WO2019013240A1

WO2019013240A1 - Thermosetting resin composition, cured film thereof, layered product, semiconductor device and methods for producing these

Info

Publication number: WO2019013240A1
Application number: PCT/JP2018/026134
Authority: WO
Inventors: 健太吉田; 健志川端; 悠岩井; 渋谷　明規
Original assignee: 富士フイルム株式会社
Priority date: 2017-07-14
Filing date: 2018-07-11
Publication date: 2019-01-17
Also published as: JPWO2019013240A1; KR102327882B1; KR20200016349A; TW201908370A; TWI763883B; JP6889260B2

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, cured film thereof, laminate, semiconductor device, and method for producing them

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

A cyclized and cured resin such as a polyimide resin or a polybenzoxazole resin is applied to various uses because it is excellent in heat resistance, insulation properties, and the like (see, for example, Non-Patent Documents 1 and 2). Although the application is not particularly limited, when the semiconductor device for mounting is taken as an example, utilization as a material of an insulating film or a sealing material can be mentioned. In addition, it is also used as a base film or a cover lay of a flexible substrate.
The above-mentioned polyimide resins and the like generally have low solubility in solvents. Therefore, as an example of applying a polyimide resin or the like on a substrate, it is dissolved in a solvent in the form of a polymer precursor before cyclization reaction, specifically, a polyimide precursor resin or a polybenzoxazole precursor resin, An example of applying to Thereafter, the polymer precursor can be cyclized by heating to form a cured resin layer (cured film).

With regard to the specific combination relating to the composition of the polymer precursor as described above, for example, Patent Document 1 contains an N-aromatic glycine derivative and a polymer precursor, to mention some examination examples. A photosensitive resin composition is disclosed. Patent Document 2 discloses a polyimide precursor containing a polyimide precursor, a thermal base generator composed of a neutral compound which is thermally decomposed by heating at a temperature of 200 ° C. or less to generate a secondary amine, and a solvent. A body resin composition is disclosed.

Unexamined-Japanese-Patent No. 2006-282880 JP 2007-56196 A

As described above, there are several studies on the component composition of the thermosetting resin composition. However, when considering its various applications or new applications, it can not be said that it has been sufficiently studied in relation to the characteristics of the resin composition and the cured film after curing.
An object of the present invention is to provide a novel thermosetting resin composition to enrich the material. In particular, a thermosetting resin composition which is excellent in suppressing the time-dependent fluctuation of the film thickness of the film formed from the thermosetting resin composition and is excellent in the strength when it is a cured film, and the cured film, laminate, semiconductor device , As well as providing methods for their manufacture.

Based on the above problems, as a result of intensive investigations by the present inventor, it was found that the above problems can be solved by adding a predetermined salt to a thermosetting resin composition. Specifically, the above problems have been solved by the following means <1>, preferably <2> to <28>.
<1> A polymer precursor selected from 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, and conjugation of the above amine compound A thermosetting resin composition wherein the pKa of the acid and the pKa of the acidic compound are 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).
The thermosetting resin composition as described in <1> whose quantity of the acidic radical of the said acidic compound is 0.9-3.0 equivalent with respect to the quantity of the amino group of <2> said amine compound.
<3> The thermosetting resin composition according to <1> or <2>, wherein the molecular weight of the amine compound is 120 to 1000.
<4> The thermosetting resin composition according to any one of <1> to <3>, wherein the amine compound is represented by the following formula (B1);

R ^B1 to R ^B3 each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms, and may be linked to each other to form a ring; provided that all of R ^B1 to R ^B3 are hydrogen atoms There is no such thing.
<5> R ^B1 and R ^{B2 in} the above formula (B1) are each independently a linear or branched alkyl group having 1 to 6 carbon atoms, a cyclopentyl group or a cyclohexyl group; R ^B3 is a hydrogen atom, The thermosetting resin composition according to <4>, which is a linear or branched alkyl group having 1 to 6 carbon atoms, a cyclopentyl group, a cyclohexyl group, or a pyridyl group.
<6> Any one of <1> to <5>, wherein the number of atoms connecting the nitrogen atom to the carbon atom is 2 to 5 at the carbon atom farthest from the nitrogen atom among the above amine compounds A thermosetting resin composition as described in 1).
The thermosetting resin composition as described in any one of <1>-<6> whose pKa of the <7> above-mentioned acidic compound is 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 formulas (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.
<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 polyimide precursor has a repeating unit represented by the 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, and 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 including a photo radical polymerization initiator.
The thermosetting resin composition as described in <12> whose <13> above-mentioned radical photopolymerization initiator is an oxime compound.
<14> The thermosetting resin composition according to any one of <1> to <13>, further containing a radically polymerizable compound.
<15> The thermosetting resin composition according to any one of <1> to <14>, further comprising an organic compound containing a Group 4 element.
<16> The thermosetting resin composition according to <15>, wherein the group 4 element is at least one element selected from the group consisting of titanium, zirconium and hafnium.
The thermosetting resin composition as described in <15> or <16> which is an at least 1 sort (s) of element selected from the group which the <17> above-mentioned 4th group element becomes from titanium and a zirconium.
<18> The thermosetting resin composition according to any one of <1> to <17>, which is for forming an interlayer insulating film for rewiring layer.
<19> A cured film formed from the thermosetting resin composition according to any one of <1> to <18>.
The laminated body which has two or more layers of the cured film as described in <20><19>.
<21> The laminate according to <20>, having 3 to 7 layers of the cured film.
The laminated body as described in <20> or <21> which has a metal layer between <22> above-mentioned cured films.
A layer forming step of applying a thermosetting resin composition according to any one of <23><1> to <18> to a substrate to form a layer, and the thermosetting resin composition obtained by forming the layer on the layer 50 And C. a heating step of heating at a temperature of 500.degree. C.
A layer forming step of applying the thermosetting resin composition according to any one of <24><1> to <18> to a substrate to form a layer, and exposing the thermosetting resin composition formed into the layer. An exposure step, a development step of developing the exposed thermosetting resin composition, and a heating step of heating the exposed thermosetting resin composition at a temperature of 50 to 500 ° C. The manufacturing method of the cured film which has.
After a cured film is formed according to the method for producing a cured film described in <25><23> or <24>, a cured film is further formed according to the method for producing a cured film described in <23> or <24> Method of producing a laminate comprising the steps of
The semiconductor device which has a cured film as described in <26><19>, or the laminated body as described in any one of <20>-<22>.
The manufacturing method of the semiconductor device which processes the cured film as described in <27><19>, or the laminated body as described in any one of <20>-<22> as a semiconductor device.
<28> A polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, an amine compound, an acidic compound, and a solvent, the pKa of the conjugate acid of the amine compound and the pKa of the acidic compound are represented by the following formula 1 A method of producing a thermosetting resin composition comprising mixing to be in the range of
3.5 ≦ (pKa of conjugate acid of amine compound + pKa of acidic compound) /2≦7.1 (Equation 1).

According to the present invention, it has become possible to provide a novel thermosetting resin composition and achieve enrichment of materials. In particular, a thermosetting resin composition which is excellent in suppressing the time-dependent fluctuation of the film thickness of the film formed from the thermosetting resin composition and is excellent in the strength when it is made a cured film, and its cured film, laminate, semiconductor device , As well as providing methods for their production.

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

Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used in the meaning including the numerical values described before and after it as the lower limit value and the upper limit value.

The descriptions of components in the present invention described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.
In the notation of groups (atomic groups) in the present specification, the notations not describing substitution and non-substitution include those having no substituent and those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, “exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Further, as light used for exposure, generally, a bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), actinic rays such as X-rays, electron beams and the like can be mentioned.
In the present specification, "(meth) acrylate" represents both or either of "acrylate" and "methacrylate", and "(meth) acrylic" is both "acrylic" and "methacrylic" or "(Meth) acryloyl" represents either or both of "acryloyl" and "methacryloyl".
In the present specification, the term "process" is included in the term if the intended function of the process is achieved, even if it can not be clearly distinguished from other processes, not only the independent process. .
In the present specification, the solid content is a mass percentage of the other components excluding the solvent with respect to the total mass of the composition. Moreover, solid content concentration means the density | concentration in 25 degreeC unless it mentions specially.
In the present specification, weight average molecular weight (Mw) and number average molecular weight (Mn) are defined as polystyrene equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise stated. In the present specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corp.) and guard columns HZ-L, TSKgel Super HZM-M, TSKgel as columns It can be determined by using Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by Tosoh Corp.). Eluents are to be determined using THF (tetrahydrofuran) unless otherwise stated. Moreover, a detection shall use the wavelength 254 nm detector of a UV ray (ultraviolet light), unless it mentions specially.
Unless otherwise stated, the physical property values in the present invention are set to a temperature of 25 ° C. and a 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" or "the resin composition of the present invention") is selected from a polyimide precursor and a polybenzoxazole precursor A thermosetting resin composition comprising a polymer precursor, a salt containing a cation derived from an amine compound and an anion derived from an acidic compound, and a pKa of a conjugate acid of the above amine compound and a pKa of the acidic compound And are in the range of Formula 1 below.
3.5 ≦ (pKa of conjugate acid of amine compound + pKa of acidic compound) /2≦7.1 (equation 1)
With such a configuration, it is possible to provide a thermosetting resin composition which has a small change in film thickness with time of a film formed from a thermosetting resin composition and is excellent in strength when it is made a cured film. That is, as a result of the present inventor's investigation, the acid compound mainly contributes to the suppression of the temporal variation of the film thickness of the film formed from the composition, and the amine compound can contribute to the film strength after curing. confirmed. However, there is an unexpected point in the formulation balance, and it has been found that the above effect can be achieved by defining the formulation balance based on pKa of both compounds through various experimental confirmation and analysis. .

