) Etc.)), alkyl 3-alkoxypropionates (e.g. methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g. methyl 3-methoxypropionate) , Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (for example, 2- Methyl alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate , Propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)) Methyl 2-alkoxy-2-methylpropanoate and ethyl 2-alkoxy-2-methylpropanoate (eg, methyl 2-methoxy-2-methylpropionate, 2-ethyl Ethoxy-2-methyl propionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, methyl 2-oxobutanoate, Ethyl 2-oxobutanoate and the like. As the ethers, preferred examples 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 and the like. Examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone. Examples of the aromatic hydrocarbons include toluene, xylene, anisole, and limonene. As a fluorene, for example, dimethyl fluorene is preferable. As preferred amines, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, and N, N-dimethylformamide are preferable. Amidine and so on.

Regarding the solvent, it is also preferable to mix two or more forms from the viewpoint of improving the coating surface shape. In the present invention, it is selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, and butyl acetate. Esters, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethylsulfinium, ethylcarbitol acetate, butylcarbidine One solvent or a mixed solvent composed of two or more kinds of alcohol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable. It is particularly preferred to use both dimethyl sulfene and γ-butyrolactone.

The content of the solvent is preferably from 5 to 80% by mass of the total solid content concentration of the thermosetting resin composition of the present invention from the viewpoint of coating properties, and is the thermosetting resin of the present invention. The total solid content concentration of the composition is more preferably 5 to 75% by mass, and the total solid content concentration of the thermosetting resin composition of the present invention is more preferably 10 to 70% by mass. It is more preferable that 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 kind or two or more kinds. When two or more solvents are contained, the total is preferably in the above range.

<Photoradical polymerization initiator> The thermosetting resin composition of the present invention may contain a photoradical polymerization initiator and be provided with photosensitivity. The photo-radical polymerization initiator that can be used in the present invention is not particularly limited, and can be appropriately selected from known photo-radical polymerization initiators. For example, a photoradical polymerization initiator that is sensitive to light from the ultraviolet region to the visible region is preferred. In addition, it may be an active agent that generates some action with a photo-excited sensitizer and generates an active radical. The photoradical polymerization initiator preferably contains at least one compound having an absorption coefficient of at least about 50 moles in a range of about 300 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of a compound can be measured by a well-known method. For example, it is preferable to perform measurement at a concentration of 0.01 g / L by using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer, manufactured by Varian Corporation) and using an ethyl acetate solvent.

After 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 is irradiated with light. In addition, hardening due to the generated free radicals can reduce the solubility in the light-irradiated portion. Therefore, for example, there is an advantage in that the regions having different solubility can be easily produced by exposing the thermosetting resin composition layer through a light mask having a pattern that shields only the electrode portion.

As the photoradical polymerization initiator, a known compound can be arbitrarily used. For example, halogenated hydrocarbon derivatives (for example, compounds having a tri-skeleton, compounds having a fluorendiazole skeleton, compounds having a trihalomethyl, etc.), fluorenyl phosphine compounds such as fluorenylphosphine oxide, and hexaarylbisimidazole Oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo-based compounds, azide compounds, and Metal compounds, organic boron compounds, iron aromatic hydrocarbon complexes, and the like. For details of these, refer to the descriptions in paragraphs 0165 to 0182 of Japanese Patent Application Laid-Open No. 2016-027357, and incorporate the contents into this specification.

As the ketone compound, for example, a compound described in paragraph 0087 of Japanese Patent Application Laid-Open No. 2015-087611 can be exemplified, and the content is incorporated into this specification. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

As the photoradical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a fluorenylphosphine compound can also be preferably used. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Application Laid-Open No. 10-291969 and a fluorenylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used. As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (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) can be used. As the aminoacetophenone-based initiator, a compound described in Japanese Patent Application Laid-Open No. 2009-191179 with a maximum absorption wavelength matching a wavelength light source such as 365 nm or 405 nm can also be used. Examples of the fluorenylphosphine-based initiator include 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide and the like. In addition, IRGACURE 819 or IRGACURETPO (trade name: both manufactured by BASF) can be used as commercially available products. Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF).

The photoradical polymerization initiator is more preferably an oxime compound. By using an oxime compound, exposure latitude can be further effectively improved. Among the oxime compounds, the exposure latitude (exposure margin) is wide, and it also functions as a photohardening accelerator, so it is particularly preferable. As specific examples of the oxime compound, a compound described in JP 2001-233842, a compound described in JP 2000-080068, and a compound described in JP 2006-342166 can be used. . Preferred examples of the oxime compound include a compound having the following structure, 3-benzyloxyiminobutane-2-one, 3-ethoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-ethoxymethyliminopentane-3-one, 2-ethoxymethylimino-1-phenylpropane-1- Ketones, 2-benzyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyl Oxyimino-1-phenylpropane-1-one and the like. In the thermosetting resin composition of the present invention, it is preferable to use an oxime compound (oxime-based photopolymerization initiator) as a photoradical polymerization initiator. The oxime-based photopolymerization initiator has a linking group of> C = NOC (= O)-in the molecule. [Chemical Formula 21] Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are manufactured by BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, JP 2012-014052) Photo radical polymerization initiator 2) described in the publication. In addition, TR-PBG-304 (manufactured by Changzhou Power Electronics New Materials Co., Ltd.), ADEKAARKLS NCI-831, and ADEKAARKLS NCI-930 (manufactured by ADEKA CORPORATION) can be used. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can be used. Furthermore, an oxime compound having a fluorine atom can also be used. Specific examples of such an oxime compound include compounds described in Japanese Patent Application Laid-Open No. 2010-262028, compounds 24, 36-40 of Japanese Patent Application No. 2014-500852, and Japanese Patent No. Compound (C-3) and the like described in paragraph 0101 of 2013-164471. Examples of the preferred oxime compound include an oxime compound having a specific substituent shown in Japanese Patent Application Laid-Open No. 2007-269779, and an oxime having a sulfur aryl group shown in Japanese Patent Laid-Open No. 2009-191061. Compounds etc.

From the standpoint of exposure sensitivity, the photo-radical polymerization initiator is selected from the group consisting of trihalomethyl tri compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, and fluorenylphosphines. 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 their salts, halomethylpyridazole compounds, and 3-aryl substituted coumarin compounds. More preferred photoradical polymerization initiators are trihalomethyl tri compounds, α-amino ketone compounds, fluorenyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and onium salts. Compound, benzophenone compound, acetophenone compound, at least selected from the group consisting of trihalomethyl tri compounds, α-amino ketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds One compound is further preferred, the use of a metallocene compound or an oxime compound is further preferred, and the oxime compound is further preferred. In addition, as the photoradical polymerization initiator, N, such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), can be used. N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-portolinylphenyl) -butanone-1 Aromatic ketones such as 2,2-methyl-1- [4- (methylthio) phenyl] -2-portalolinyl-acetone-1, alkyl anthraquinones, and other quinones that are condensed with aromatic rings Compounds, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin, alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, and the like. A compound represented by the 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, Carbon interrupted by an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, cyclopentyl, cyclohexyl, an alkenyl group having 2 to 12 carbon atoms, and one or more oxygen atoms At least one substituted phenyl or biphenyl group of an alkyl group of 2 to 18 and an alkyl group of 1 to 4 carbons, R ^I01 is a group represented by formula (II), or is the same as R ^I00 The groups, R ^I02 to R ^I04 are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen. [Chemical Formula 23] In the formula, R ^I05 to R ^I07 are the same as R ^I02 to R ^{I04 in} the formula (I).

As the photoradical polymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication No. WO2015 / 125469 can also be used.

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 still more preferably relative to the total solid content of the thermosetting resin composition of the present invention. It is 0.5 to 15% by mass, and more preferably 1.0 to 10% by mass. The photo radical polymerization initiator may contain only one kind, or may contain two or more kinds. When two or more kinds of photo-radical polymerization initiators are contained, the total thereof is preferably in the above 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. A thermal radical polymerization initiator is a compound that generates radicals by the energy of heat and starts or promotes the polymerization reaction of a 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. Therefore, higher heat resistance can be achieved. Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Laid-Open 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 still more preferably relative to the total solid content of the thermosetting resin composition of the present invention. It is 5 to 15 mass%. The thermal radical polymerization initiator may contain only one kind, or may contain two or more kinds. When two or more types of thermal radical polymerization initiators are contained, the total is preferably in the above range.

<Polymerizable Compound> When the photosensitive property is imparted to the thermosetting resin composition of the present invention, it is preferable to include a radical polymerizable compound.

As the radically polymerizable compound, a compound having a radically polymerizable group can be used. Examples of the radical polymerizable group include groups having an ethylenically unsaturated bond such as vinylphenyl, vinyl, (meth) acrylfluorenyl, and allyl. The radical polymerizable group (meth) acrylfluorenyl is preferred.

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

The molecular weight of the radically polymerizable compound is preferably 2000 or less, more preferably 1500 or less, and still more preferably 900 or less. The lower limit of the molecular weight of the radical 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 bifunctional or more radically polymerizable compound containing two or more polymerizable groups, and contains at least one trifunctional or more radical A polymerizable compound is more preferred. Moreover, it may be a mixture of a bifunctional radically polymerizable compound and a trifunctional or more radically polymerizable compound. The number of functional groups of the radically polymerizable compound refers to the number of radically polymerizable groups in one molecule.

Specific examples of the radical polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amidines. It is preferably an ester of an unsaturated carboxylic acid and a polyhydric alcohol compound, and an amine of an unsaturated carboxylic acid and a polyamine compound. In addition, it is also preferable to use an addition reaction product of an unsaturated carboxylic acid ester or amidoamine having an affinity substituent such as a hydroxyl group or an amine group with a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or Dehydration condensation reactants of polyfunctional carboxylic acids and the like. In addition, unsaturated carboxylic acid esters or amidoamines having an electrophilic substituent such as an isocyanate group or an epoxy group, and an addition reaction product of a monofunctional or polyfunctional alcohol, amine, or thiol, and a halogen group or toluene Substituted reactants of unsaturated carboxylic acid esters or amidoamines having detachable substituents such as sulfonyloxy groups and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. As another example, instead of the unsaturated carboxylic acid, a compound group substituted with a vinyl benzene derivative such as unsaturated phosphonic acid, styrene, vinyl ether, allyl ether, or the like can be used. As a specific example, the descriptions in paragraphs 0113 to 0122 of Japanese Patent Application Laid-Open No. 2016-027357 can be referred to, and the contents are incorporated into this specification.

In addition, a radical polymerizable compound is also a compound having a boiling point of 100 ° C. or higher under normal pressure. As examples thereof, polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, neopentaerythritol tri (Meth) acrylate, neopentaerythritol tetra (meth) acrylate, dinepentaerythritol penta (meth) acrylate, dinepentaerythritol hexa (meth) acrylate, hexanediol (formaldehyde) Group) acrylic acid esters, trimethylolpropane tris (acryloxypropyl) ether, tris (acryloxyethyl) isotricyanate, glycerol or trimethylolethane, etc. in polyfunctional alcohols Compounds which are subjected to (meth) acrylation after addition of ethylene oxide or propylene oxide, Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Patent Publication No. 51-037193 (Meth) acrylic acid urethanes described in the gazette, polyester acrylates described in the gazettes of JP-A-48-064183, JP-A-49-043191, and JP-A-52-030490 Polyfunctional, such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid Acrylate or methacrylate esters, and mixtures of these. In addition, compounds described in paragraphs 0254 to 0257 of Japanese Patent Application Laid-Open No. 2008-292970 are also suitable. In addition, polyfunctional (meth) acrylates obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group and an ethylenically unsaturated bond, such as glycidyl (meth) acrylate, and the like can also be mentioned. Moreover, as a preferable radical polymerizable compound other than the above, it is possible to use a ring having a ring described in Japanese Patent Application Laid-Open No. 2010-160418, Japanese Patent Application Laid-Open No. 2010-129825, and Japanese Patent No. 4364216 A compound or cardo resin having two or more groups having an ethylenically unsaturated bond. Furthermore, as another example, Japanese Unexamined Patent Publication No. 46-043946, Japanese Unexamined Patent Publication No. 1-040337, Japanese Unexamined Patent Publication No. 1-040336, and Japanese Unexamined Patent Publication No. 2 A vinylphosphonic acid-based compound and the like described in JP-025493. In addition, a compound containing a perfluoroalkyl group described in Japanese Patent Application Laid-Open No. 61-022048 can also be used. Furthermore, the "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pages 300 to 308 (1984) can also be used as the introducer of the photocurable monomer and oligomer.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese Patent Application Laid-Open No. 2015-034964 can be preferably used and incorporated into this specification.