<Polymer precursor>
The thermosetting resin composition of the present invention comprises a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor. As a polymer precursor, a polyimide precursor is more preferable, and it is further more preferable that it is a polyimide precursor containing the repeating unit represented by Formula (1) mentioned later.

<< Polyimide Precursor >>
The polyimide precursor preferably contains a repeating unit represented by the following formula (1).

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

A ¹ and A ² in the formula (1) are each independently an oxygen atom or NH, preferably an oxygen atom.
R ¹¹¹ in the 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 consisting of a combination thereof, having 2 to 6 carbon atoms 20 linear aliphatic group, branched aliphatic group having 3 to 20 carbon atoms, cyclic aliphatic group having 3 to 20 carbon atoms, aromatic group having 6 to 20 carbon atoms, or a combination thereof Group is preferable, and an aromatic group having 6 to 20 carbon atoms is more preferable.

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

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

As the diamine, specifically, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1 2,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4- Aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophorone diamine; meta and para phenylene diamine, diaminotoluene, 4,4'- and 3 , 3'-Diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl agent 4,4'- and 3,3'-diaminodiphenylmethane, 4,4'- and 3,3'-diaminodiphenylsulfone, 4,4'- and 3,3'-diaminodiphenyl sulfide, 4,4 ' -And 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 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-Bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 4,4'-diamino Paraterphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (2-Aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis (4-aminophenyl) anthracene, 3,3′-dimethyl-4,4′-diaminodiphenyl Sulfone, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene 1,3-bis (4-aminophenyl) benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'- Diaminooctafluorobiphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9,9-bis (4 -Aminophenyl) -10-hydroanthracene, 3,3 ', 4,4'-tetraaminobiphenyl, 3,3', 4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diamino Anthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis (4-aminophenyl) fluorene, 4 4'-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5 -Dimethyl-paraphenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-paraphenylenediamine, 2,4,6-trimethyl-metaphenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, 2 , 7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-aminophenyl) ethane, diaminobenzanilide, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 3-Bis (4-aminophenyl) hexafluoropropane, 1,4-bis (4-amino) Phenyl) octafluorobutane, 1,5-bis (4-aminophenyl) decafluoropentane, 1,7-bis (4-aminophenyl) tetradecafluoroheptane, 2,2-bis [4- (3-aminophenoxy] ) Phenyl] hexafluoropropane, 2,2-bis [4- (2-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] hexa Fluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-bis (trifluoromethyl) phenyl] hexafluoropropane, parabis (4-amino-2-trifluoromethylphenoxy) benzene, 4 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4 -Amino-3-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenyl sulfone, 4,4'-bis (3-amino-5-trifluoromethylphenoxy) ) Diphenylsulfone, 2,2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl] hexafluoropropane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminobiphenyl From 4,4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,2 ', 5,5', 6,6'-hexafluorotrizine and 4,4'-diaminoquaterphenyl At least one selected diamine is mentioned.

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

Moreover, the diamine which has an at least 2 or more alkylene glycol unit in a principal chain is also mentioned as a preferable example. Preferred are diamines containing two or more ethylene glycol chains and / or propylene glycol chains together in one molecule, more preferably diamines not containing an aromatic ring. As a specific example, 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 (trade names, manufactured by HUNTSMAN), 1- (2- (2- (2 (2) -Aminopropoxy) ethoxy) propoxy) propan-2-amine, 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propan-2-amine and the like, but it is limited thereto I will not.
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, The structure of Jeffamine.RTM. EDR-176 is shown below.

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

R ¹¹¹ is preferably represented by —Ar ⁰ — L — Ar ⁰ — from the viewpoint of the flexibility of the resulting cured film. However, Ar ⁰ is each independently an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 10 carbon atoms), and L is substituted with a fluorine atom Aliphatic hydrocarbon group having 1 to 10 carbon atoms, -O-, -CO-, -S-, -SO ₂ -or -NHCO-, and a group consisting of a combination of two or more of the above is there. 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- More preferable. The aliphatic hydrocarbon group here is preferably an alkylene group. The aromatic hydrocarbon group (preferably a phenylene group) constituting Ar ⁰ may have an arbitrary substituent T (for example, a hydroxy group) within the range where the effects of the present invention are exhibited.

R ¹¹¹ is a divalent organic group represented by the following formula (51) or formula (61) from the viewpoint of i-ray transmittance in the case of imparting photosensitivity to a thermosetting resin composition preferable. In particular, the divalent organic group represented by the formula (61) is more preferable from the viewpoint of i ray transmittance and availability.
Formula (51)

In formula (51), R ⁵⁰ to R ⁵⁷ each independently represent a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ⁵⁰ to R ⁵⁷ represents a fluorine atom, a methyl group or a fluoromethyl group, It is a difluoromethyl group or a trifluoromethyl group.
As the monovalent organic group of R ⁵⁰ to R ^57, a C 1 to C 10 (preferably C 1 to 6) unsubstituted alkyl group, a C 1 to 10 (preferably C 1 to 6) fluorine group And alkylated alkyl groups.
Formula (61)

In formula (61), R ⁵⁸ and R ⁵⁹ each independently represent a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group.
As a diamine compound giving the structure of the formula (51) or (61), dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2 ' Examples include '-bis (fluoro) -4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like. One of these may be used, or two or more of these may be used in combination.

R ¹¹⁵ in Formula (1) represents a tetravalent organic group. As a tetravalent organic group, the tetravalent organic group containing an aromatic ring is preferable, and the group represented by following formula (5) or Formula (6) is more preferable. The benzene ring in the formula may have a substituent T (for example, a hydroxy group).
Formula (5)

In formula (5), R ¹¹² is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO. _2- , -NHCO-, and a group selected from a combination thereof, and is preferably a single bond, an alkylene group of 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO- It is more preferable that it is a group selected from -S- and -SO _2- , and -CH _2- , -C (CF ₃ ) _2- , -C (CH ₃ ) _2- , -O-, -CO Further preferred is a divalent group selected from the group consisting of-, -S- and -SO _2- .

Formula (6)

The tetravalent organic group which ^R115 in Formula (1) represents specifically, the tetracarboxylic acid residue etc. which remain after removing an acid dianhydride group from tetracarboxylic acid dianhydride are mentioned. The tetracarboxylic acid dianhydride may be used alone or in combination of two or more. The tetracarboxylic acid dianhydride is preferably a compound represented by the following formula (O).
Formula (O)

In formula (O), R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ has the same meaning as ^{R 115} in formula (1). Specifically, the tetravalent organic group of Formula (5) or (6) is mentioned.

Specific examples of tetracarboxylic acid dianhydride include pyromellitic acid, pyromellitic acid dianhydride (PMDA), 3,3 ′, 4,4′-biphenyltetracarboxylic acid dianhydride, 3,3 ′, 4 4,4'-diphenyl sulfide tetracarboxylic acid dianhydride, 3,3 ', 4,4'-diphenyl sulfone tetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3 ', 4,4'-Diphenylmethanetetracarboxylic dianhydride, 2,2', 3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3 ', 4'-biphenyltetracarboxylic acid Dianhydride, 2,3,3 ', 4'-benzophenonetetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride 1,4,5,7-naphthalenetetracarboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) Propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydride, 1,4,5,6-Naphthalenetetracarboxylic dianhydride, 2,2 ', 3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrene tetracarboxylic acid dianhydride, 1, -Bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride And at least one selected from these alkyl derivatives having 1 to 6 carbon atoms and / or alkoxy derivatives having 1 to 6 carbon atoms.

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

R ¹¹³ and R ¹¹⁴ in the formula (1) each independently represent a hydrogen atom or a monovalent organic group. In the case of imparting photosensitivity to a thermosetting resin composition to obtain a photosensitive resin composition, etc., it is preferable that at least one of R ¹¹³ and R ¹¹⁴ contains a radically polymerizable group, and both of them be radically polymerizable More preferably, The radically polymerizable group is a group capable of undergoing a crosslinking reaction by the action of a radical, and a preferred example is a group having an ethylenically unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth) acryloyl group, and a group represented by the following formula (III).

In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, with a methyl group being more preferred.
In 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, 1 carbon atom Preferred is 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3. The repeat number is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3. Here, the (poly) oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.
Examples of suitable R ²⁰¹ are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butanediyl group, 1,3-butanediyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group And —CH ₂ CH (OH) CH ₂ —, and ethylene, propylene, trimethylene and —CH ₂ CH (OH) CH ₂ — are more preferable.
Particularly preferably, R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethylene group.

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

From the viewpoint of solubility in organic solvents, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and more preferably an alkyl group substituted with an aromatic group.
The carbon number of the alkyl group is preferably 1 to 30 (in the case of cyclic, 3 or more). The alkyl group may be linear, branched or cyclic. Examples of linear or branched alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl and octadecyl groups. And isopropyl, isobutyl, sec-butyl, t-butyl, 1-ethylpentyl and 2-ethylhexyl groups. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic alkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group. As the polycyclic cyclic alkyl group, for example, an adamantyl group, norbornyl group, bornyl group, camphenyl group, decahydronaphthyl group, tricyclodecanyl group, tetracyclodecanyl group, camphoroyl group, dicyclohexyl group and pinenyl group Can be mentioned. Among them, a cyclohexyl group is most preferable in terms of coexistence with high sensitivity. Moreover, as an alkyl group substituted by the aromatic group, the linear alkyl group substituted by the aromatic group mentioned later is preferable.
Specific examples of the aromatic group include substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene Ring, naphthacene ring, chrysene ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring , Indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolizine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phena Tororin ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxathiin ring, a phenothiazine ring or a phenazine ring. The benzene ring is most preferred.