In addition, the following compounds described in Japanese Patent Application Laid-Open No. 10-062986 as Formulas (1) and (2) together with specific examples thereof can also be used as radical polymerizable compounds, which compounds are added to polyfunctional alcohol A compound obtained by (meth) acrylated with ethylene oxide or propylene oxide.

Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese Patent Application Laid-Open No. 2015-187211 can also be used as other radical polymerizable compounds, and these contents are incorporated into this specification.

As the radically polymerizable compound, dipentaerythritol triacrylate (as a commercially available product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), and dipentaerythritol tetraacrylate (as a commercially available product: KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta (meth) acrylate (KAYARAD D as a commercial product) -310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; Shin-Nakamura Chemical Co., Ltd.) and such (meth) acrylfluorenyl groups are preferably bonded via ethylene glycol residues and propylene glycol residues. These types of oligomers can also be used.

As a commercially available product of a radically polymerizable compound, for example, SR-494, which is a four-functional acrylate having four ethoxyl chains, and 2 which has four vinyloxy chains, are manufactured by Sartomer Company, Inc. Functional methyl acrylate, SR-209, 231, 239 manufactured by Sartomer Company, Inc., DPCA-60 as a 6-functional acrylate having 6 pentyloxy chains, and 3 having 3 TPA-330, trifunctional acrylate with isobutene chain, 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 (made by Kyoeisha chemical Co., Ltd.), BLEMMER PME400 (made by NOF CORPORATION.), Etc.

As the radical polymerizable compound, there are those described in Japanese Patent Application Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Application No. 2-032293, and Japanese Patent Application No. 2-016765. Urethane acrylates are 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. Oxyethane-based urethane compounds are also preferred. Further, as the radical polymerizable compound, it is also possible to use an amine group in the molecule described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-Open No. 1-105238. Structure or sulfide structure.

The radical polymerizable compound may be a radical polymerizable compound having an acid group such as a carboxyl group or a phosphate 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 an unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to give an acid. Radical polymerizable compounds are more preferred. Particularly preferred is a radically polymerizable compound in which an unreacted hydroxyl group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to give an acid group, and the aliphatic polyhydroxy compound is neopentaerythritol and / or dioxin Compounds of pentaerythritol. As a commercial item, M-510, M-520, etc. are mentioned as a polyacid 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 range, it is excellent in manufacturing or handling properties, and further, it is excellent in developability. In addition, the polymerizability was good.

From the viewpoint of suppressing warpage caused by controlling the elastic coefficient of the cured film, the thermosetting resin composition of the present invention can preferably use a monofunctional radically polymerizable compound as the radically polymerizable compound. As the monofunctional radical polymerizable compound, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxy can be preferably used. Ethyl (meth) acrylate, carbitol (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, (Meth) acrylic acid such as N-hydroxymethyl (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 and the like. As the monofunctional radical polymerizable compound, in order to suppress volatilization before exposure, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable.

<<< Polymerizable compound other than the above-mentioned radically polymerizable compound >> The thermosetting resin composition of this invention can contain the polymerizable compound other than the said radically polymerizable compound. Examples of the polymerizable compound other than the above radical polymerizable compound include compounds having a methylol group, an alkoxymethyl group, or a fluorenylmethyl group; epoxy compounds; oxetane compounds; benzofluorene compounds .

(Compounds having methylol, alkoxymethyl, or methyloxymethyl) Compounds having methylol, alkoxymethyl, or methyloxymethyl are represented by the following formulae (AM1), (AM4), or (AM5) The compound represented by) is more preferable.

[Chemical Formula 24] (In the formula, t represents an integer of 1 to 20, R ⁴ represents a t-valent organic group having 1 to 200 carbon atoms, R ⁵ represents a group represented by -OR ⁶ or -OCO-R ⁷ , and 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.)

[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 having 1 to 10 carbon atoms.)

[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 having 1 to 10 carbon atoms, and R ⁵⁰⁷ represents an organic group having 1 to 10 carbon atoms.)

Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (the above are the 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 (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (the above are trade names, 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-diethoxymethyl-p-cresol) Cresol) and so on.

Specific examples of the compound represented by the formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, and HML- TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, 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 having an epoxy group)) As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. The epoxy undergoes a crosslinking reaction based on a temperature of 200 ° C or lower, and it is difficult to cause film shrinkage because it does not cause a dehydration reaction derived from crosslinking. Therefore, by containing an epoxy compound, low-temperature hardening and warping 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 the epoxy compound include polyalkylene glycol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, propylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. Epoxy group-containing epoxy resins such as polyalkylene glycol-type epoxy resins and polymethyl (glycidyloxypropyl) siloxanes 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) Trademarks) EXA-4850-150, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822 (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), etc. Among these, a polyethylene oxide-based epoxy resin is preferred from the viewpoint of suppressing warpage and excellent heat resistance. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, and RIKARESIN (registered trademark) BEO-60E are preferred because they contain polyethylene oxide groups.

(Oxetane compound (compound having oxetanyl group)) Examples of the oxetane compound include a compound having two or more oxetane rings in one molecule, and 3-ethyl 3-Hydroxymethoxybutane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, 3-ethyl-3- ( 2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester, and the like. 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. More than two.

(Benzofluorene compound (compound with polybenzoxazolyl group)) The benzofluorene compound does not generate outgassing during hardening due to the cross-linking reaction originating from the ring-opening addition reaction, thereby reducing heat shrinkage and suppressing warpage. It is better.

Preferred examples of the benzofluorene compound include Ba-type benzofluorene, Bm-type benzofluorene (the above are trade names, manufactured by Shikoku Chemicals Corporation), benzofluorene adducts of polyhydroxystyrene resins, Novolak dihydrobenzofluorene compound. These may be used alone, or two or more kinds may be mixed.

When a polymerizable compound is contained, its content is preferably more than 0% by mass and 60% by mass or less based on 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 even more preferably 30% by mass or less. The polymerizable compound may be used singly or in combination of two or more kinds. When two or more kinds are used at the same time, the total amount thereof is preferably within the above range.

<Migration inhibitor> The thermosetting resin composition of the present invention preferably further contains a migration inhibitor. By including a migration inhibitor, the transfer of metal ions originating 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 thereof include a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, Compounds such as azole ring, pyridine ring, pyridyl ring, pyrimidine ring, pyrimidine ring, piperidine ring, piperidine ring, terminal phenoline ring, 2H-pyran ring, 6H-pyran ring, and tricyclic ring) Mercapto compounds, hindered phenol compounds, salicylic acid derivative compounds, hydrazine derivative compounds. In particular, triazole compounds such as 1,2,4-triazole and benzotriazole, and tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

Moreover, an ion trapping agent that captures anions such as halogen ions can also be used.

As other migration inhibitors, the rust inhibitor described in Japanese Patent Application Laid-Open No. 2013-015701, paragraph 0094, the compound described in Japanese Patent Application Laid-Open No. 2009-283711, paragraphs 0073 to 0076, and Japanese Patent Laid-Open No. 2011 can be used. Compounds described in paragraph 0052 of Japanese Patent Publication No. -059656, compounds described in paragraphs 0114, 0116, and 0118 of Japanese Patent Application Laid-Open No. 2012-194520.

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% by mass based on the total solid content of the thermosetting resin composition, and more preferably 0.05 to 2.0% by mass, 0.1 It is more preferably -1.0% by mass. The migration inhibitor may be only one, or may be two or more. When two or more migration inhibitors are used, the total is preferably in the above range.

<Polymerization inhibitor> The thermosetting resin composition of the present invention preferably contains a polymerization inhibitor. As the polymerization inhibitor, for example, hydroquinone, 4-methoxyphenol, di-third-butyl-p-cresol, catechol, p-third-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis (3-methyl-6-third butylphenol), 2,2'-methylenebis (4- Methyl-6-third butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, N-nitroso-diphenylamine, N-phenylnaphthylamine, ethylenediene Amine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol ether diamine tetraacetic acid, 2,6-di-third-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, and the like. In addition, the polymerization inhibitors described in paragraph 0060 of Japanese Patent Laid-Open No. 2015-127817 and the compounds described in paragraphs 031 to 0046 of International Publication No. WO2015 / 125469 can also be used. The following compounds (Me is methyl) 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% by mass, and 0.02 to 3% by mass relative to the total solid content of the thermosetting resin composition of the present invention. % Is more preferred, and 0.05 to 2.5% by mass is particularly preferred. The polymerization inhibitor may be only one kind, or two or more kinds. When there are two or more kinds of polymerization inhibitors, the total is preferably in the above range.

<Metal Adhesive Improver> The thermosetting resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to a metal material used for an electrode, wiring, or the like. Examples of the metal adhesion improving agent include a silane coupling agent.

Examples of the silane coupling agent include compounds described in paragraphs 062 to 0073 of Japanese Patent Application Laid-Open No. 2014-191002, compounds described in paragraphs 0063 to 0071 of International Publication WO2011 / 080992A1, and Japanese Patent Laid-Open The compounds described in paragraphs 0060 to 0061 of 2014-191252, the compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Laid-Open No. 2014-041264, and the compounds described in paragraph 0055 of international publication WO2014 / 097594. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of Japanese Patent Application Laid-Open No. 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 improver, compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Laid-Open No. 2014-186186 and sulfides described in paragraphs 0032 to 0043 of Japanese Patent Application Laid-Open No. 2013-072935 can be used.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and particularly preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the polymer precursor. By making it more than the said lower limit value, the adhesiveness of the cured film after a hardening process and a metal layer becomes favorable, and by making it below the said upper limit value, the heat resistance and mechanical characteristics of the cured film after a hardening process become favorable. The metal adhesion improver may be only one kind, or two or more kinds. When two or more kinds are used, it is preferable that the total is in the above range.

<Hardening accelerator> The thermosetting resin composition of this invention may contain a hardening accelerator. The hardening accelerator may be a thermal hardening accelerator or a light hardening accelerator. <<< Heat hardening accelerator> The heat hardening accelerator is preferably a salt of a quaternary ammonium cation and a carboxylic acid anion. The quaternary ammonium cation is preferably represented by the following formula (Y1-1). [Chemical Formula 30]

In the formula (Y1-1), R ^N1 represents an Nn-valent (Nn is an integer of 1 to 12) organic group, and an Nn-valent hydrocarbon group is preferred. Examples of the hydrocarbon group include an Nn-valent group containing an alkane (carbon number of 1 to 12 is preferred, 1 to 6 is more preferred, and 1 to 3 are particularly preferred), and an Nn-valent group containing an olefin (2 to carbon number) 12 is preferred, 2 to 6 are more preferred, 2 to 3 are particularly preferred), and Nn-valent groups containing aromatic hydrocarbons (6 to 22 carbons are preferred, 6 to 18 are more preferred, 6 to 10 are Very good) or a combination of these. Among them, the aromatic hydrocarbon group of the R ^N1 system is preferable. As long as the effect of the present invention is not impaired, R ^N1 may have the aforementioned substituent T. R ^N2 to R ^N5 each independently represent a hydrogen atom or a hydrocarbon group (carbon number 1 to 36 is preferred, 1 to 24 is more preferred, 1 to 12 is particularly preferred), and alkyl (carbon number 1 to 36 is more preferred, 1 to 24 are more preferred, 1 to 23 are particularly preferred), alkenyl (2 to 36 carbons are preferred, 2 to 24 are more preferred, 2 to 23 are particularly preferred), alkynyls (1 to 36 carbons) For preference, 1 to 24 are more preferred, 1 to 23 are particularly preferred), and aryl (6 to 22 carbons are preferred, 6 to 18 are more preferred, and 6 to 10 are particularly preferred). The alkyl group, alkenyl group, and alkynyl group may be linear or branched, and may be cyclic or chain. R ^N6 is alkyl (carbon number 1 to 36 is preferred, 2 to 24 is more preferred, 4 to 18 is particularly preferred), alkenyl (carbon number 2 to 36 is preferred, 2 to 24 is more preferred, 4 -18 is particularly preferred), alkynyl (2 to 36 carbons is preferred, 2 to 24 is more preferred, 4 to 18 is particularly preferred), aryl (6 to 22 is preferred, 6 to 18 is preferred) More preferably, 6-10 are particularly preferred). Alkyl, alkenyl, and alkynyl may be linear or branched, and may be cyclic or chain. At this time, an alkyl group, an alkenyl group, an alkynyl group, and an aryl group may include a hetero atom-containing linking group Lh in the middle of the chain or in the connection with the mother core. Examples of the hetero atom-containing linking group Lh include -O-, -S-, -CO-, -NR ^N -or a linking group composed of a combination of these. The number of atoms constituting the linking group Lh containing a hetero atom is preferably from 1 to 12, more preferably from 1 to 6, and particularly preferably from 1 to 3. The number of atoms in the specific group of the linking group Lh containing a hetero atom is preferably from 1 to 12, more preferably from 1 to 6, and particularly preferably from 1 to 3. The definition of R ^N is the same as above. As long as the effect of the present invention is not impaired, R ^N6 may further have the aforementioned substituent T. Nn represents an integer from 1 to 12; an integer from 1 to 6 is more preferred; an integer from 1 to 3 is particularly preferred. No is preferably an integer of 1 to 12, an integer of 1 to 6 is more preferred, an integer of 1 to 3 is particularly preferred. Each of R ^N2 to R ^N6 may be bonded to each other to form a ring.