Moreover, it is also preferable that a polyimide precursor has a fluorine atom in a structural unit. 10 mass% or more is preferable, and, as for the fluorine atom content in a polyimide precursor, 20 mass% or less is more preferable. There is no particular upper limit, but 50% by mass or less is practical.

Further, for the purpose of improving the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with the repeating unit represented by the formula (1). Specifically, as the diamine component, bis (3-aminopropyl) tetramethyldisiloxane, bis (paraaminophenyl) octamethylpentasiloxane and the like can be mentioned.

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

In formula (1-A), A ¹¹ and A ¹² each 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 And a hydrogen atom or a monovalent organic group is represented, and at least one of R ¹¹³ and R ¹¹⁴ is a group containing a radical polymerizable group, preferably a radical polymerizable group.

A ¹¹ , A ¹² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ each independently have the same meaning as A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (1), and the preferred ranges are also the same. is there.
R ¹¹² has the same meaning as R ¹¹² in Formula (5), and the preferred range is also the same.

In the polyimide precursor, the repeating structural unit represented by formula (1) may be of one type, or of two or more types. Moreover, the structural isomer of the repeating unit represented by Formula (1) may be included. The polyimide precursor may also contain other types of repeating structural units in addition to the repeating unit of the above-mentioned formula (1).

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

The weight average molecular weight (Mw) of the polyimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and still more preferably 10,000 to 50,000. Also, the number average molecular weight (Mn) is preferably 800 to 250000, more preferably 2000 to 50000, and still more preferably 4000 to 25000.
The degree of dispersion of the polyimide precursor is preferably 1.5 to 3.5, and more preferably 2 to 3.

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

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

<< Polybenzoxazole Precursor >>
It is preferable that the polybenzoxazole precursor used by this invention contains the repeating unit represented by following formula (2).

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

In Formula (2), R ¹²¹ represents a divalent organic group. The divalent organic group is preferably a group containing an aliphatic group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 and particularly preferably 1 to 6) and an aromatic group (having 6 to 22 carbon atoms, The group containing at least one of 6 to 14 is more preferable, and 6 to 12 is particularly preferable. As a group containing the aromatic group which comprises ^R121 , the example of ^R111 of the said Formula (1) is mentioned. As said aliphatic group, a linear aliphatic group is preferable. R ¹²¹ is preferably derived from 4,4′-oxydibenzoyl chloride.
In Formula (2), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same meaning as R ¹¹⁵ in the formula (1), and preferred ranges are also the same. R ¹²² is preferably derived from 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group, and have the same meaning as R ¹¹³ and R ¹¹⁴ in the above formula (1), and preferred ranges are also the same.

The polybenzoxazole precursor may contain other types of repeating structural units in addition to the repeating unit of the above-mentioned formula (2).
The precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating structural unit, from the viewpoint of suppressing the occurrence of warpage of the cured film accompanying ring closure.

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

In the formula (SL), preferable Z includes those in which R ^5s and R ^6s in the b structure are a phenyl group. The molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. Molecular weight can be determined by commonly used gel permeation chromatography. By making the said molecular weight into the said range, the elastic modulus after dehydration ring-closing of a polybenzoxazole precursor can be reduced, and the effect which can control curvature, and the effect of improving solubility can be compatible.

When the precursor contains a diamine residue represented by the formula (SL) as another type of repeating structural unit, it further contains tetracarboxylic acid dianhydride to acid dianhydride group in terms of improving alkali solubility. It is preferable to include a tetracarboxylic acid residue remaining after removal as a repeating structural unit. Examples of such tetracarboxylic acid residues include the examples of R ¹¹⁵ in the formula (1).

The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and still more preferably 10,000 to 50,000. Also, the number average molecular weight (Mn) is preferably 800 to 250000, more preferably 2000 to 50000, and still more preferably 4000 to 25000.
The degree of dispersion of the polybenzoxazole precursor is preferably 1.5 to 3.5, and more preferably 2 to 3.

The content of the polymer precursor in the thermosetting resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total solid content of the composition, and 40% by mass. % Is more preferably 50% by mass or more, still more preferably 60% by mass or more, and still more preferably 70% by mass or more. In addition, the content of the polymer precursor in the thermosetting resin composition of the present invention is preferably 99.5% by mass or less and 99% by mass or less based on the total solid content of the composition. The content is more preferably 98% by mass or less, still more preferably 95% by mass or less, still more preferably 93% by mass or less, and still more preferably 90% by mass or less.
The thermosetting resin composition of the present invention may contain only one type of polymer precursor, or may contain two or more types. When it contains 2 or more types, it is preferable that a total amount becomes said range.

<A salt containing a cation derived from an amine compound and an anion derived from an acidic compound>
The composition of the present invention comprises a salt comprising a cation derived from an amine compound and an anion derived from an acidic compound. In the present invention, the compounding ratio of these compounds in the salt containing the cation derived from the amine compound and the anion derived from the acidic compound can be appropriately set according to the application and the required characteristics, but the amount of amino group of the amine compound In contrast, the range in which the amount of the acid group of the acidic compound is 0.5 equivalent or more is preferable, the range of 0.7 equivalent or more is more preferable, and the range of 0.9 equivalent or more is particularly preferable. As the upper limit value, a range in which the amount of acid groups of the acidic compound is 5.0 equivalents or less is preferable, a range of 4.0 equivalents or less is more preferable, and a range of 3.0 equivalents or less is particularly preferable. By setting the amount of the acid group to 0.5 equivalent or more, the film thickness fluctuation with time can be more effectively suppressed, and by being 3.0 equivalents or less, the imidization at the time of heat curing is promoted. Film strength tends to be further improved.

In the thermosetting resin composition of the present invention, the specific value (A-pKa) defined by the pKa of the conjugate acid of the amine compound contained therein and the pKa of the acidic compound satisfy the range of Formula 1 below.
A-pKa = (pKa of conjugate acid of amine compound + pKa of acidic compound) / 2 Formula (1a)
3.5 ≦ A−pKa ≦ 7.1 (Equation 1)
The lower limit value of A-pKa is preferably 3.8 or more, 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 particularly contributes to suppressing the change in film thickness with time by setting the value to the upper limit value or less. On the other hand, the strength of a cured film increases by setting it as the said lower limit or more.
The absolute value of the difference between the molecular weight of the amine compound and the molecular weight of the acidic compound is preferably 30 or more, more preferably 50 or more, more preferably 70 or more, and particularly preferably 80 or more. . The upper limit value is not particularly limited, but is practically 500 or less. By setting the absolute value of the difference to 30 or more, the ratio of the amine compound to the acid compound remaining in the film at the time of heat curing increases, and the curing reaction is more effectively promoted.
In the salt containing a cation derived from an amine compound and an anion derived from an acidic compound, the total amount added does not have to satisfy the above conditions, and at least one of them is within a range where the effects of the present invention are exhibited. It is sufficient if the above conditions are satisfied. Specifically, it is preferable that 70% by mass or more of the salt containing the cation derived from the amine compound contained in the thermosetting resin composition and the anion derived from the acidic compound satisfy the above conditions, and 80% by mass The above is more preferable, and 90% by mass or more is particularly preferable. The upper limit is 100% by mass or less.

The content of the salt containing the cation derived from the amine compound and the anion derived from the acidic compound in the thermosetting resin composition of the present invention is 0.1 parts by mass or more with respect to 100 parts by mass of the polymer precursor It is preferably 0.2 parts by mass or more, and more preferably 0.4 parts by mass or more. The content of the salt is also preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and still more preferably 2 parts by mass or less with respect to 100 parts by mass of the polymer precursor. It is more preferably 1.8 parts by mass or less, still more preferably 1.5 parts by mass or less.
Also, apart from the above-mentioned salts, in the thermosetting resin composition, a part of the acidic compound and the amine compound does not form a salt and excludes the presence as an acidic compound or as an amine compound. It is not something to do. In addition to the above salts, a part of the acidic compound may form a salt with a quaternary ammonium cation of a curing accelerator described later.