In this embodiment, specific examples of the carboxylic acid anion paired with the quaternary ammonium cation include anions derived from a compound represented by any one of the formulae AC2 to AC5 exemplified by the acidic compound. The molecular weight of the thermosetting accelerator in the present invention is preferably 100 or more and less than 2000, and more preferably 200 to 1,000. As an example of the heat hardening accelerator in the present invention, an acidic compound that generates a base when heated to 40 ° C. or higher and an ammonium salt having an anion and an ammonium cation having a pKa1 of 0 to 4 are described in WO2015 / 199219, and This content is 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% by mass based on the total solid content of the composition. The lower limit is more preferably 0.05% by mass or more, and more preferably 0.1% by mass or more. The upper limit is more preferably 10% by mass or less, and further preferably 5% by mass or less. The thermosetting accelerator can be used alone or in combination of two or more. When two or more kinds are used, the total amount is preferably in the above range. Moreover, the composition of this invention can also be comprised so that a thermosetting accelerator may not be contained substantially. By not substantially containing, it means that it is less than 0.01 mass%, and 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 photo-hardening accelerator in the present invention refers to a person who generates an alkali by exposure and does not show activity under normal conditions of normal temperature and pressure. However, if an electromagnetic wave is irradiated and heated as an external stimulus, the alkali is generated ( Alkaline substances) are not particularly limited. The alkali generated by exposure functions as a catalyst when the polymer precursor is hardened by heating, and therefore can be preferably used. In this invention, a well-known thing can be used as a photohardening accelerator. For example, examples include transition metal complexes, those having structures such as ammonium salts, those having a hydrazone moiety and a carboxylic acid that are potentialized by forming a salt, and ionic compounds and amines whose base components are neutralized by forming a salt. Non-ionic compounds, such as carbamate derivatives, oxime ester derivatives, and fluorenyl compounds, which are potentially made base by amine ester bonds or oxime bonds.

Examples of the light hardening accelerator according to the present invention include a light hardening accelerator having a cinnamate structure as disclosed in Japanese Patent Application Laid-Open No. 2009-080452 and International Publication No. 2009/123122, such as Japan Japanese Unexamined Patent Publication No. 2006-189591 and Japanese Unexamined Patent Publication No. 2008-247747 disclose light curing accelerators having a urethane structure, such as Japanese Unexamined Patent Publication No. 2007-249013 and Japanese Unexamined Patent Publication No. 2008-003581. Although a photo-hardening accelerator having an oxime structure and a formazan oxime structure is disclosed in the above, it is not limited to these, and a structure of a known hardening accelerator can also be used.

Examples of the photohardening accelerator include compounds described in paragraphs 0185 to 0188, 0199 to 0200, and 0202 of Japanese Patent Application Laid-Open No. 2012-093746, and 0022 to 0069 of Japanese Patent Application Laid-Open No. 2013-194205. The compounds described in paragraphs, the compounds described in paragraphs 0026 to 0074 of JP 2013-204019, and the compounds described in paragraph 0052 of International Publication WO2010 / 064631.

As commercially available products for light hardening accelerators, 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% by mass based on the total solid content of the composition. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and more preferably 20% by mass or less. The light hardening accelerator can be used alone or in combination of two or more. When two or more kinds are used, the total amount is preferably in the above range.

<Organic compound containing a Group 4 element> The composition of the present invention preferably contains an organic compound containing a Group 4 element (hereinafter, sometimes referred to as an "organic titanium compound"). As the organic compound containing a Group 4 element, an organic compound containing at least one kind selected from a titanium atom, a zirconium atom, and a hafnium atom is preferable, and an organic compound containing at least one kind selected from a titanium atom and a zirconium atom is more preferable . The organic compound containing at least one selected from the group consisting of a titanium atom and a zirconium atom is preferably a compound containing an organic group and a titanium atom or a zirconium atom. The total number of titanium atoms and zirconium atoms in one molecule is preferably one. . The organic group is not particularly limited, and a group composed of a hydrocarbon group, a combination of a hydrocarbon group, and a hetero atom is preferred. As the hetero atom, an oxygen atom, a sulfur atom, and a nitrogen atom are preferred. In the present invention, at least one cyclic group in the organic group is preferred, and at least two cyclic groups are more preferred. The cyclic group is preferably selected from a 5-membered ring cyclic group and a 6-membered ring cyclic group, and more preferably selected from a 5-membered ring cyclic group. As the 5-membered ring cyclic group, cyclopentadienyl is preferred. The organic titanium compound or the like used in the present invention preferably contains 2 to 4 cyclic groups in one molecule. The organic titanium compound and the like in the present invention are preferably represented by the following formulae (P-1) to (P-3), and more preferably a compound represented by the formula (P-1). [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 selected from an alkyl group, a halogen atom, and an alkylsulfonyloxy group. The aryl group is preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms. Specific examples include phenyl, 1-naphthyl, and 2-naphthyl. As the alkyl group, 1 to 12 carbons are preferred, 1 to 6 are more preferred, and 1 to 3 are more preferred. Specific examples include methyl, ethyl, propyl, octyl, and isopropyl , Third butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl and the like. Examples of the halogen atom include F, Cl, Br, and I. The alkyl group constituting the alkylsulfonyloxy group is preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms. Specific examples include methyl, ethyl, and propyl. Group, octyl, isopropyl, third butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl and the like. The said substituent may have a substituent. Examples of the substituent include the substituent T, and specific examples include a halogen atom (F, Cl, Br, I), a hydroxyl group, a carboxyl group, an amine group, a cyano group, an aryl group, an alkoxy group, and an aromatic group. Oxy, fluorenyl, alkoxycarbonyl, aryloxycarbonyl, fluorenyl, monoalkylamino, dialkylamino, monoarylamino, diarylamino, and the like.

R ^P1 to R ^P4 are a halogen atom, a hydroxyl group, or an organic group (other than a cyclopentadienyl group). Examples of the organic group include an alkyl group (carbon number of 1 to 12 is preferred, 1 to 6 is more preferred, and 1 to 3 is more preferred), and an alkenyl group (carbon number of 2 to 12 is preferred, 2 to 6) For better, 2 to 3 are more preferred), aryl (6 to 22 carbons is preferred, 6 to 18 is more preferred, 6 to 10 is more preferred), alkoxy (1 to 12 carbons) For the better, 1 to 6 is more preferable, 1 to 3 is more preferable), aryloxy group (carbon number 6 to 22 is better, 6 to 18 is more preferable, 6 to 10 is more preferable), alkane Sulfosulfonyloxy (carbon number 1 to 12 is preferred, 1 to 6 is more preferred, 1 to 3 is more preferred), arylsulfonyloxy (carbon number 1 to 12 is preferred, 1 to 6) For the better, 1 to 3 is more preferred), fluorenyloxy (2 to 12 carbons is preferred, 2 to 6 is more preferred, 2 to 3 is more preferred), arylfluorenyloxy (7 to carbons) -23 is more preferable, 7-19 is more preferable, and 7-11 is more preferable. R ^P0 is an organic linking group of the ligand in the formula (carbon number 2 to 12 is preferred, 2 to 6 is more preferred, 2 to 4 is more preferred, and the hetero linking group Lh may not be used), for example Examples include β-diketone ligands. Examples of β-diketone include acetoacetone and acetoacetate. Examples of R ^P0 include a structure of the following formula (P-3 (a)). * It is a bond with an oxygen atom. [Chemical Formula 32] R ^P11 is the same group as R ^P1 . R ^P12 to R ^P14 are a hydrogen atom or a substituent T. Among the substituents T, an alkyl group (carbon number 1 to 12 is preferred, 1 to 6 is more preferred, and 1 to 3 is more preferred) or an alkoxy group (carbon number 1 to 12 is preferred, 1 to 6) More preferably, 1 to 3 are further preferred) are more preferred. 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 , R ^P11 to R ^P14 include an alkyl group, an alkenyl group, an aryl group, or a linking group containing these groups, it may have an optional substituent T within the range equivalent to the effect of the present invention. (E.g. hydroxyl, carboxyl, halogen atom, etc.). When there are a plurality of R, R ^P1 to R ^P4 , and when there are a plurality of R ^P11 , R ^P12 to R ^{P14, they} may be the same as or different from each other. In addition, two or more groups adjacent to each other through or without the linking group L described below may be bonded to form a ring. Linker L-based alkylene (carbon number 1 to 12 is preferred, 1 to 6 is more preferred, 1 to 3 is particularly preferred), alkenyl (carbon number 2 to 12 is preferred, 2 to 6 is more preferred) (Better), O, CO, NR ^N , S, or a combination thereof is more preferred. In addition to the hydrogen atom, the number of atoms constituting the linking group L is preferably from 1 to 12, more preferably from 1 to 6, and particularly preferably from 1 to 3. The number of linking atoms of the linking group L is preferably 10 or less, and more preferably 8 or less. The lower limit is 1 or more. The above-mentioned number of connected atoms refers to the minimum number of atoms that are located on the path between the predetermined structural parts and related to the connection. For example, when -CH ₂ -C (= O) -O-, the number of atoms constituting the linking group is 6, but the number of connecting atoms is 3.

The organic compound containing a Group 4 element used in the present invention is preferably selected from the group consisting of a titanocene compound, a tetraalkoxy titanium compound, a titanium halide, a titanium chelate, a zirconocene compound, and a hafnium compound. The titanocene compound, the zirconocene compound and the hafnium compound are more preferable, and the titanocene compound and the zirconocene compound are more preferably selected.

The molecular weight of an organic titanium compound or the like is preferably 50 to 2000, and more preferably 100 to 1,000.