<< Amine compound >>
The amine compound in the present invention means a compound having an amine site (-N <) in the molecule (however, it can not be ammonia (NH ₃ )). Specifically, the amine compound in the present invention is preferably a compound 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 combine with 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, or 1 to 20 carbon atoms More preferably, it is a heteroaryl group having 2 to 10 carbon atoms, particularly preferably 3 to 6 carbon atoms. As a hetero atom contained in heteroaryl group, an oxygen atom, a nitrogen atom, and a sulfur atom are mentioned. The heteroaryl group is preferably a 5- or 6-membered ring group, and examples thereof include pyrrolyl group, pyridyl group, pyrazolyl group, imidazolyl group, benzimidazolyl group, triazolyl group, thiazolyl group, oxazolyl group and the like. The heteroaryl group is preferably substituted at the carbon atom position with nitrogen. When R ^B1 to R ^B3 are organic groups having 1 to 20 carbon atoms, they may have the following substituent T within the range where the effects of the present invention are exhibited.
As the optional substituent T, a linear or branched alkyl group (having 1 to 24 carbon atoms is preferable, 1 to 12 is more preferable, and 1 to 6 is particularly preferable), and a cycloalkyl group (3 to 24 carbon atoms is preferable) , 3 to 12 is more preferable, and 3 to 6 is particularly preferable, straight-chain or branched alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 and particularly preferably 2 to 6), cycloalkenyl Group (preferably 3 to 24 carbon atoms, more preferably 3 to 12 carbon atoms, particularly preferably 3 to 6 carbon atoms), hydroxy group, hydroxyalkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, 1 to 6 The number of hydroxy groups is preferably 1 to 6, and more preferably 1 to 3. The alkyl group may be linear or branched, linear or cyclic), hydroxyalkenyl group (carbon The number 2 to 24 is preferable, 2 to 12 is more preferable, and 2 to 6 is particularly preferable. The number of hydroxy groups is preferably 1 to 6 and more preferably 1 to 3. The alkenyl group may be linear or branched, and a chain Or cyclic, amino group (preferably having 0 to 24 carbon atoms, more preferably 0 to 12 and particularly preferably 0 to 6), aminoalkyl group (preferably having 1 to 24 carbon atoms, and 1 to 12 carbon atoms) The number of amino groups is preferably 1 to 6, and more preferably 1 to 3. The alkyl group may be linear or branched, linear or cyclic), amino alkenyl group (carbon The number 2 to 24 is preferable, 2 to 12 is more preferable, and 2 to 6 is particularly preferable. The number of amino groups is preferably 1 to 6 and more preferably 1 to 3. The alkenyl group may be linear or branched, and a chain Even ring , A thiol group or a thiol alkyl group (preferably having a carbon number of 1 to 24, more preferably 1 to 12, particularly preferably 1 to 6; the number of thiol groups is preferably 1 to 6, more preferably 1 to 3). The alkyl group may be linear or branched, and may be linear or cyclic, or a thiol alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 6 carbon atoms; 1 to 6 is preferable, 1 to 3 is more preferable, and the alkenyl group may be linear, branched, linear or cyclic), carboxyl group, carboxyalkyl group (preferably having a carbon number of 1 to 24, and 1 to 12) More preferably, 1 to 6 is particularly preferable; the number of carboxyl groups is preferably 1 to 6, more preferably 1 to 3. The alkyl group may be linear or branched, and may be linear or cyclic) Carboxyalkenyl group (preferably having a carbon number of 2 to 24, more preferably 2 to 12, particularly preferably 2 to 6; the number of carboxyl groups is preferably 1 to 6, more preferably 1 to 3, alkenyl groups are linear And may be branched, linear or cyclic), an acyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and particularly preferably 2 to 3 carbon atoms), and an acyloxy group (preferably 2 to 12 carbon atoms, 2 to 6 is more preferable, 2 to 3 is particularly preferable, aryloyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 and particularly preferably 7 to 11), aryloyl oxy group (having 7 to carbon atoms) 23 is preferable, 7 to 19 is more preferable, and 7 to 11 is particularly preferable), a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), oxo group (= O), i Amino group (= ^NR N), an alkylidene group ^{_{(= C (R N) 2}} ) , and the like. Among them, as a substituent, a hydroxy group, an amino group, a carboxyl group, a halogen atom and the like are preferable. ^RN is a hydrogen atom or an alkyl group (preferably having a carbon number of 1 to 12, more preferably 1 to 6, still more preferably 1 to 3), with a hydrogen atom being preferred. When the substituent T is a group capable of forming a salt such as a carboxyl group, the salt may be formed with a counter ion (for example, ammonium ion).

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

Each of R ^B1 and R ^B2 is preferably independently an alkyl group having 1 to 20 carbon atoms (which may be linear, branched, linear or cyclic). This alkyl group may have a substituent T. More preferably, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched hydroxyalkyl group having 1 to 6 carbon atoms (the number of hydroxy groups is preferably 1 to 6, more preferably 1 to 3) A linear or branched aminoalkyl group having 1 to 6 carbon atoms (the number of amino groups is preferably 1 to 6, more preferably 1 to 3), a cycloalkyl group having 3 to 8 carbon atoms (more preferably It is preferable that it is a cyclopentyl group or a cyclohexyl group).
R ^B3 is preferably a hydrogen atom, an alkyl group having 1 to 12 carbons (preferably 1 to 6) (which may be linear, branched, linear or cyclic), or a heteroaryl group having 1 to 6 carbons. More preferably, R ^B3 is a hydrogen atom, a linear or branched alkyl group having 1 to 12 (preferably 1 to 6) carbon atoms, a linear or 1 to 12 (preferably 1 to 6) carbon atoms or Branched hydroxyalkyl group (the number of hydroxy groups is preferably 1 to 6, more preferably 1 to 3), linear or branched aminoalkyl group having 1 to 12 carbon atoms (preferably 1 to 6) (amino group Is preferably 1 to 6, more preferably 1 to 3), cycloalkyl having 3 to 8 carbon atoms (more preferably a cyclopentyl or cyclohexyl group), or heteroaryl having 3 to 6 carbon atoms Preferably, it is a pyridyl group).

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

The above-mentioned amine compound preferably has two or more atoms connecting the nitrogen atom to the carbon atom, of the carbon atom farthest from the nitrogen atom. The upper limit of the number of linking atoms is preferably 20 or less, more preferably 12 or less, still more preferably 8 or less, and particularly preferably 5 or less. Since the amine compound has a strong interaction with copper, it may be easily localized on the surface of copper used for wiring. When the substituent of the amine compound is in this range, the polarity of the surface can be properly maintained even if the amine is unevenly distributed in the copper wiring, so that the decrease in adhesion to the insulating film can be more effectively suppressed. Specifically, when R ^B1 is a cyclohexyl group, the number of atoms connecting the above nitrogen atom and the farthest carbon atom is opposite to the carbon (α carbon) substituted with the nitrogen atom of the six-membered ring when R ^B1 is a cyclohexyl group. The side carbon atom is the farthest carbon atom. This is the third carbon atom in view of the α carbon. Therefore, the number of atoms connecting the third carbon atom and the alpha carbon is two.

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

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

As specific examples of the amine compound, in addition to the compounds described in Examples described later, the compounds described in paragraphs 0204 and 0205 of JP-A-2011-221494 can be used, and the contents thereof are incorporated in the present specification. .

It is preferable that the compounding quantity of the amine compound which comprises a salt with respect to 100 mass parts of polymer precursors is 20 mass parts or less, It is more preferable that it is 10 mass parts or less, It is more preferable that it is 5 mass parts or less The content is more preferably 3 parts by mass or less, still more preferably 2 parts by mass or less. The lower limit 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, and 0.3 parts by mass or more. The content is more preferably 0.5 parts by mass or more.
The salt may have only a cation derived from one kind of amine compound, or may have a cation derived from two or more kinds of amine compounds. When it contains 2 or more types, it is preferable that a total amount becomes said range.
In addition to salts containing a cation derived from an amine compound used in the present invention and an anion derived from an acidic compound, a salt containing a cation derived from ammonia may be included. However, it is preferable not to substantially contain a salt containing a cation derived from ammonia. The content of the salt containing a cation derived from ammonia is 5% by mass or less of the content of the salt containing a cation derived from an amine compound and an anion derived from an acidic compound as substantially free. The content is preferably 3% by mass or less, more preferably 1% by mass or less.

<< Acid compound >>
The acidic compound in the present invention refers to a compound exhibiting a pH of less than 7 in an aqueous solution. Preferred is a compound having an acid group, and as the acid group, a group that generates free hydrogen in an aqueous solution is preferable. For example, the compound which has a sulfonic acid group, a carboxyl group, a phosphonic acid group, a phosphoric acid group, a boronic acid group etc. is mentioned, The compound which has 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, preferred is a compound represented by any one of the following formulas (AC1) to (AC5).

In the formula, R ^A1 represents a hydroxyl group or a monovalent organic group. As this monovalent organic group, a linear or branched alkyl group (having 1 to 12 carbon atoms is preferable, 1 to 6 is more preferable, and 1 to 3 is particularly preferable), and a cycloalkyl group (3 to 24 carbon atoms) 3 to 12 are more preferable, and 3 to 6 are particularly preferable, an aryl group (having 6 to 22 carbon atoms is more preferable, 6 to 18 is more preferable, and 6 to 10 is particularly preferable), heteroaryl group (1 carbon atom) To 12 are preferable, and 1 to 6 are more preferable. Among them, preferred is a linear or branched alkyl or aryl group having the above-mentioned carbon number. These groups may or may not further have a substituent T. Examples thereof include groups in which an alkyl group and an aryl group are combined (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and particularly preferably 7 to 11 carbon atoms), and aralkyl groups (preferably 7 to 23 carbon atoms) 7 to 19 is more preferable, and 7 to 11 is particularly preferable, or an alkylaryl group (having 7 to 23 carbon atoms is preferable, 7 to 19 is more preferable, and 7 to 11 is particularly preferable).

Each of R ^A2 to R ^A6 independently represents a hydrogen atom or a monovalent organic group. As this monovalent organic group, the group and carboxyl group which were described by said R ^<A1 > are mentioned, The same group as the group described by R ^<A1> is more preferable. The monovalent organic group may or may not further have a substituent T.
R ^A7 to R ^A12 each independently represent a hydrogen atom or a monovalent organic group, preferably a hydrogen atom. As this monovalent organic group, the same group as the above R ^A1 can be mentioned, and the preferred range is also the same. The monovalent organic group may or may not further have a substituent T.
R ^A13 represents a hydrogen atom or a monovalent organic group, and is preferably a monovalent organic group. As this monovalent organic group, the same group as the above R ^A1 can be mentioned, and the preferred range is also the same. The monovalent organic group may or may not further have a substituent T.