Specific examples of the organic titanium compound include tetraethylpropoxy titanium, tetra (2-ethylhexyloxy) titanium, diisopropoxy bis (ethyl ethyl acetate) titanium, and diisopropoxy bis (Acetylpyruvate) Titanium, the following compounds, or the compounds listed in the examples described later. [Chemical Formula 33]

Further, as the organic compound containing a titanium atom among organic titanium compounds, di-cyclopentadienyl-Ti-dichloride (bis (cyclopentadienyl) titanium dichloride), di-cyclo 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 Cyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5, 6-tetrafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-difluorophenyl-1-yl, bis (cyclopentadienyl) -bis (2 , 6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (methylsulfonamido) phenyl ] Titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butylbisarylroyl-amino) phenyl] titanium, bis (cyclopentadienyl) ) Bis [2,6-difluoro-3- (N-ethylethylamidoamino) Group] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-methylethylamidoamino) phenyl] titanium, bis (cyclopentadienyl) bis [2 , 6-difluoro-3- (N-ethylpropanylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethyl- ( 2,2-dimethylbutylfluorenyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl- (2,2-dimethyl Butanyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-pentyl- (2,2-dimethylbutylfluorenyl) amino) phenyl ] Titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl)-(2,2-dimethylbutylfluorenyl) phenyl] titanium, bis (cyclopentadienyl) ) Bis [2,6-difluoro-3- (N-methylbutylfluorenylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-methyl Pentamylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethylcyclohexylcarbonylamino) phenyl] titanium, bis (cyclopentyl Dienyl) bis [2,6-difluoro-3- (N-ethylisobutylamidinoamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6- Difluoro-3- (N-ethylethylamidoamino) 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- (hexadecylsulfonylamino) 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-pentane Heptyl) phenyl) sulfonamido)] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl- (4-toluenylmethyl) -sulfonamido) (Yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (pyrrolidin-2,5-dione-1-yl) phenyl] titanium, bis (cyclopentyl Dienyl) bis [2,6-difluoro-3- (3,4-dimethyl-3-pyrrolidin-2,5-dione-1-yl) phenyl] titanium, bis (cyclopentane Alkenyl) bis [2,6-difluoro-3- (phthalimide) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (isobutyl Oxycarbonylamino) 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 (cyclopentadienyl) bis [2,6-difluoro-3- (Phenoxycarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-phenylthiourea) phenyl] titanium, bis (cyclopentane Alkenyl) bis [2,6-difluoro-3- (3-butylthiourea) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-benzene base ) Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-butylurea) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 -Difluoro-3- (N, N-diethylamidoamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3,3-dimethyl Urea) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (ethylamidoamino) phenyl] titanium, bis (cyclopentadienyl) bis [2, 6-difluoro-3- (butylfluorenylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (decylfluorenylamino) phenyl] titanium, bis ( Cyclopentadienyl) bis [2,6-difluoro-3- (octadecylamidoamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (isobutylfluorenylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- ( 2-ethylhexylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-methylbutylfluorenylamino) phenyl] titanium, bis ( Cyclopentadienyl) bis [2,6-difluoro-3- (neopentylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- ( 2,2-dimethylbutylfluorenylamino) 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-chloropropanylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3 -Phenylpropenylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-chloromethyl-2-methyl-3-chloropropanyl) Amine) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3,4-xylylamino) phenyl] titanium, bis (cyclopentadiene ) Bis [2,6-difluoro-3- (4-ethylbenzylideneamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2 , 4,6-mesityl-tolylcarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (benzylideneamino) phenyl] titanium, Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-phenylpropyl) benzylideneamino) phenyl] titanium, bis (cyclopentadienyl) Bis [2,6-difluoro-3- (N- (3-ethylheptyl) -2,2-dimethylpentamylamino] phenyl titanium, bis (cyclopentadienyl) bis [ 2,6-difluoro-3- (N-isobutyl- (4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro- 3- (N-isobutylbenzylideneamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexylmethylneopentyl) Amine) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (oxetan-2-ylmethyl) benzylamino) Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-ethylheptyl) -2,2-dimethylbutylfluorenylamino) phenyl] titanium Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-phenylpropyl- (4-tolylmethyl) amino) phenyl] titanium, bis (cyclopentyl Dienyl) bis [2,6-difluoro-3- (N- (oxetanyl-2-ylmethyl)-(4-tolylmethyl) amino) phenyl] titanium, bis ( Cyclopentadienyl) bis [2,6-difluoro-3- (N- (4-toluenylmethyl) benzylideneamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (4-toluenylmethyl)-(4-toluenylmethyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2 , 6-difluoro-3- (N-butylbenzylideneamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl- (4-tolylmethyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl- (4-toluenyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (2,4-dimethylpentyl) -2,2-dimethylbutylfluorenylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2,4-dimethylpentyl) -2,2-dimethylpentamylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- ( (4-Tolylmethylamino) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2,2-dimethylpentamylamino) benzene Group] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2,2-dimethyl-3-ethoxypropylamidoamino) phenyl] titanium, bis ( Cyclopentadienyl) bis [2,6-difluoro-3- (2,2-dimethyl-3-allyloxypropylamidoamino) phenyl] titanium, bis (cyclopentadienyl ) Bis [2,6-difluoro-3- (N-allylethylfluorenylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2 -Ethylbutylfluorenylamino) benzene Group] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexylmethylbenzylamino) phenyl] titanium], bis (cyclopentadienyl) Bis [2,6-difluoro-3- (N-cyclohexylmethyl- (4-tolylmethyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-di Fluoro-3- (N- (2-ethylhexyl) benzylideneamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isopropyl Benzamidineamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-phenylpropyl) -2,2-dimethyl Pentylfluorenyl) 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-dimethylpentamyl) amino) phenyl] titanium, bis (cyclopentadiene Group) bis [2,6-difluoro-3- (N-butylbenzylideneamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- ( N- (2-ethylhexyl) -2,2-dimethylpentamyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N -already -2,2-dimethylpentanylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isopropyl-2,2-di Methylpentamylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-phenylpropyl) neopentylamino) Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl-2,2-dimethylpentamylamino) phenyl] titanium, bis ( Cyclopentadienyl) bis [2,6-difluoro-3- (N- (2-methoxyethyl) benzylideneamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-benzylbenzylideneamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-benzyl -(4-tolylmethyl) amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (2-methoxyethyl)-(4-tolyl) amino) phenyl] titanium, bis (cyclopentadienyl) Dienyl) bis [2,6-difluoro-3- (N- (4-methylphenylmethyl) -2,2-dimethylpentamylamino) phenyl] titanium, bis (cyclo Pentadienyl) bis [2,6-difluoro-3- (N- (2-methoxyethyl) -2,2-dimethylpentamylamino) phenyl] titanium, bis (cyclo Pentadienyl) bis [2,6-difluoro-3- (N-cyclohexylmethyl- (2-ethyl-2-methylheptyl) amino) phenyl] titanium, bis (cyclopentyl Dienyl) bis [2,6-difluoro-3- (N-butyl- (4-chlorobenzylidene) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2, 6-difluoro-3- (N-hexyl- (2-ethyl-2-methylbutylfluorenyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3 -(N-cyclohexyl-2,2-dimethylpentamyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (oxy Pentyl-2-ylmethyl) -2,2-dimethylpentanyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N -Cyclohexyl- (4-chlorobenzyl) (Yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexyl- (2-chlorobenzyl) amino) phenyl] titanium, bis (Cyclopentadienyl) bis [2,6-difluoro-3- (3,3-dimethyl-2-azinodinone-1-yl) phenyl] titanium, bis (cyclopentadiene Alkenyl) bis [2,6-difluoro-3-isocyanatephenyl) titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethyl- (4-toluene) Sulfofluorenyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl- (4-tolylsulfonyl) amino) benzene Group] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl- (4-tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentyl Dienyl) 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-chloropropylfluorenyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2, 6-difluoro-3- (N- (3-phenylpropanyl) -2,2-dimethyl-3-chloropropanyl) amino) phenyl] titanium, bis (cyclopentadienyl) ) [2,6-difluoro-3- (N-cyclohexylmethyl- (2,2-dimethyl-3-chloropropanyl) amino) phenyl] titanium, bis (cyclopentadienyl) Bis [2,6-difluoro-3- (N-isobutyl- (2,2-dimethyl-3-chloropropylamidino) phenyl] titanium, bis (cyclopentadienyl) bis [2 , 6-difluoro-3- (N-butyl- (2-chloromethyl-2-methyl-3-chloropropylfluorenyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (butylthiocarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (phenylthiocarbonylamino) (Yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-isocyanatephenyl) 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) Amine) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isobutyl- (4-tolylsulfonyl) amino) phenyl] titanium ,double Cyclopentadienyl) bis [2,6-difluoro -3- (N-butyl - (2,2-dimethyl-3-chloropropyl acyl) amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-phenylpropanyl) -2,2-dimethyl-3-chloropropylfluorenyl) amino) benzene Group] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexylmethyl- (2,2-dimethyl-3-chloropropanyl) amino) Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isobutyl- (2,2-dimethyl-3-chloropropylfluorenyl) phenyl] Titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl- (2-chloromethyl-2-methyl-3-chloropropylamidino) amino) benzene Group] 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- Dimethylbutylfluorenyl) amino) phenyl] titanium, bis (methylcyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl-2,2-dimethylpentamylamine) (Yl) phenyl] titanium, bis (methylcyclopentadienyl) bis [2,6-difluoro-3- (N-ethylethylamidoamino) phenyl] titanium, bis (methylcyclopentyl Dienyl) bis [2,6- Fluoro-3- (N-ethylpropylamidoamino) phenyl] titanium, bis (trimethylsilylcyclopentadienyl) bis [2,6-difluoro-3- (N-butyl -2,2-dimethylpropanylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (2-methoxyethyl) -Trimethylsilylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butylhexyldimethylsilylamino) benzene Group] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethyl- (1,1,2-trimethylpropyl) dimethylsilylamine group ) Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-ethoxymethyl-3-methyl-2-azafluorenone-1-yl) benzene Yl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-allyloxymethyl-3-methyl-2-azepinone-1-yl) phenyl ] Titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-chloromethyl-3-methyl-2-azafluorenone-1-yl) phenyl] titanium, bis (Cyclopentadienyl) bis [2,6-difluoro-3- (N-benzyl-2,2-dimethylpropanylamino) phenyl] titanium, bis (cyclopentadienyl) Bis [2,6-difluoro-3- (5,5-di 2-Pyrrolidone-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (6,6-diphenyl-2-piperidone-1) -Yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (2,3-dihydro-1,2-benzoisothiazol-3-one (1,1-dioxide) -2-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl- (4-chlorobenzylhydrazone) Group) amino group) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl- (2-chlorobenzylidene) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isopropyl- (4-chlorobenzylidene) 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-chlorobenzylidene) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro -3- (N-butyl- (4-chlorobenzylidene) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-benzyl -2,2-dimethylpentanylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (2-ethylhexyl) -4 -Tolyl-sulfofluorenyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-oxaheptyl) benzyl) Amine) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3,6-dioxadecyl) benzylamino) phenyl Titanium, bis (cyclopentane Group) bis [2,6-difluoro-3- (trifluoromethylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- ( Trifluoroethylfluorenylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-chlorobenzylidene) amino) phenyl] titanium, bis (Cyclopentadienyl) bis [2,6-difluoro-3- (4-chlorobenzylidene) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-di Fluoro-3- (N- (3,6-dioxadecyl) -2,2-dimethylpentamylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 -Difluoro-3- (N- (3,7-dimethyl-7-methoxyoctyl) benzylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2, 6-difluoro-3- (N-cyclohexylbenzylamino) phenyl] titanium and the like.