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

The molecular weight of the acidic compound is preferably 50 or more, more preferably 60 or more, still more preferably 70 or more, and still more preferably 80 or more. 1000 or less are preferable, 700 or less are more preferable, 500 or less are more preferable, 300 or less are more preferable, and 200 or less are especially preferable. In addition, by setting the molecular weight of the acidic compound to 1000 or less, it becomes difficult to remain in the film in the heat curing step, the curing reaction proceeds effectively, and the film strength tends to be improved. By setting the molecular weight to 50 or more, the composition is less likely to volatilize during storage, and the film thickness change with time can be more effectively suppressed.

The compounding 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, and still more preferably 5 parts by mass or less, It may be 3 parts by mass or less. The lower limit 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, and 0.3 parts by mass or more. Even more preferably, it may be 0.5 parts by mass or more.
The acidic compound may have only an anion derived from one type of acidic compound, or may have an anion derived from two or more types of acidic compounds. When it contains 2 or more types, it is preferable that a total amount becomes said range.

<Solvent>
The thermosetting resin composition of the present invention contains a solvent. As the solvent, known solvents can optionally be used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides and amides.
As esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone , Δ-valerolactone, alkyl alkyl oxyacetate (eg, methyl alkyl oxyacetate, ethyl alkyl oxyacetate, butyl alkyl oxy acetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate etc.) ), 3-alkyloxypropionic acid alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, 3-methoxypropionate) Ethyl acid, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate etc.), 2-alkyloxypropionic acid alkyl esters (eg methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2 -Propyl alkyl oxypropionate etc. (eg methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyl Methyl oxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate etc.), methyl pyruvate , Pyruvate Chill, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like as preferred.
As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. are mentioned as a suitable thing.
Preferred examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like.
As aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene etc. may be mentioned as suitable.
As a sulfoxide, for example, dimethyl sulfoxide is mentioned as a suitable one.
Examples of suitable amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like.

The solvent is also preferably in the form of a mixture of two or more from the viewpoint of improving the coated surface properties and the like.
In the present invention, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ- Butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and one solvent selected from propylene glycol methyl ether acetate, or two or more Mixed solvents are preferred. The combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

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

<Photo radical polymerization initiator>
A photoradical polymerization initiator may be contained in the thermosetting resin composition of the present invention to impart photosensitivity.
There is no restriction | limiting in particular as a radical photopolymerization initiator which can be used by this invention, It can select suitably from well-known radical photopolymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferred. In addition, it may be an activator which produces an active radical by causing an action with a photoexcited sensitizer.
The photoradical polymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 in the range of about 300 to 800 nm (preferably 330 to 500 nm). The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with a UV-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

Since the thermosetting resin composition of the present invention is applied to a substrate such as a semiconductor wafer by forming a thermosetting resin composition layer by containing a photo radical polymerization initiator, light is applied. By irradiation, curing due to the generated radicals occurs, and the solubility in the light irradiation part can be reduced. Therefore, for example, by exposing the thermosetting resin composition layer through a photomask having a pattern for masking only the electrode portion, it is possible to easily produce regions having different solubility according to the pattern of the electrode. There is.

A well-known compound can be used arbitrarily as a radical photopolymerization initiator. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acyl phosphine compounds such as acyl phosphine oxides, hexaarylbiimidazole, oxime derivatives, etc. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. It can be mentioned. The details thereof can be referred to the description in paragraphs [0165] to [0182] of JP-A-2016-027357, the contents of which are incorporated herein.

As a ketone compound, the compound as described in Paragraph 0087 of Unexamined-Japanese-Patent No. 2015-087611 is illustrated, for example, This content is integrated in this specification. Among commercial products, Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

As a radical photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acyl phosphine compound can also be used suitably. More specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 and an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used.
As a hydroxyacetophenone type initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127 (trade name: all manufactured by BASF Corporation) can be used.
As aminoacetophenone initiators, commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF Corporation) can be used.
As the aminoacetophenone initiator, a compound described in JP-A-2009-191179 in which the absorption maximum wavelength is matched to a wavelength light source such as 365 nm or 405 nm can also be used.
Examples of the acylphosphine initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and the like. In addition, IRGACURE 819 or IRGACURETPO (trade name: all manufactured by BASF), which are commercially available products, can be used.
Examples of metallocene compounds include IRGACURE-784 (manufactured by BASF).

As a photo radical polymerization initiator, More preferably, an oxime compound is mentioned. By using an oxime compound, it is possible to more effectively improve the exposure latitude. The oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also serves as a light curing accelerator.
As specific examples of the oxime compound, compounds described in JP-A-2001-233842, compounds described in JP-A-2000-80068, and compounds described in JP-A-2006-342166 can be used.
Preferred oxime compounds include, for example, compounds of the following structures, 3-benzoximinobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxy Iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like. In the thermosetting resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as a radical photopolymerization initiator. The oxime-based photopolymerization initiator has a> C = N—O—C (= O) — linking group in the molecule.

As commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF Corporation), Adeka Optomer N-1919 (manufactured by ADEKA Co., Ltd.), light described in JP 2012-14052 A Radical polymerization initiators 2) are also suitably used. In addition, TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), Adeka ARKules NCI-831 and Adeka ARKLS NCI-930 (manufactured by ADEKA Corporation) can also be used. Also, DFI-091 (manufactured by Daitoke Mix Co., Ltd.) can be used.
Furthermore, it is also possible to use an oxime compound having a fluorine atom. As specific examples of such oxime compounds, compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in paragraph 0345 of JP-A-2014-500852, JP-A-2013 And the compound (C-3) described in paragraph 0101 of JP-164471-A, and the like.
As the most preferable oxime compound, an oxime compound having a specific substituent described in JP-A-2007-269779, an oxime compound having a thioaryl group shown in JP-A-2009-191061, and the like can be mentioned.

The photo radical polymerization initiator is a trihalomethyl triazine compound, a benzyl dimethyl ketal compound, an α-hydroxy ketone compound, an α-amino ketone compound, an acyl phosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triaryl from the viewpoint of exposure sensitivity. Imidazole dimer, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complex and salts thereof, halomethyl oxadiazole compounds, 3-aryl substituted coumarin compounds Compounds are preferred.
Further preferable photoradical polymerization initiators are trihalomethyl triazine compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salt compounds, benzophenone compounds, acetophenone compounds, More preferred is at least one compound selected from the group consisting of trihalomethyl triazine compounds, α-amino ketone compounds, oxime compounds, triarylimidazole dimers and benzophenone compounds, still more preferably metallocene compounds or oxime compounds, oxime compounds Is even more preferred.
In addition, photo radical polymerization initiators include N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), etc. Aromatic ketones such as -2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, alkylanthraquinones, etc. Also usable are quinones fused with the aromatic ring of the above, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, and benzyl derivatives such as benzyl dimethyl ketal. Moreover, the compound represented by following formula (I) can also be used.

In the formula (I), R ¹⁰⁰ represents 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, An alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, and 2 to carbon atoms interrupted by one or more oxygen atoms 18 alkyl group and at least one substituted phenyl group of the alkyl group having 1 to 4 carbon atoms or a biphenylyl,, R ^I01 is a group represented by formula (II), the same as R ^I00 And each of R ¹⁰² to R ¹⁰⁴ is independently an alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons, or a halogen.

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

Further, as the photoradical polymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication WO 2015/125469 can also be used.

When the radical photopolymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass with respect to the total solid content of the thermosetting resin composition of the present invention. % By mass, more preferably 0.5 to 15% by mass, and still more preferably 1.0 to 10% by mass. The photo radical polymerization initiator may contain only one kind, or two or more kinds. When 2 or more types of radical photopolymerization initiators are contained, it is preferable that the sum total is the said range.

<Thermal radical polymerization initiator>
The thermosetting resin composition of the present invention may contain a thermal radical polymerization initiator within the scope of the present invention.
The thermal radical polymerization initiator is a compound that generates radicals by the energy of heat and initiates or accelerates a polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the polymer precursor can be advanced along with the cyclization of the polymer precursor, so that a higher degree of heat resistance can be achieved.
Specific examples of the thermal radical polymerization initiator include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-63554.

When the heat radical polymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass with respect to the total solid content of the thermosetting resin composition of the present invention. It is mass%, more preferably 5 to 15 mass%. The thermal radical polymerization initiator may contain only one type, or may contain two or more types. When 2 or more types of thermal radical polymerization initiators are contained, it is preferable that the sum total is the said range.

<Polymerizable compound>
<< Radically Polymerizable Compound >>
It is preferable that the thermosetting resin composition of this invention contains a radically polymerizable compound, when providing photosensitivity.

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

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

2000 or less are preferable, as for the molecular weight of a radically polymerizable compound, 1500 or less are more preferable, and 900 or less are more preferable. The lower limit of the molecular weight of the radically polymerizable compound is preferably 100 or more.

The thermosetting resin composition of the present invention preferably contains at least one difunctional or higher radically polymerizable compound containing two or more polymerizable groups, from the viewpoint of developability, and a trifunctional or higher radically polymerizable compound It is more preferable to include at least one of Moreover, the mixture of a bifunctional radically polymerizable compound and a trifunctional or more than trifunctional radically polymerizable compound may be sufficient. The number of functional groups of the radically polymerizable compound means the number of radically polymerizable groups in one molecule.

Specific examples of the radically polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid etc.), esters thereof and amides, and preferably Esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyhydric amine compounds. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxy group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, a monofunctional or a polyfunctional Dehydration condensation products with functional carboxylic acids and the like are also suitably used. Also, addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as isocyanate group and epoxy group with monofunctional or polyfunctional alcohols, amines and thiols, and halogen groups Also suitable are substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as tosyloxy group with monofunctional or polyfunctional alcohols, amines and thiols. As another example, instead of the above unsaturated carboxylic acid, it is also possible to use unsaturated phosphonic acid, a vinyl benzene derivative such as styrene, a vinyl ether, an allyl ether or the like, and a group of compounds replaced. As a specific example, the description in paragraphs [0113] to [0122] of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated in the present specification.

Further, the radically polymerizable compound is also preferably a compound having a boiling point of 100 ° C. or higher under normal pressure. Examples thereof include polyethylene glycol di (meth) acrylate, trimethylol ethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin, trimethylolethane and the like A compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then converting to (meth) acrylate, JP-B-48-4170. Urethane (meth) acrylates as described in Japanese Patent Application Publication No. 50-6034 and Japanese Patent Application Publication No. 51-37193; Japanese Patent Application Publication No. 48-64183; Japanese Patent Publication No. 49-43191; JP-A-52-30490 mentions polyester acrylates, polyfunctional acrylates and methacrylates such as epoxy acrylates which is a reaction product of an epoxy resin and (meth) acrylic acid, and mixtures thereof it can. In addition, compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Moreover, the polyfunctional (meth) acrylate etc. which are obtained by making the compound which has cyclic ether groups, such as a glycidyl (meth) acrylate, and an ethylenic unsaturated bond react with polyfunctional carboxylic acid can also be mentioned.
Moreover, as a preferable radically polymerizable compound other than the above-mentioned, it has a fluorene ring and is described in Unexamined-Japanese-Patent No. 2010-160418, Unexamined-Japanese-Patent No. 2010-129825, patent 4364216 etc., and an ethylenically unsaturated bond is described. It is also possible to use a compound having two or more groups and a cardo resin.
Further, as other examples, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and JP-A-2-25493 are described. And the like. Further, compounds containing a perfluoroalkyl group described in JP-A-61-22048 can also be used. Furthermore, Journal of Japan Adhesive Association vol. 20, no. Also those introduced as photopolymerizable monomers and oligomers on pages 7, 300-308 (1984) can be used.

Besides the above, the compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964 can also be preferably used, and the contents thereof are incorporated in the present specification.

Further, compounds described after addition of ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated as described in Formula (1) and Formula (2) together with specific examples thereof in JP-A-10-62986 are also available. It can be used as a radically polymerizable compound.

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

As radically polymerizable compounds, dipentaerythritol triacrylate (commercially available as KAYARAD D-330; Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; Nippon Kayaku ( A-TMMT: Shin-Nakamura Chemical Co., Ltd., dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; Nippon Kayaku Co., Ltd.), dipentaerythritol hexa ( (Meta) acrylate (commercially available: KAYARAD DPHA; Nippon Kayaku Co., Ltd., A-DPH; Shin-Nakamura Chemical Co., Ltd.), and these (meth) acryloyl groups are ethylene glycol and propylene glycol residues. Preferred is a structure linked via an interface. These oligomer types can also be used.

Commercial products of radically polymerizable compounds include, for example, SR-494 which is a tetrafunctional acrylate having 4 ethyleneoxy chains manufactured by Sartomer, SR-209 manufactured by Sartomer which is a difunctional methacrylate having 4 ethyleneoxy chains. 231, 239, DPCA-60 which is a hexafunctional acrylate having 6 pentylene oxy chains manufactured by Nippon Kayaku Co., Ltd., TPA-330 which is a trifunctional acrylate having 3 isobutylene oxy chains, urethane oligomer UAS- 10, UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA- 40H (Nippon Kayaku Co., Ltd. product), UA-306H, UA-306T, UA-3 6I, (manufactured by Kyoeisha Chemical (Co.)) AH-600, T-600, AI-600, Blemmer PME400 (manufactured by NOF Corporation) and the like.

As radically polymerizable compounds, urethane acrylates and the like as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293 and JP-B-2-16765. JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, JP-B-62-39418 and urethane compounds having an ethylene oxide skeleton as described in JP-B-58-49860 and JP-B-62-39418 are also suitable. Furthermore, as radically polymerizable compounds, compounds having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909, JP-A-1-105238, can be used. It can also be used.

The radically polymerizable compound may be a radically polymerizable compound having an acid group such as a carboxyl group or a phosphoric acid group. The radically polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an unreacted hydroxy group of the aliphatic polyhydroxy compound is reacted with a nonaromatic carboxylic acid anhydride to produce an acid. Radically polymerizable compounds having a group are more preferred. Particularly preferably, in the radically polymerizable compound in which a nonaromatic carboxylic acid anhydride is reacted with an unreacted hydroxy group of the aliphatic polyhydroxy compound to give an acid group, the aliphatic polyhydroxy compound is pentaerythritol and / or It is a compound which is dipentaerythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
The preferred acid value of the radically polymerizable compound having an acid group is 0.1 to 40 mg KOH / g, particularly preferably 5 to 30 mg KOH / g. If the acid value of the radically polymerizable compound is in the above range, the production and handling properties are excellent, and furthermore, the developability is excellent. Moreover, the polymerizability is good.

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

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

(Compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group)
The compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group is preferably a compound represented by the following formula (AM1), (AM4) or (AM5).

(Wherein 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 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.

(Wherein, 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 carbon And R ⁴⁰⁷ represents an organic group having 1 to 10 carbon atoms.

Wherein 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. 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 (all trade names, manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML- PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX -290 (trade name, Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacecoxymethyl-p-cresol, etc. .

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

(Epoxy compound (compound having an epoxy group))
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group crosslinks at a temperature of 200 ° C. or less, and a film contraction does not easily occur because a dehydration reaction derived from crosslinking does not occur. For this reason, containing an epoxy compound is effective for suppressing the low temperature curing and warpage of the composition.

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

Examples of epoxy compounds are: bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resin such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether; Examples include epoxy group-containing silicones such as (oxypropyl) siloxane and the like, but are not limited thereto. 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 (R) EXA-4710, Epiclon (R) HP-4770, Epiclon (R) EXA-859 CRP, Epiclon (R) EXA-1514, Epiclon (R) EXA-4880, Epiclon (R) EXA-4850-150, Epiclon (registered trademark) EXA-4850-1000, Epiclon (registered trademark) EXA-4816, Epiclon (registered trademark) EXA-4822 (trade names, manufactured by DIC Corporation), Rikaresin (registered trademark) ) BEO-60E (brand name, Shin Nippon Rika (stock ), EP-4003S, EP-4000S (trade name, (Ltd.) and the like manufactured by ADEKA). Among these, the epoxy resin containing a polyethylene oxide group is preferable at the point which is excellent in suppression of curvature, and heat resistance. For example, Epiclon (registered trademark) EXA-4880, Epiclon (registered trademark) EXA-4822, and Rikaresin (registered trademark) BEO-60E are preferable because they contain polyethylene oxide groups.

(Oxetane Compound (Compound Having an Oxetanyl Group))
Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyl oxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, Examples thereof include 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester and the like. As a specific example, Aon oxetane series (for example, OXT-121, OXT-221, OXT-191, OXT-223) manufactured by Toagosei Co., Ltd. can be suitably used, and these can be used alone. Or you may mix 2 or more types.

(Benzoxazine compound (compound having a benzoxazolyl group))
The benzoxazine compound is preferable because degassing does not occur at the time of curing because of the crosslinking reaction derived from the ring opening addition reaction, and further, the thermal shrinkage is reduced to suppress the occurrence of warpage.

Preferred examples of the benzoxazine compound include B-a type benzoxazine, B-m type benzoxazine (all trade names, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, phenol novolac type Dihydrobenzoxazine compounds are included. These may be used alone or in combination of two or more.

When the polymerizable compound is contained, the content is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the thermosetting resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less and still more preferably 30% by mass or less.
Although a polymeric compound may be used individually by 1 type, you may mix and use 2 or more types. When using 2 or more types together, it is preferable that the total amount becomes said range.

<Migration inhibitor>
The thermosetting resin composition of the present invention preferably further contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress migration of metal ions derived from the metal layer (metal wiring) into the thermosetting resin composition layer.
The migration inhibitor is not particularly limited, but a heterocyclic ring (a pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring Compounds having pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thioureas and mercapto group, hindered phenol compounds And salicylic acid derivative compounds and hydrazide 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.

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

Examples of other migration inhibitors include rust inhibitors described in paragraph 0094 of JP-A-2013-15701, compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, and JP-A-2011-59656. The compounds described in paragraph 0052, the compounds described in paragraphs 0114, 0116 and 0118 of JP 2012-194520 A, and the like can be used.

The following compounds can be mentioned as specific examples of the migration inhibitor.

When the thermosetting resin composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the thermosetting resin composition. And more preferably 0.1 to 1.0% by mass.
The migration inhibitor may be used alone or in combination of 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.
Examples of the polymerization inhibitor include hydroquinone, 4-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butyl catechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4 ' -Thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1 -Nitroso 2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, bis (4) Preferably, -hydroxy-3,5-tert-butyl) phenylmethane or the like is used. Furthermore, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication WO 2015/125469 can also be used.
In addition, the following compounds can be used (Me is a methyl group).

When the thermosetting resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is 0.01 to 5% by mass based on the total solid content of the thermosetting resin composition of the present invention. It is preferably from 0.02 to 3% by mass, particularly preferably from 0.05 to 2.5% by mass.
The polymerization inhibitor may be used alone or in combination of two or more. When two or more polymerization inhibitors are used, the total is preferably in the above range.

Metal adhesion improver
The thermosetting resin composition of the present invention preferably contains a metal adhesion improver for improving the adhesion to a metal material used for electrodes, wiring and the like. Examples of the metal adhesion improver include silane coupling agents.