Among organic titanium compounds and the like, as the organic compound containing a zirconium atom or the compound containing a hafnium atom, (cyclopentadienyl) trimethylzirconium, (cyclopentadienyl) triphenylzirconium, ( Cyclopentadienyl) tribenzyl zirconium, (cyclopentadienyl) trichlorozirconium, (cyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) dimethyl (methoxy) zirconium , Cyclopentadienyl methyl dichlorozirconium, (methyl cyclopentadienyl) trimethyl zirconium, (methyl cyclopentadienyl) triphenyl zirconium, (methyl cyclopentadienyl) Benzyl zirconium, (methylcyclopentadienyl) trichlorozirconium, (methylcyclopentadienyl) dimethyl (methoxy) zirconium, (dimethylcyclopentadienyl) trimethyl zirconium (Trimethylcyclopentadienyl) trimethyl zirconium, (trimethylsilyl cyclopentadienyl) trimethyl zirconium, (tetramethylcyclopentadienyl) trimethyl zirconium, ( Pentamethylcyclopentadienyl) trimethylzirconium, (pentamethylcyclopentadienyl) triphenylzirconium, (pentamethylcyclopentadienyl) tribenzylzirconium, (pentamethylcyclopentadienyl) Dienyl) trichlorozirconium, (pentamethylcyclopentadienyl Trimethoxy zirconium, (pentamethylcyclopentadienyl) dimethyl (methoxy) zirconium, (cyclopentadienyl) triethyl zirconium, (cyclopentadienyl) tripropyl zirconium, ( Cyclopentadienyl) trinepentyl zirconium, (cyclopentadienyl) tris (diphenylmethyl) zirconium, (cyclopentadienyl) dimethylzirconium hydride, (cyclopentadienyl) triazine Zirconyl ethoxy, (cyclopentadienyl) zirconium triisopropoxide, (cyclopentadienyl) zirconium triphenoxy, (cyclopentadienyl) dimethyl isopropoxy zirconium, (cyclo (Pentadienyl) diphenyl isopropoxy zirconium, (cyclopentadienyl) dimethoxy zirconium chloride, (cyclopentadienyl) methoxy zirconium chloride, (cyclopentadienyl) Diphenoxy zirconium chloride, (cyclopentadienyl) phenoxy zirconium dichloride, (cyclopentadienyl) tris (phenyldimethylsilyl) zirconium, (n-butylcyclopentane Alkenyl) dimethyl-n-butoxy zirconium, (benzylcyclopentadienyl) di-m-tolyl methyl zirconium, (trifluoromethylcyclopentadienyl) tribenzyl zirconium, (diphenyl Cyclopentadienyl) dinorbornyl methyl zirconium, (tetraethylcyclopentadienyl) tribenzyl zirconium, (Penta-trimethylsilylcyclopentadienyl) tribenzyl zirconium, (pentamethylcyclopentadienyl) trineopentyl zirconium, (pentamethylcyclopentadienyl) methyl dichloride Zirconium, (pentamethylcyclopentadienyl) triethoxy zirconium, (pentamethylcyclopentadienyl) triphenoxy zirconium, (pentamethylcyclopentadienyl) methoxydichloro Zirconium, (pentamethylcyclopentadienyl) diphenoxy zirconium chloride, (pentamethylcyclopentadienyl) phenoxy zirconium dichloride, (indenyl) trimethyl zirconium, (indene) Group) tribenzyl zirconium, (indenyl) zirconium trichloride, (indenyl) trimethoxy zirconium,

(Indenyl) triethoxy zirconium, bis (cyclopentadienyl) dimethyl zirconium, bis (cyclopentadienyl) diphenyl zirconium, bis (cyclopentadienyl) diethyl zirconium, bis (Cyclopentadienyl) dibenzyl zirconium, bis (cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) zirconium dichloride (bis (cyclopentadienyl) dichloride Zirconium), bis (cyclopentadienyl) zirconium dihydrogen, bis (cyclopentadienyl) zirconium chlorohydride, bis (methylcyclopentadienyl) dimethyl zirconium, bis (methylcyclopentadiene) Group) dibenzylzirconium, bis (methylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) dimethylzirconium, bis (pentamethylcyclopentadienyl) dibenzyl Zirconyl, bis (pentamethylcyclopentadienyl) dichlorozirconium, bis (pentamethylcyclopentadienyl) chloromethyl zirconium, bis (pentamethylcyclopentadienyl) hydrogen methyl zirconium, (Cyclopentadienyl) (pentamethylcyclopentadienyl) dimethyl zirconium, bis (cyclopentadienyl) di neopentyl zirconium, bis (cyclopentadienyl) di-m-tolyl zirconium Bis (cyclopentadienyl) di-p-tolyl zirconium, bis (cyclopentadienyl) bis (diphenylmethyl) Base) zirconium, bis (cyclopentadienyl) dibromozirconium, bis (cyclopentadienyl) methylzirconium chloride, bis (cyclopentadienyl) ethylzirconium chloride, bis (cyclopentadienyl) Cyclohexyl chloride zirconium, bis (cyclopentadienyl) phenyl zirconium chloride, bis (cyclopentadienyl) benzyl chloride zirconium, bis (cyclopentadienyl) hydrogen methyl zirconium, bis (cyclopentadiene) Base) zirconyl methoxychloride,

Bis (cyclopentadienyl) ethoxyzirconium chloride, bis (cyclopentadienyl) (trimethylsilyl) methyl zirconium, bis (cyclopentadienyl) bis (trimethylsilyl) ) Zirconium, bis (cyclopentadienyl) (triphenylsilyl) methyl zirconium, bis (cyclopentadienyl) (tri (dimethylsilyl) silyl) methyl zirconium, bis ( Cyclopentadienyl) (trimethylsilyl) (trimethylsilylmethyl) zirconium, bis (methylcyclopentadienyl) diphenyl zirconium, bis (ethylcyclopentadienyl) ) Dimethyl zirconium, bis (ethylcyclopentadienyl) dichlorozirconium, bis (propylcyclopentadienyl) dimethylzirconium, bis (propylcyclopentadienyl) zirconium dichloride, bis (N-butylcyclopentadienyl) zirconium dichloride, bis (third butylcyclopentadienyl) bis (trimethylsilyl) zirconium, bis (hexylcyclopentadienyl) zirconium dichloride, Bis (cyclohexylcyclopentadienyl) dimethyl zirconium, bis (dimethylcyclopentadienyl) dimethyl zirconium, bis (dimethylcyclopentadienyl) zirconium dichloride, bis (dimethyl) Cyclopentadienyl) ethoxyzirconium chloride, bis (ethylmethylcyclopentadienyl) Zirconium dichloride, bis (propylmethylcyclopentadienyl) zirconium dichloride, bis (butylmethylcyclopentadienyl) zirconium dichloride, bis (trimethylcyclopentadienyl) zirconium dichloride, bis (Tetramethylcyclopentadienyl) zirconium dichloride, bis (cyclohexylmethylcyclopentadienyl) dibenzyl zirconium, bis (trimethylsilylcyclopentadienyl) dimethylzirconium, bis (trimethyl Silylcyclopentadienyl) dichlorozirconium, bis (trimethylgermanylcyclopentadienyl) dimethylzirconium, bis (trimethylgermanylcyclopentadienyl) diphenyl Zirconium, bis (trimethylstannylcyclopentadienyl) dimethyl zirconium, bis (trimethylstannylcyclopentadienyl) dibenzyl zirconium, bis (trifluoromethylcyclopentyl) Dienyl) dimethyl zirconium, bis (trifluoromethylcyclopentadienyl) norbornyl zirconium, bis (indenyl) dibenzyl zirconium, bis (indenyl) dichlorozirconium, bis (indenyl) Zirconium dibromo, bis (tetrahydroindenyl) dichlorozirconium, bis (fluorenyl) dichlorozirconium, (propylcyclopentadienyl) (cyclopentadienyl) dimethyl zirconium, (cyclohexylmethyl) Cyclopentadienyl) (cyclopentadienyl) dibenzyl zirconium, (pentatrimethylsilane Cyclopentadienyl) (cyclopentadienyl) dimethyl zirconium, (trifluoromethylcyclopentadienyl) (cyclopentadienyl) dimethyl zirconium, ethylidene bis (indenyl) di Methyl zirconium, ethyl bis (indenyl) dichlorozirconium, ethyl bis (tetrahydroindenyl) dimethyl zirconium, ethylene bis (tetrahydroindenyl) zirconium dichloride, dimethylmethylene Silylbis (cyclopentadienyl) dimethyl zirconium, dimethylmethylenesilylbis (cyclopentadienyl) dichlorozirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) ) Zirconium dimethyl, isopropylidene (cyclopentadienyl) (9-fluorenyl) dichlorozirconium, [phenyl (methyl) propylidene] (9-fluorenyl) (cyclopentadienyl) ) Dimethyl zirconium, diphenylene (cyclopentadienyl) (9-fluorenyl) dimethyl zirconium, ethylene (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, Cyclohexyl (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclopentyl (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclobutyl (9- Fluorenyl) (cyclopentadienyl) dimethyl zirconium, dimethylmethylene silyl (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, dimethyl Silylbis (2,3,5-trimethylcyclopentadienyl) dimethylzirconium, dimethylmethylenesilylbis (2,3,5-trimethylcyclopentadienyl) dichloride Zirconium, dimethylmethylenesilylbis (indenyl) dichlorozirconium, propylene (bis (cyclopentadienyl)) dimethylzirconium, propylene (bis (cyclopentadienyl)) bis (trimethyl) Silyl) zirconium,

Acrylic (cyclopentadienyl) (tetramethylcyclopentadienyl) dimethyl zirconium, Acrylic (cyclopentadienyl) (fluorenyl) dimethyl zirconium, Acrylic bis (cyclo Pentadienyl) dimethyl zirconium, ethylidene bis (cyclopentadienyl) dibenzyl zirconium, ethylidene bis (cyclopentadienyl) zirconium dihydrogen, ethylidene bis (indenyl) di Phenyl zirconium, ethylidene bis (indenyl) methyl chloride zirconium, ethylidene bis (tetrahydroindenyl) dibenzyl zirconium, isopropylidene (cyclopentadienyl) (methyl cyclopentadiene) Base) zirconium dichloride, isopropylidene (cyclopentadienyl) (octahydrofluorenyl) zirconium dihydride, dimethylmethylenesilyl bis (cyclopentadienyl) dineopentyl zirconium, dimethyl Methylmethylenesilylbis (cyclopentadienyl) zirconium dihydrogen, dimethylmethylenesilylbis (methylcyclopentadienyl) zirconium dichloride, dimethylmethylenesilylbis (dimethyl) Cyclopentadienyl) zirconium dichloride, dimethylmethylenesilyl bis (tetrahydroindenyl) dichlorozirconium, dimethylmethylenesilyl (cyclopentadienyl) (fluorenyl) dichlorozirconium, Dimethylmethylenesilyl (cyclopentadienyl) (fluorenyl) zirconium dihydrogen, dimethylmethylenesilyl Methylcyclopentadienyl) (fluorenyl) zirconium dihydrogen, dimethylmethylenesilylbis (3-trimethylsilylcyclopentadienyl) zirconium dihydrogen, dimethylmethylenesilylbis (indene) Group) dimethylzirconium, diphenylmethylenesilylbis (indenyl) dichlorozirconium, phenylmethylmethylenesilylbis (indenyl) dichlorozirconium. In addition, a compound such as a zirconium atom in which these compounds are substituted with a hafnium atom can also be used.

The content of the organic titanium compound and the like is preferably 0.1 to 30% by mass based on the total solid content of the composition of the present invention. The lower limit is more preferably 1.0% by mass or more, more preferably 1.5% by mass or more, and particularly preferably 2.0% by mass or more. The upper limit is more preferably 25% by mass or less, 15% by mass or less is more preferable, 10% by mass or less is further preferable, and 5% by mass or less is particularly preferable. Organic titanium compounds and the like can be used alone or in combination of two or more. When two or more kinds are used, the total amount is preferably in the above range. 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 hot alkali generator is preferably 100: 1 to 1: 100, more preferably 90:10 to 10:90, and 40: 60 to 20:80 is more preferable. By setting this range, it is possible to achieve a higher ring closure rate and a higher glass transition temperature of the polymer precursor at a low temperature.

By blending an organic titanium compound or the like in the composition of the present invention, it is possible to achieve a further higher ring opening rate and a further higher glass transition temperature at a low temperature of the heterocyclic polymer-containing precursor. By setting this blending amount to the above range, a particularly high effect can be obtained.

<Other additives> The thermosetting resin composition of the present invention can be added to various additives, such as a thermal acid generator, a sensitizing dye, a chain transfer agent, and a surfactant, as needed, as long as the effects of the present invention are not impaired. , Higher fatty acid derivatives, inorganic particles, hardeners, hardening catalysts, fillers, antioxidants, ultraviolet absorbers, aggregation inhibitors and the like. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the composition.

<< Thermal acid generator> The 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. Examples of the thermal acid generator include compounds described in paragraph 0059 of Japanese Patent Application Laid-Open No. 2013-167742.

The content of the thermal acid generator is preferably 0.01 parts by mass or more with respect to 100 parts by mass of the polymer precursor, and more preferably 0.1 parts by mass or more. When the thermal acid generator is contained in an amount of 0.01 parts by mass or more, the crosslinking reaction and the cyclization of the polymer precursor are promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved. From the viewpoint of electrical insulation of the cured film, the content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and particularly preferably 10 parts by mass or less. As the thermal acid generator, only one kind may be used, or two or more kinds may be used. When two or more kinds are used, the total amount is preferably within the above range.