Examples of the silane coupling agent include compounds described in paragraphs 0062 to 0073 of JP-A 2014-191002, compounds described in paragraphs 0063 to 0071 of International Publication WO 2011/080992 A1, and compounds described in JP-A 2014-191252. The compounds described in paragraphs 0060 to 0061, the compounds described in paragraphs 0045 to 0052 in JP-A-2014-41264, and the compounds described in paragraph 0055 of International Publication WO 2014/097594. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. Moreover, it is also preferable to use the following compound as a silane coupling agent. In the following formulas, Et represents an ethyl group.

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

The content of the metal adhesion modifier is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, particularly preferably 0 based on 100 parts by mass of the polymer precursor. And in the range of 5 to 5 parts by mass. By setting it as the said lower limit or more, the adhesiveness of the cured film after a hardening process and a metal layer becomes favorable, and the heat resistance of the cured film after a hardening process and mechanical characteristics become favorable by below the said upper limit. The metal adhesion improver may be used alone or in combination of two or more. When using 2 or more types, it is preferable that the sum is the said range.

<Hardening accelerator>
The thermosetting resin composition of the present invention may contain a curing accelerator. The curing accelerator may be a thermal curing accelerator or a light curing accelerator.
<< Thermosetting accelerator >>
The heat curing accelerator is preferably a salt of a quaternary ammonium cation and a carboxylate anion. The quaternary ammonium cation is preferably represented by the following formula (Y1-1).

In the formula ^{(Y1-1), R N1} is Nn number (Nn is an integer of 1 to 12) represents an organic group, preferably an Nn-valent hydrocarbon group. The hydrocarbon group may be an alkane-containing Nn-valent group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 and particularly preferably 1 to 3), and an alkene Nn-valent group (2 to 12 carbon atoms). Is preferable, 2 to 6 is more preferable, and 2 to 3 is particularly preferable, and an aromatic hydrocarbon-containing Nn-valent group (having 6 to 22 carbon atoms is preferable, 6 to 18 is more preferable, and 6 to 10 is particularly preferable. Or combinations thereof. Among them, R ^N1 is preferably an aromatic hydrocarbon group. R ^N1 may have the aforementioned substituent T within the range not impairing the effects of the present invention.
R ^N2 ~ ^{R N5} are independently a hydrogen atom or a hydrocarbon group (having 1 to 36 carbon atoms, more preferably 1 to 24, particularly preferably 1 to 12) represents, an alkyl group (C 1 - 36 is preferable, 1 to 24 is more preferable, 1 to 23 is particularly preferable, an alkenyl group (having 2 to 36 carbon atoms is preferable, 2 to 24 is more preferable, and 2 to 23 is particularly preferable), and an alkynyl group (carbon number is 1 to 36 is preferable, 1 to 24 is more preferable, and 1 to 23 is particularly preferable, and an aryl group (having 6 to 22 carbon atoms is preferable, 6 to 18 is more preferable, and 6 to 10 is particularly preferable). The alkyl group, the alkenyl group and the alkynyl group may be linear or branched and may be cyclic or linear.
R ^N6 is an alkyl group (preferably 1 to 36 carbon atoms, more preferably 2 to 24 carbon atoms, and particularly preferably 4 to 18 carbon atoms), and an alkenyl group (preferably 2 to 36 carbon atoms, more preferably 2 to 24 carbon atoms, and 4 to 18 carbon atoms. , An alkynyl group (preferably having a carbon number of 2 to 36, more preferably 2 to 24, and particularly preferably 4 to 18), and an aryl group (preferably having a carbon number of 6 to 22, preferably 6 to 18). To 10 are particularly preferable). The alkyl group, the alkenyl group and the alkynyl group may be linear or branched, cyclic or linear. At this time, in the alkyl group, the alkenyl group, the alkynyl group and the aryl group, a linking group Lh containing a hetero atom may be interposed in the middle of the chain or in the linkage with the mother nucleus. As the linking group Lh containing a hetero atom, a linking group consisting of —O—, —S—, —CO—, —NR ^N — or a combination thereof is mentioned. The number of atoms constituting the linking group Lh containing a hetero atom is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3. The number of atoms intervening in a specific group of the linking group Lh containing a hetero atom is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3. ^RN is as defined above. R ^N6 may further have the above-mentioned substituent T within the range not impairing the effects of the present invention.
Nn represents an integer of 1 or more and 12 or less, an integer of 1 to 6 is more preferable, and an integer of 1 to 3 is particularly preferable.
No is preferably an integer of 1 to 12, more preferably an integer of 1 to 6, and particularly preferably an integer of 1 to 3.
Two or more of R ^N2 to R ^N6 may be combined with each other to form a ring.

In this embodiment, specific examples of the carboxylate anion paired with the above-mentioned quaternary ammonium cation include anions derived from the compounds represented by any one of formulas AC2 to AC5 exemplified as the above-mentioned acidic compound.
The molecular weight of the thermosetting accelerator in the present invention is preferably 100 or more and less than 2000, more preferably 200 to 1000.
Examples of the thermal curing accelerator in the present invention include an acidic compound which generates a base when heated to 40 ° C. or higher described in WO 2015/199219, and an ammonium salt having an anion with an pKa 1 of 0 to 4 and an ammonium cation. The contents of these are incorporated herein.

When a heat curing accelerator is used, the content of the heat curing accelerator in the composition is preferably 0.01 to 50% by mass with respect to the total solid content of the composition. The lower limit is more preferably 0.05% by mass or more and further preferably 0.1% by mass or more. 10 mass% or less is more preferable, and, as for the upper limit, 5 mass% or less is more preferable.
The heat curing accelerator may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount is the said range. Moreover, the composition of this invention can also be set as the structure which does not contain a thermosetting accelerator substantially. Substantially free means less than 0.01% by mass, and more preferably less than 0.005% by mass, relative to the total solid content of the composition.

<< photo-curing accelerator >>
The thermosetting resin composition used by this invention may contain the photocuring accelerator. The photo-curing accelerator in the present invention generates a base upon exposure, and does not show activity under ordinary conditions of normal temperature and pressure, but when irradiation and heating of electromagnetic waves are performed as an external stimulus, the base ( It is not particularly limited as long as it generates a basic substance). The base generated by exposure to light serves as a catalyst for curing the polymer precursor by heating, and thus can be suitably used.
In the present invention, known photocuring accelerators can be used. For example, such as a transition metal compound complex, one having a structure such as an ammonium salt, or one in which an amidine moiety is made latent by forming a salt with a carboxylic acid, the base component is neutralized by forming a salt Examples thereof include ionic compounds, and non-ionic compounds such as carbamate derivatives, oxime ester derivatives, and acyl compounds in which the base component is made latent by urethane bonds or oxime bonds.

As the photocuring accelerator according to the present invention, for example, a photocuring accelerator having a cinnamic acid amide structure as disclosed in JP-A-2009-80452 and WO2009 / 123122 pamphlet, JP-A-2006- Photocuring accelerators having a carbamate structure as disclosed in Japanese Patent Application Publication Nos. 189591 and 2008-247747; oxime structures as disclosed in Japanese Patent Application Publication Nos. 2007-249013 and 2008-003581; Although the photocuring accelerator etc. which have a carbamoyl oxime structure etc. are mentioned, it is not limited to these, In addition, the structure of a well-known photocuring accelerator can be used.

In addition, as a photocuring accelerator, compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of JP 2012-93746 A, compounds described in paragraphs 0022 to 0069 of JP 2013-194205 A, and The compounds described in paragraphs 0026 to 0074 of JP2013-204019, and the compounds described in paragraph 0052 of International Publication WO2010 / 064631 are mentioned as examples.

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

When a photo-curing accelerator is used, the content of the photo-curing accelerator in the composition is preferably 0.1 to 50% by mass with respect to the total solid content of the composition. As for a minimum, 0.5 mass% or more is more preferable, and 1 mass% or more is further more preferable. The upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less.
The photocuring accelerator may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount is the said range.

<Organic compounds containing Group 4 elements>
The composition of the present invention preferably contains an organic compound containing a Group 4 element (hereinafter sometimes referred to as "organic titanium compound etc.").
The organic compound containing a Group 4 element is preferably an organic compound containing at least one selected from titanium atom, zirconium atom and hafnium atom, and contains at least one selected from titanium atom and zirconium atom More preferably, it is an organic compound. The organic compound containing at least one selected from titanium atom and zirconium atom is preferably a compound containing an organic group and titanium atom or zirconium atom, and the number of titanium atoms and zirconium atoms in one molecule is In total, one is preferred. The organic group is not particularly limited, but is preferably a hydrocarbon group or a group consisting of a combination of a hydrocarbon group and a hetero atom. The hetero atom is preferably an oxygen atom, a sulfur atom or a nitrogen atom.
In the present invention, at least one of the organic groups is preferably a cyclic group, and more preferably at least two are cyclic groups. The cyclic group is preferably selected from a 5-membered cyclic group and a 6-membered cyclic group, and more preferably selected from a 5-membered cyclic group. As a 5-membered cyclic group, a cyclopentadienyl group is preferable. In addition, the organic titanium compound and the like used in the present invention preferably contain 2 to 4 cyclic groups in one molecule.
Organic titanium compounds and the like in the present invention are preferably represented by the following formulas (P-1) to (P-3), and more preferably compounds represented by formula (P-1).