<<< Sensitizing dye> The thermosetting resin composition of this invention may contain a sensitizing dye. The sensitizing dye absorbs a specific active radiation and becomes an electronically excited state. The sensitized dye in an electronically excited state is brought into contact with a thermal hardening accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, and the like, thereby causing the effects of 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, refer to the descriptions in paragraphs 0161 to 0163 of Japanese Patent Application Laid-Open No. 2016-027357, and incorporate the contents into this 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% by mass, and 0.1 to 15% by mass relative to the total solid content of the thermosetting resin composition of the present invention. % Is more preferable, and 0.5 to 10% by mass is further more preferable. The sensitizing dye may be used singly or in combination of two or more kinds.

<<< 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 the third edition of the Polymer Dictionary (The Society of Polymer Science, Japan, 2005) pages 683-684. As the chain transfer agent, for example, a compound group having SH, PH, SiH, and GeH in a molecule is used. The radicals are generated by supplying hydrogen to low-active radicals, or by deprotonation after oxidation. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptopolybenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazol) 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 based on 100 parts by mass of the total solid content of the thermosetting resin composition of the present invention. -10 mass parts is more preferable, and 1-5 mass parts is more preferable. The chain transfer agent may be only one kind, or two or more kinds. When there are two or more kinds of chain transfer agents, the total range is preferably the above 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 non-ionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. The following surfactants are also preferred. 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% by mass based on the total solid content of the thermosetting resin composition of the present invention, and more preferably 0.005. To 1.0% by mass. The surfactant may be only one kind, or two or more kinds. When there are two or more surfactants, it is preferable that the total is in the above range.

<<< Higher fatty acid derivative> In order to prevent polymerization inhibition by oxygen, the thermosetting resin composition of the present invention may be added with a higher fatty acid derivative such as behenic acid or ammonium behenate. It exists locally 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 based on the total solid content of the thermosetting resin composition of the present invention. The higher fatty acid derivative may be only one, or may be two or more. When there are two or more types of higher fatty acid derivatives, the total is preferably in the above range.

<Restrictions on Other Contained Substances> From the viewpoint of coating surface properties, 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 less than 0.6% by mass. Extraordinary.

In addition to the above Group 4 metals, the metal content of the thermosetting resin composition of the present invention is preferably less than 5 mass ppm (parts per million), and less than 1 mass ppm from the viewpoint of insulation properties. For further preference, less than 0.5 mass ppm is particularly preferred. Examples of metals to be suppressed include sodium, potassium, magnesium, calcium, iron, chromium, and nickel. When a plurality of metals are included, the total of these metals is preferably within the above range. In addition, as a method for reducing the metal impurities inadvertently contained in the thermosetting resin composition of the present invention, as a raw material constituting the thermosetting resin composition of the present invention, a material having a small metal content can be selected. The raw materials of the thermosetting resin composition of the invention are filtered by a filter, and the inside of the device is lined with polytetrafluoroethylene or the like, and distillation is performed under conditions that minimize contamination.

Regarding the thermosetting resin composition of the present invention, in consideration of the use as a semiconductor material, from the viewpoint of wiring corrosion, 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 is particularly good. Among them, those present in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and more preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of a chlorine atom and a bromine atom, or a chloride ion and a bromine ion is the said range, 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 storage container, for the purpose of suppressing impurities from being mixed into the raw materials or the composition, it is also preferable to use a multi-layer bottle composed of six types of six-layer resin and a six-layer resin bottle having a seven-layer structure. Examples of such containers include those described in Japanese Patent Application Laid-Open No. 2015-123351.

<Preparation of composition> The thermosetting resin composition of this invention can be prepared by mixing each said component. The mixing method is not particularly limited, and can be performed by a conventionally known method. The thermosetting resin composition of the present invention is exemplified by including a pKa of a conjugated acid of an amine compound and a pKa of an acidic compound in the range of Formula 1 to be selected from a polyimide precursor and a polybenzoxazole. The case where the polymer precursor, the amine compound, the acidic compound, and the solvent are mixed in the precursor. The thermoplastic resin of the present invention is exemplified by including a pKa of a conjugated acid of an amine compound and a pKa of an acidic compound within the range of Formula 1. In the case of a step of mixing a polymer precursor, a salt including a cation derived from an amine compound and a salt derived from an anion derived from an acidic compound, and a solvent, In addition, for the purpose of removing foreign matters such as garbage and particles in the composition, it is preferable to perform filtration using a filter. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be previously cleaned with an organic solvent. 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. In addition, various materials can be filtered multiple times. When filtering multiple times, it can be circular filtering. In addition, filtration may be performed after pressurization. When filtering is performed after pressurization, the pressure for pressurizing 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 a filter and an impurity removal treatment using an adsorbent. As the adsorbent, a known adsorbent can be used. Examples include inorganic adsorbents such as silica gel and zeolites, and organic adsorbents such as activated carbon.

<Curable film, laminated body, semiconductor device, and manufacturing method thereof> Next, a cured film, a laminated body, a semiconductor device, and the manufacturing method thereof will be described. The cured film of the present invention is obtained by curing the thermosetting resin composition of the present invention. The film thickness of the cured film of the present invention can be, for example, 0.5 μm or more, and can be 1 μm or more. The upper limit value can be set to 100 μm or less, and can also be set to 30 μm or less.

Two or more layers of the cured film of the present invention can be used as a laminate. A laminated system having two or more layers of the cured film of the present invention preferably has a metal layer between the cured films. These metal layers are preferably used as metal wiring such as a redistribution layer.

Examples of the applicable fields of the cured film of the present invention include insulating films for semiconductor devices, interlayer insulating films for rewiring layers, and stress buffer films. Other examples include a case where a sealing film, a substrate material (a base film or a cover film of a flexible printed circuit board, an interlayer insulating film), or an insulating film for practical mounting purposes is patterned by etching. For these uses, see, for example, Science & technology Co., Ltd., "High Functionality and Application Technology of Polyimide" April 2008, Yamoto Kakimoto / Supervision, CMC Technology Library "Basis of Polyimide Materials" And development "November 2001.

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

The method for producing a cured film of the present invention includes using the thermosetting resin composition of the present invention. Specifically, the method 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 applying a thermosetting resin composition formed into a layer at 50 to 500 ° C. The object is heated. When photosensitivity is imparted to the thermosetting resin composition, it is preferable to include an exposure step for performing exposure after the layer forming step and performing the exposure to the above-mentioned exposed thermosetting resin composition layer (resin layer). Manufacturing method of developing processing step of developing processing. After the development, it is preferable that the exposed resin layer can be further hardened by heating at 50 to 500 ° C (more preferably 150 to 400 ° C). In addition, as described above, when using a thermosetting resin composition imparted with photosensitivity, the composition can be hardened by exposure in advance, and then desired processing can be performed as needed (for example, the following lamination), and then heating can be performed. Let it harden further.

The manufacturing method of the laminated body of this invention includes the manufacturing method of the cured film of this invention. According to the manufacturing method of the laminated body of the present invention, according to the above-mentioned method for manufacturing a cured film, after the cured film is formed, the layer-forming step and the heating step of the thermosetting resin composition are sequentially performed again, or when photosensitivity is imparted, again It is preferable to sequentially perform the layer formation step, the exposure step, and the development processing step (the heating step is performed if necessary). In particular, it is preferable that the above steps are performed 2 to 5 times in order (that is, 3 to 6 times in total). By laminating the cured film in this manner, a laminated body can be obtained. In the present invention, a metal layer is particularly preferably provided at a portion where a hardened film is provided. These details will be described below.

<< Layer Forming Step >> A manufacturing method of a preferred embodiment of the present invention includes a layer forming step in which a thermosetting resin composition is applied to a substrate to form a layer. The type of the substrate can be appropriately set depending on the application, but is not particularly limited, and examples thereof include semiconductor manufacturing substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, and vapor-deposited films , Magnetic film, reflective film, metal substrates such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, electrode plate for plasma display panel (PDP), etc. In the present invention, a semiconductor manufacturing substrate is particularly preferred, and a silicon substrate is more preferred. When a thermosetting resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer becomes a substrate. As a method of applying a thermosetting resin composition to a substrate, coating is preferred. Specifically, as a method of application, a dip coating method, an air knife coating method, a curtain coating method, a 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. 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 inkjet method are more preferred. By adjusting the appropriate solid content concentration or coating conditions according to the method, a resin layer having a desired thickness can be obtained. In addition, the coating method can be appropriately selected according to the shape of the substrate. As long as it is a circular substrate such as a wafer, a spin coating method, a spray coating method, an inkjet method, or the like is preferred, and as long as it is a rectangular substrate, slit coating A method, a spray method, an inkjet method, or the like is preferable. In the case of the spin coating method, it can be applied at a rotation speed of 500 to 2000 rpm for about 10 seconds to 1 minute.

<< Drying Step> In the manufacturing method of the present invention, after the thermosetting resin composition layer is formed, the layer forming step may include a step of drying to remove a solvent. The preferred drying temperature is 50 to 150 ° C, more preferably 70 to 130 ° C, and more preferably 90 to 110 ° C. The drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.

<< Exposure Step >> The production method of the present invention may include an exposure step in which the thermosetting resin composition layer is exposed. The exposure amount is not particularly limited as long as the thermosetting resin composition can be hardened. For example, it is preferable to irradiate 100 to 10,000 mJ / cm ² in terms of exposure energy conversion at a wavelength of 365 nm, and more preferably to irradiate 200 to 8000 mJ / cm ² good. The exposure wavelength can be appropriately set within a range of 190 to 1000 nm, and 240 to 550 nm is more preferable. Regarding the exposure wavelength, if it is described in terms of the relationship with the light source, (1) semiconductor lasers (wavelengths 830nm, 532nm, 488nm, 405nm etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g Ray (wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), wide (3 wavelengths of g, h, and i-rays), (4) excimer laser, KrF excimer laser (wavelength 248nm) , ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet light; EUV (wavelength 13.6nm), (6) electron beam, etc. Regarding the thermosetting resin composition of the present invention, exposure by a high-pressure mercury lamp is particularly preferable, and exposure by an i-ray is preferable. Thereby, particularly high exposure sensitivity can be obtained.

<<< Developing process step> The manufacturing method of this invention may include a developing process step, and develops the exposed thermosetting resin composition layer. By performing development, when the negative type is used, the unexposed part (non-exposed part) is removed, and when the positive type is used, the exposed part (exposed part) is removed. The development method is not particularly limited as long as a desired pattern can be formed. For example, a development method such as spin-on immersion, spraying, dipping, or ultrasonic waves can be used. The development is performed using a developing solution. The developer can be used without particular limitation as long as the unexposed portion (non-exposed portion) can be removed. It is preferred that the developing solution contains an organic solvent. In the present invention, it is preferred that the developer contains an organic solvent having a ClogP of -1 to 5, and more preferably contains an organic solvent having a ClogP of 0 to 3. ClogP can be calculated as a calculated value by inputting a structural formula using ChemBioDraw. As the organic solvent, as the esters, for example, ethyl acetate, n-butyl acetate, pentyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, and butyric acid can be suitably cited. Ethyl ester, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (example: methyl alkoxyacetate , Ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate Esters, etc.), 3-alkoxypropanoic acid alkyl esters (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate) Esters, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (example: 2 -Methyl alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate Esters, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.)) Methyl 2-alkoxy-2-methylpropanoate and ethyl 2-alkoxy-2-methylpropanoate (eg, methyl 2-methoxy-2-methylpropionate, 2-ethyl Ethoxy-2-methyl propionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, methyl 2-oxobutanoate, 2 -Ethyl oxobutyrate and the like, and examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and methyl cellosolve acetic acid. Ester, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, and the like, as well as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N- Methyl-2-pyrrolidone and the like, as well as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, and the like, and as fluorenes, dimethylene, etc. Alas. In the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred. An organic solvent of 50% by mass or more of the developer is more preferable, an organic solvent of 70% by mass or more is more preferable, and an organic solvent of 90% by mass or more is more preferable. In addition, 100% by mass of the developing solution may be an organic solvent.

The development time is preferably 10 seconds to 5 minutes. The temperature at the time of development is not particularly limited, and can usually be performed at 20 to 40 ° C. After the treatment with the developer, processing can be performed. Rinse is preferably performed in a solvent different from the developer. For example, it is possible to rinse using a solvent contained in the thermosetting resin composition. The rinse time is preferably 5 seconds to 1 minute.

<< Heating Step> In the manufacturing 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 a polymer precursor is performed. The composition of the present invention may contain a radical polymerizable compound other than the polymer precursor, and in this step, curing of the radical polymerizable compound other than the unreacted polymer precursor may be performed. The heating temperature (highest 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. Regarding heating, it is preferred to perform the heating at a temperature increase rate of 1 to 12 ° C./minute from the temperature at the start of heating, to 2 to 10 ° C./minute, and more preferably to 3 to 10 ° C./minute. By setting the temperature increase rate to 2 ° C / min or more, it is possible to prevent excessive volatilization of the amine while ensuring productivity. By setting the temperature increase rate to 12 ° C / min or less, the residual stress of the cured film can be reduced. 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 step of starting heating to the highest heating temperature. For example, when the thermosetting resin composition is applied to a substrate and dried, the temperature after drying is, for example, from 30 to 200 ° C lower than the boiling point of the solvent contained in the thermosetting resin composition. It is preferable that the temperature is gradually increased. 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. In particular, in the case of forming a multilayer laminate, it is preferable to heat at a heating temperature of 180 to 320 ° C from the viewpoint of the adhesion between layers of the cured film, and it is more preferable to heat it at 180 to 260 ° C. Although the reason for this is uncertain, the reason is considered to be as follows. That is, by setting the temperature to this temperature, the ethynyl groups of the polymer precursors between the layers undergo a cross-linking reaction.

Heating can be performed in stages. As an example, the temperature can be raised from 25 ° C to 180 ° C at 3 ° C / min, and maintained at 180 ° C for 60 minutes, from 180 ° C to 200 ° C at 2 ° C / minute, and held at 200 ° C for 120 minutes. . The heating temperature as the pretreatment step is preferably 100 to 200 ° C, more preferably 110 to 190 ° C, and still more preferably 120 to 185 ° C. In this pre-treatment process, as described in US Specification No. 9159547, it is also preferable to perform the treatment while irradiating ultraviolet rays. The characteristics of the film can be improved by these pre-treatment steps. The pre-treatment step can be performed in a short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pre-treatment may be two or more steps. For example, the pre-treatment step 1 may be performed in a range of 100 to 150 ° C, and then the pre-treatment step 2 may be performed in a 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 / minute.

The heating step is preferably performed in an environment with a low temperature concentration by flowing an inert gas such as nitrogen, helium, and 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> The manufacturing method of the present invention preferably includes a metal layer forming process for forming a metal layer on the surface of the thermosetting resin composition layer after the development process. The metal layer is not particularly limited, and conventional types of metals can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper and aluminum are more preferred, and copper is further preferred. The method for forming the metal layer is not particularly limited, and a conventional method can be applied. For example, the methods described in Japanese Patent Application Laid-Open No. 2007-157879, Japanese Patent Application No. 2001-521288, Japanese Patent Application Laid-Open No. 2004-214501, and Japanese Patent Application Laid-Open No. 2004-101850 can be used. For example, methods such as photolithography, peeling, electrolytic plating, electroless plating, etching, printing, and combinations can be considered. More specifically, a patterning method using a combination of sputtering, photolithography, and etching, and a patterning method using a combination of photolithography and electrolytic plating are mentioned. The thickness of the metal layer is preferably 0.1 to 50 μm at the thickest wall thickness, and more preferably 1 to 10 μm.

<<< Lamination Step> It is preferable that the manufacturing method of the present invention further includes a lamination step. The lamination step includes performing one of the above-mentioned layer formation step, the above-mentioned exposure step, and the above-mentioned development processing step in order when the above-mentioned layer formation step and heating step are sequentially performed again, or when photosensitivity is provided to the thermosetting resin composition. Series of steps. Of course, the lamination step may further include the above-mentioned drying step or heating step. When the lamination step is performed after the lamination step, a surface activation treatment step may be performed after the heating step, the exposure step, or the metal layer formation step. As the surface activation treatment, a plasma treatment is exemplified. The lamination step is preferably performed 2 to 5 times, and more preferably 3 to 5 times. For example, a resin layer such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer having a structure of 3 or more and 7 or less is preferable, and 3 or more and 5 or less is more preferable. That is, in the present invention, in particular, after the metal layer is provided, the layer forming step and the heating step of the thermosetting resin composition are sequentially performed, or when the photocurability is provided to the thermosetting resin composition, the steps are sequentially performed. The step of forming the layer, the step of exposing, and the step of developing (the heating step is performed if necessary) are preferred to cover the metal layer. By alternately laminating the thermosetting resin composition layer (resin) and the metal layer forming process, the thermosetting resin composition layer (resin layer) and the metal layer can be alternately laminated.

The present invention also discloses a semiconductor device including the cured film or the laminated body of the present invention. As a specific example of a semiconductor device using the thermosetting resin composition of the present invention in the formation of an interlayer insulating film for a redistribution layer, refer to the description and drawings of paragraphs 0213 to 0218 of Japanese Patent Application Laid-Open No. 2016-027357. 1 and incorporate them into this manual. [Example]

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, usage amounts, proportions, processing contents, and processing steps shown in the following examples are within the scope 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 (drying at 140 ° C for 12 hours) and 16.33 g (131.58 mmol) of 3-hydroxybenzyl alcohol suspended in 50 mL of N-methylpyrrolidone, And dried by molecular sieves. The suspension was heated at 100 ° C for 3 hours. A few minutes after heating, a clear solution was obtained. 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 while maintaining the temperature at -10 ± 4 ° C, 16.12 g (135.5 mmol) of thionyl chloride was added over 10 minutes. During the addition of thionyl chloride, the viscosity increased. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, the reaction mixture was added dropwise with dissolving 11.08 g (58.7 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone at 20 to 23 ° C over 20 minutes. Solution. Then, 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 again stirred for 30 minutes in 4 liters of water and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C for 3 days. In the polyfluorene imide 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] While removing water in a drying reactor equipped with a stirrer, a capacitor, and a flat-bottom applicator equipped with an internal thermometer, 20.0 g (64.5 mmol) of oxodiphthalic dianhydride was suspended in diethylene glycol di Methyl ether in 140mL. 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, and 10.7 g (135 mmol) of pyridine were further added, and the mixture was stirred at 60 ° C. for 18 hours. Next, the mixture was cooled to -20 ° C, and then 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. Next, the mixture was warmed to room temperature and stirred for 2 hours, and then 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added. Thus, a transparent solution was obtained. Next, a solution obtained by dissolving 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of NMP was added to the obtained transparent liquid by dropwise addition over 1 hour. During the addition of 4,4'-diaminodiphenyl ether, the viscosity was increased. Next, 5.6 g of methanol (17.5 mmol) 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 again stirred for 30 minutes in 4 liters of water and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C for 3 days. In this polyimide precursor, Mw = 23500 and Mn = 8800.

(Synthesis Example 3) [derived from oxophthalic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2-hydroxyethyl methacrylate, and 4,4'- [Synthesis of polyamine imide precursor resin A-3 of diamine diphenyl ether]] While removing water in a drying reactor equipped with a stirrer, a capacitor, and a flat-bottom applicator equipped with an internal thermometer, the 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 further added, and the mixture was stirred at 60 ° C. for 18 hours. Next, the mixture was cooled to -20 ° C, and then 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. Next, the mixture was warmed to room temperature and stirred for 2 hours, and then 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added. Thus, a transparent solution was obtained. Next, a solution obtained by dissolving 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of NMP was added to the obtained transparent liquid by dropwise addition over 1 hour. During the addition of 4,4'-diaminodiphenyl ether, the viscosity was increased. Next, 5.6 g of methanol (17.5 mmol) 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 again stirred for 30 minutes in 4 liters of water and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C for 3 days. In this 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'-oxodibenzoxyl chloride Synthesis of -4] 28.0 g (76.4 mmol) of 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 200 g of N-methylpyrrolidone by stirring. Next, 12.1 g (153 mmol) of pyridine was added, and while maintaining the temperature at -10 to 0 ° C, 20.7 g (70.1 mmol) of 4,4'-oxodibenzophene chloride was added dropwise over 1 hour. Ear) A solution prepared by dissolving in 75 g of N-methylpyrrolidone. After stirring for 30 minutes, 1.00 g (12.7 mmol) of acetamidine 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 again stirred for 30 minutes in 6 liters of water and filtered again. Then, the polybenzoxazole precursor resin was dried at 45 ° C for 3 days under reduced pressure. In this 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. The obtained solution was concentrated at 35 ° C under reduced prices, thereby obtaining a salt of N, N-dicyclohexylmethylamino and maleic acid.

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

<Molecular weight measurement method> The molecular weight (weight average molecular weight, number average molecular weight) of the polymer precursor is defined by gel permeation chromatography (GPC measurement) as a polystyrene conversion value. 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 the column. System). The eluate was measured using THF (tetrahydrofuran).

<Method for determining pKa> << Acidic Compound> About pKa of an acidic compound, 50 mg of an acidic compound is added to 50 mL of water, and a 0.01N sodium hydroxide aqueous solution is used as a titration solution. AT-420 manufactured by KYOTO ELECTRONICS MANUFACTURING CO., LTD. Is used. (Trade name) An automatic potential difference titration device was measured at 25 ° C. The pH at which half of the amount of the sodium hydroxide aqueous solution required to neutralize the acid group was added was taken as the pKa of the acidic compound. <<< Amine compound> About pKa of conjugate acid of amine compound, 50 mg of amine compound was added to 50 mL of water, 0.01N hydrochloric acid was used as a titration solution, and AT-420 (trade name) manufactured by KYOTO ELECTRONICS MANUFACTURING CO., LTD. Was used. The potential difference automatic titration device was measured at 25 ° C. The pH at which half of the amount of hydrochloric acid required to neutralize the amine group was added was taken as pKb. The value subtracted from the value of 14 to pK [b] is taken as the pKa of the amine conjugate acid. << Sulfuric acid compound and the like> Basically, the measurement is performed by the above method, but the pKa of the strong acid, that is, the sulfonic acid, may not be obtained by this method. In these cases, literature values measured in water (Angew. Chem. Int. Ed. 2016, 55, 350-354) are used.

The pKa relationship (A-pKa) between 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 acid compound) / 2 Formula (1a)

<Preparation of thermosetting resin composition> Each component described in the following table was blended, and a filter having a pore width of 0.8 μm was subjected to pressure filtration at a pressure of 3.0 MPa to obtain heat. A 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, and Examples 63 to 69 were added with amine compounds and acidic compounds. Comparative Examples 2, 3, An amine compound or an acidic compound is added to 7, 8.

<Film thickness change> << Film thickness over time> Each thermosetting resin composition described in the following table was applied to a silicon wafer by a spin coating method 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 having a thickness of about 15 μm on the silicon wafer. This value is taken as the film thickness over time. <<< Film thickness over time >> Each thermosetting resin composition described in the following table was placed in a glass container and sealed, and it was left to stand at 25 ° C for 14 days before applying and obtaining a time-lapse front film. At the same thickness, a spin coating method was applied to a silicon wafer 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 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 over time. <<< Film thickness change rate >> The film thickness change rate was calculated by the following formula. Film thickness change rate [%] = | film thickness over time-film thickness over time | / film thickness over time × 100 film thickness change rate A: less than 10% B: more than 10% and less than 15% C: 15 % Or more and less than 20% D: 20% or more

<Film strength> Each thermosetting resin composition described in the following table was applied to a silicon wafer by a spin coating method 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, and a uniform thermosetting resin composition layer having a thickness of about 15 μm was obtained on the silicon wafer. The obtained thermosetting resin composition layer (resin layer) was heated at a temperature rising rate of 10 ° C / min in a nitrogen environment, and after heating to 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 the cured film from the silicon wafer. The peeled cured film was made into a test piece with a width of 3 mm and a sample length of 30 mm using a punch. A tensile tester (Tensilon) was used at a crosshead speed of 300 mm / min along the long side of the film in an environment of 25 ° C and 65% RH (relative humidity) in accordance with JIS-K6251. Was measured. The evaluation was performed five times, and the average value was used for the elongation (break elongation) at the time of film breakage. A: 60% or more B: 55% or more and less than 60% C: 50% or more and less than 55% D: less than 50%

<Adhesiveness> A thermosetting resin composition layer was formed by applying each of the thermosetting resin compositions described in the following table to a copper wafer by a spin coating method. 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, and a uniform thermosetting resin composition layer having a thickness of about 15 μm was obtained on the copper wafer. The obtained thermosetting resin composition layer (resin layer) was heated at a temperature increase rate of 10 ° C / min in a nitrogen environment, and after reaching 250 ° C, it was heated for 3 hours to form a copper wafer. Hardened film. A cross-cut test was performed on this substrate by cutting at 1 mm intervals in accordance with JIS K5600-5-6: 1999, and the adhesion between the cured film and the copper wafer was evaluated. A From the total area of the hardened film of copper wafer glass is less than 2% B From the total area of the hardened film of copper wafer glass is 2% or more and less than 5% C From the total area of the hardened film of copper wafer glass is 5% Above and less than 10% D The total area of the hardened film from copper wafer glass is 10% or more

<Corrosiveness (Cu corrosion)> Each thermosetting resin composition described in the following table was applied to a copper wafer by a spin coating method to form a thermosetting resin composition layer. 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, and a uniform thermosetting resin composition layer having a thickness of about 15 μm was obtained on the copper wafer. The obtained thermosetting resin composition layer was heated at a temperature increase rate of 10 ° C / min in a nitrogen environment, and after reaching 250 ° C, it was heated for 3 hours to form a cured film on the copper wafer. This substrate was put into a constant temperature and humidity layer having a temperature of 85 ° C and a humidity of 85% for 24 hours. The corrosion-prone portions were observed with an optical microscope, and the corrosion-produced areas were measured with respect to the area of the copper wafer on which one side of the cured film was provided. The area is several percent. A: less than 5% B: 5% or more and less than 10% C: 10% or more and less than 20% D: 20% or more

<Analytical properties> The thermal radical resin composition described in the following table contains a photoradical polymerization initiator (photosensitive resin composition) applied to a copper wafer by a spin coating method to form heat. A 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, thereby obtaining a uniform thermosetting resin composition layer having a thickness of about 15 μm on the silicon wafer. The exposure layer (Karl-Suss MA150 [trade name]) was used to expose the thermosetting resin composition layer through a mask having a pattern of lines and spaces (step: 5 to 20 μm). 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 with cyclopentanone for 75 seconds, and spin-on immersion development was performed. The line width of the developed part was evaluated on the following criteria. When the exposed width of the developed base substrate is within ± 10% of the mask size, it is judged that the line width has been analyzed, and it means that the analyzed line width is approximately smaller than that of the light-irradiated portion and the light-non-irradiated portion. The greater the solubility process of the developer, the better the results. A The analyzed line width is 5 μm or more and less than 10 μm B The analyzed line width is 10 μm or more and less than 15 μm C The analyzed line width is 15 μm or more, or no image appears

<Glass Transition Temperature (Tg)> After each thermosetting resin composition is passed through a filter having a pore width of 0.8 μm and pressure-filtered at a pressure of 0.3 MPa, it is spin-coated on a silicon wafer . The silicon wafer to which the thermosetting resin composition was applied was dried at 100 ° C. for 5 minutes on a hot plate to form a thermosetting resin composition layer with a uniform thickness of 10 μm on the silicon wafer. A stepper (Nikon NSR 2005 i9C) was used to fully expose the thermosetting resin composition layer on the silicon wafer at an exposure energy of 400 mJ / cm ² to obtain a resin layer. However, when a thermosetting resin composition containing no photoradical polymerization initiator was used, no exposure was performed. After heating the resin layer at 200 ° C. for 3 hours, the resin layer was immersed in a hydrofluoric acid aqueous solution to peel the resin layer from the silicon wafer. The Tg of the peeled resin layer was measured using a viscoelasticity measuring device Rhosol-E4000 (manufactured by UBM Co Ltd). Specifically, the Tg of the resin layer was measured as a temperature at which the loss tangent (tan δ) measured using a viscoelasticity measuring device under a constant temperature rising condition became maximum. The temperature of the resin layer was increased from 0 ° C. to 350 ° C. at a temperature increase rate of 5 ° C., and Tg was measured with a strain angle of 0.1 ° being applied to the resin layer at a cycle of 100 Hz. A: 270 ° C or more B: 260 ° C or more and less than 270 ° C C: 250 ° C or more and less than 260 ° C D: 240 ° C or more and less than 250 ° C E: 230 ° C or more and less than 240 ° C F: 220 ° C or more and less than 230 ° C G: less than 220 ° C

[Table 1] The unit of the "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". It is the same after Table 2. [Table 2]

[table 3]

[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 amine compound listed in the table is used

(C) Acidic compounds

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

(E) Photo-radical polymerization initiator (both 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) Radical polymerizable compound (both are trade names) SR-209: SR-209 (manufactured by Sartomer Company, Inc.) SR-231: SR-231 (manufactured by Sartomer Company, Inc.) SR-239: SR- 239 (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 improver H-1: The following compound H-2: The following compound H-3: The following compound

[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 compounds J-2: The following compounds J-3: The following compounds

[Chemical Formula 36]

(K) Organic compound Orgatix TC-100 containing Group 4 elements, titanium diisopropoxybis (acetamidine) acetone manufactured by Matsumoto Fine Chemical Co. Ltd. [Chemical Formula 37]

Orgatix TC-401, titanium tetraacetamidine acetone manufactured by Matsumoto Fine Chemical Co. Ltd. [Chemical Formula 38]

Orgatix TC-710, titanium diisopropoxybis (ethyl acetate) made by Matsumoto Fine Chemical Co. Ltd. [Chemical Formula 39]

Orgatix TC-201, titanium di-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.

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

Bis (cyclopentadienyl) titanium dichloride [Chemical Formula 41]

Bis (cyclopentadienyl) dimethyl titanium [Chemical Formula 42]

Bis (cyclopentadienyl) zirconium dichloride [Chemical Formula 43]

Bis (cyclopentadienyl) phosphonium dichloride [Chemical Formula 44]

IRGACURE 784 [Chemical Formula 45]

It is clear from the results in the above table that it is known that using an amine compound and an acidic compound, the pKa of the conjugate acid of the amine compound and the pKa of the acid compound is one-half of the sum (A-pKa) of the heat in the range of 3.5 to 7.1 In the curable resin composition, the change in film thickness is excellent, and the strength of the cured film is high (Examples 1 to 85). In addition, the samples in the examples all satisfied the requirements for use with respect to the adhesion properties, the corrosion resistance of copper, and the analytical properties when they were photosensitive. On the other hand, those who do not contain an amine compound or an acidic compound (Comparative Examples 1 to 3, 6 to 8) and A-pKa are less than 3.5 (Comparative Examples 4, 9) and greater than 7.1 (Comparative Examples 5, 10). ), The suppression of film thickness change or the film strength is poor.

<Example 100> The thermosetting resin composition of Example 48 was used to coat 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 having a thickness of 15 μm on the silicon wafer. Using a stepper (NSR 2005 i9C [trade name], manufactured by NIKON CORPORATION), a thermosetting resin composition layer on a silicon wafer was exposed at a exposure energy of 500 mJ / cm ² through a mask having a hole having a diameter of 10 μm. exposure. This resin layer was developed with cyclopentanone for 60 seconds, thereby forming holes having a diameter of 10 μm. Next, the temperature was raised at a temperature increase rate of 10 ° C / min in a nitrogen environment, and after reaching 250 ° C, it was heated for 3 hours to obtain a cured film (final cured film). After cooling to room temperature, a copper foil layer (metal layer) having a thickness of 2 μm was formed on the surface of the cured film by a vapor deposition method so as to cover the above-mentioned holes, and the excess portion of the copper foil layer was removed by dry etching. . Furthermore, using the same type of thermosetting resin composition on the surface of the metal layer and the cured film, and filtering the thermosetting resin composition again in the same manner as described above, and heating the patterned film for 3 hours, As shown in FIG. 1, a laminated body composed of a cured film / metal layer / cured film was produced. It was found that this cured film is excellent in insulation and can be suitably used as an interlayer insulating film for a redistribution layer. In FIG. 1, 201 to 204 represent hardened films, 301 to 303 represent metal layers, 401 to 403 represent grooves formed between the hardened film and the hardened film, and 500 represents a laminated body. Furthermore, as a result of manufacturing a semiconductor device using this interlayer insulating film for a redistribution layer, it was confirmed that the operation was normal.

201 ～ 204‧‧‧hardened film

301 ～ 303‧‧‧metal layer

401 ～ 403‧‧‧slot

500‧‧‧layer

FIG. 1 shows a schematic view of a laminated body manufactured in this embodiment.

Claims (28)

A thermosetting resin composition comprising: a polymer precursor selected from the group consisting of 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 conjugate 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 conjugate acid of the amine compound + pKa of the acid compound) /2≤7.1 (the formula 1). The thermosetting resin composition according to item 1 of the patent application range, wherein the amount of the acid group of the acidic compound is 0.9 to 3.0 equivalents based on 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 to 1,000. The thermosetting resin composition according to 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 connected to each other to form a ring. However, not all of R ^B1 to R ^B3 are hydrogen atoms. The thermosetting resin composition according to item 4 of the scope of the patent application, wherein R ^B1 and R ^{B2 of} the formula (B1) are each independently a linear or branched alkyl group having 1 to 6 carbon atoms and cyclopentane. Or a cyclohexyl group, R ^B3 is 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. The thermosetting resin composition according to claim 1 or claim 2, wherein in the amine compound, the number of the connected nitrogen atom and the carbon atom of the carbon atom having the farthest distance from the nitrogen atom is the number of the carbon atom. 2 to 5. The thermosetting resin composition according to claim 1 or claim 2, wherein the acid compound has a pKa of 2 or less. The thermosetting resin composition according to 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 to 500. The thermosetting resin composition according to item 1 or item 2 of the scope of patent application, wherein the polyimide precursor has a repeating unit represented by formula (1), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹¹ 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 item 12 of the application, 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 item 15 of the patent application scope, 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 in the patent application range, 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 item 1 or 2 of the scope of patent application, which is for forming an interlayer insulating film for a redistribution layer. A cured film formed from the thermosetting resin composition according to any one of the scope of claims 1 to 18 of the scope of patent application. A laminated body having two or more layers of a hardened film as described in item 19 of the scope of patent application. The laminated body according to item 20 of the patent application scope, which has 3 to 7 layers of the cured film. The laminated body according to item 20 of the patent application scope, 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 claims 1 to 18 to a substrate to form a layer; and heating the layer; In the step, the layer of the thermosetting resin composition is heated at a temperature of 50 to 500 ° C. A method for manufacturing a cured film, comprising: a layer forming step of applying the thermosetting resin composition described in any one of claims 1 to 18 to a substrate to form a layer; Steps: exposing the thermosetting resin composition formed into a layer; developing treatment step; performing the development treatment on the exposed thermosetting resin composition; and a heating step, at a temperature of 50 to 500 ° C. The exposed thermosetting resin composition is heated. A method for manufacturing a laminated body, after forming a hardened film according to the method for manufacturing a hardened film described in item 23 or 24 of the scope of patent application, further comprising hardening as described in item 23 or 24 of the scope of patent application The method of manufacturing a film is a step of forming a cured film. A semiconductor device having a cured film as described in claim 19 of the scope of patent application. A method for 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, which comprises selecting a p-imine precursor and a polybenzene so that the pKa of the conjugate acid of the amine compound and the pKa of the acidic compound fall within the range of the following formula 1. The step of mixing the polymer precursor, the amine compound, the acidic compound, and the solvent in the oxazole precursor, 3.5≤ (pKa of the conjugate acid of the amine compound + pKa of the acidic compound) /2≤7.1 (Equation 1).