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

Each R is 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 preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and still more preferably 6 to 10 carbon atoms. Specific examples thereof include phenyl, 1-naphthyl and 2-naphthyl groups. The alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 and still more preferably 1 to 3. Specifically, methyl group, ethyl group, propyl group, octyl group, isopropyl group, t-butyl And isopentyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like. The halogen atom includes F, Cl, Br and I. The alkyl group constituting the alkylsulfonyloxy group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 and still more preferably 1 to 3. Specifically, methyl group, ethyl group, propyl group, octyl group And isopropyl group, t-butyl group, isopentyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like.
The substituent may further have a substituent. Examples of the substituent include a substituent T and the like, and specifically, a halogen atom (F, Cl, Br, I), a hydroxy group, a carboxyl group, an amino group, a cyano group, an aryl group, an alkoxy group, And aryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyloxy groups, monoalkylamino groups, dialkylamino groups, monoarylamino groups, and diarylamino groups.

R ^P1 to R ^P4 are a halogen atom, a hydroxy group or an organic group (excluding a cyclopentadienyl group). As the organic group, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and further preferably 1 to 3), and an alkenyl group (preferably having 2 to 12 carbon atoms, and more preferably 2 to 6 carbon atoms) -3 is more preferable, an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 and still more preferably 6 to 10 carbon atoms), and an alkoxy group (preferably having 1 to 12 carbon atoms, and more preferably 1 to 6) , 1 to 3 is further preferable, an aryloxy group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 and still more preferably 6 to 10 carbon atoms), an alkylsulfonyloxy group (preferably having 1 to 12 carbon atoms, -6 is more preferable, 1 to 3 is more preferable, arylsulfonyloxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and still more preferably 1 to 3) Acyloxy group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 and still more preferably 2 to 3), aryloyl oxy group (having 7 to 23 carbon atoms, preferably 7 to 19 more preferably 7 to 11) And further preferred).
R ^P0 is an organic linking group constituting a ligand in the formula (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 and further preferably 2 to 4, and may have a hetero linking group Lh And, for example, β-diketone ligands. Examples of the β-diketone include acetylacetonate and ethylacetoacetate, and examples of R ^P0 include a structure of the following formula (P-3 (a)). * Is a bond with an oxygen atom.

R ^P11 is a group having the same ^meaning as R ^P1 .
R ^P12 to R ^P14 are a hydrogen atom or a substituent T. Among the substituents T, in particular, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and further preferably 1 to 3) or an alkoxy group (preferably having 1 to 12 carbon atoms, 1 to 6 is more preferred) Preferably, 1 to 3 are more preferable.
px is an integer of 1 to 4. py is an integer of 0 to 4. Py + px = 4

When R, R ^P1 to R ^P4 and R ^P11 to R ^P14 contain an alkyl group, an alkenyl group, an aryl group or a linking group containing any of these groups, they are further optionally substituted within the scope of achieving the effects of the present invention It may have a group T (for example, a hydroxy group, a carboxyl group, a halogen atom, etc.).
When there are a plurality of R, R ^P1 to R ^P4 and when there are a plurality of R ^P11 and R ^P12 to R ^P14 , they may be the same as or different from each other. Also, two or more adjacent groups may be bonded to form a ring via the following linking group L or not.
The linking group L is an alkylene group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 and particularly preferably 1 to 3), an alkenylene group (preferably 2 to 12 carbon atoms, more preferably 2 to 6), O It is preferable that it is group which concerns on, CO, NR ^N , S, or its combination. The number of atoms constituting the linking group L is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3, excluding hydrogen atoms. The number of linking atoms of linking group L is preferably 10 or less, and more preferably 8 or less. The lower limit is 1 or more. The number of connected atoms means the minimum number of atoms involved in connection, which is located in a path connecting predetermined structural parts. For example, in the case of —CH ₂ —C (= O) —O—, the number of atoms constituting the linking group is 6, but the number of linking atoms is 3.

The organic compound containing a Group 4 element used in the present invention is preferably selected from titanocene compounds, tetraalkoxytitanium compounds, titanium acylate compounds, titanium chelate compounds, zirconocene compounds and hafnocene compounds, and titanocene compounds, zirconocene compounds and It is more preferably selected from hafnocene compounds, and still more preferably selected from titanocene compounds and zirconocene compounds.

The molecular weight of the organic titanium compound or the like is preferably 50 to 2,000, and more preferably 100 to 1,000.

Specific examples of the organic titanium compound and the like include tetraisopropoxytitanium, tetrakis (2-ethylhexyloxy) titanium, diisopropoxybis (ethylacetoacetate) titanium, diisopropoxybis (acetylacetonato) titanium, the following compounds, or The compounds listed in the examples below are exemplified.

Further, among organic titanium compounds and the like, as an organic compound containing a titanium atom, di-cyclopentadienyl-Ti-di-chloride (bis (cyclopentadienyl) titanium dichloride), di-cyclopentadienyl-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-difluoro Phenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,4-difluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bi -2,3,4,5,6-pentafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-methyl Cyclopentadienyl-Ti-bis-2,4-difluorophenyl-1-yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium Bis (cyclopentadienyl) bis [2,6-difluoro-3- (methylsulfonamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butylbiaroyl-amino] ) Phenyl] titanium, bis (cyclopentadienyl) bis [2, 6- difluoro-3- (N- ethylacetylamino) phenyl] titanium, bis ( Pentadienyl) bis [2,6-difluoro-3- (N-methylacetylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethylpropionylamino) phenyl] titanium Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethyl- (2,2-dimethylbutanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 -Difluoro-3- (N-butyl- (2,2-dimethylbutanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-pentyl- (2,2, 2-Dimethylbutanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl)-(2 2,2-Dimethylbutanoyl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-methylbutyrylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2 , 6-Difluoro-3- (N-methylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethylcyclohexylcarbonylamino) phenyl] titanium, bis ( Cyclopentadienyl) bis [2,6-difluoro-3- (N-ethylisobutyrylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethylacetyl) Amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (2,2,5,5-tetramethyl-1,2,5-azadisilolizidin-1-yl) phenyl] titanium, bis (cyclopentadi) (Enyl) bis [2,6-difluoro-3- (octylsulfonamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (4-tolylsulfonamido) phenyl] titanium, bis (Cyclopentadienyl) bis [2,6-difluoro-3- (4-dodecylphenylsulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (4- (1) -Pentylheptyl) phenylsulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (ethyl) Sulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-((4-bromophenyl) -sulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,2, 6-Difluoro-3- (2-naphthylsulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (hexadecylsulfonylamido) phenyl] titanium, bis (cyclopentadienyl) ) Bis [2,6-difluoro-3- (N-methyl- (4-dodecylphenyl) sulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-methyl) -4- (1-Pentylheptyl) phenyl) sulfonylamide)] titanium, bis (cyclopentadienyl) ) Bis [2,6-difluoro-3- (N-hexyl- (4-tolyl) -sulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (pyrrolidine-) 2,5-Dion-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3,4-dimethyl-3-pyrrolidine-2,5-dioni-1-] ) Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (phthalimido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-isobutoxycarbonyl (Amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (ethoxycarbonylamino) phenyl] titanium, bis ( Clopentadienyl) bis [2,6-difluoro-3-((2-chloroethoxy) -carbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (phenoxycarbonyl) Amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-phenylthioureido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3 -(3-Butylthioureido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-phenylureido) phenyl] titanium, bis (cyclopentadienyl) bis [2,2, 6-Difluoro-3- (3-butylureido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-di] Luoro-3- (N, N-diacetylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3,3-dimethylureido) phenyl] titanium, bis (cyclopentadi) Enyl) bis [2,6-difluoro-3- (acetylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (butyrylamino) phenyl] titanium, bis (cyclopentadienyl) ) Bis [2,6-difluoro-3- (decanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (octadecanoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (isobutyrylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-ethylhexanoyl] Amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-methylbutanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro- 3- (pivaloylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2,2-dimethylbutanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2 , 6-Difluoro-3- (2-ethyl-2-methylheptanoylamino) phenyl] titanium, bis (cyclopentadienyl) Bis [2,6-difluoro-3- (cyclohexylcarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2,2-dimethyl-3-chloropropanoylamino) Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-phenylpropanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-Chloromethyl-2-methyl-3-chloropropanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3,4-xyloylamino) phenyl] titanium Bis (cyclopentadienyl) bis [2,6-difluoro-3- (4-ethylbenzoylamino) phenyl] titanium Bis (cyclopentadienyl) bis [2,6-difluoro-3- (2,4,6-mesitylcarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (Benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-phenylpropyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [ 2,6-Difluoro-3- (N- (3-ethylheptyl) -2,2-dimethylpentanoylamino) phenyl titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- Isobutyl- (4-tolyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isobuty] Benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexylmethylpivaloylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,2, 6-Difluoro-3- (N- (oxolan-2-ylmethyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-ethylheptyl)- 2,2-Dimethylbutanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-phenylpropyl- (4-tolyl) amino) phenyl] titanium, Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (oxolan-2-ylmethyl)-(4-toluy) ) Amino) phenyl) titanium, bis (cyclopentadienyl) bis [2, 6- difluoro-3- (N- (4- toluylmethyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2 , 6-Difluoro-3- (N- (4-toluylmethyl)-(4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butylbenzoyl) Amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl- (4-tolyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-Hexyl- (4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (2,4-dimethylpentyl) -2,2-dimethyl] Butanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2,4-dimethylpentyl) -2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclo) Pentadienyl) bis [2,6-difluoro-3-((4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-diphenyl Oro-3- (2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2,2-dimethyl-3-ethoxypropanoylamino) phenyl Titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2,2-dimethyl-3-allyloxypropanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,2, 6-Difluoro-3- (N-allylacetylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-ethylbutanoylamino) phenyl] titanium, bis (cyclopenta) Dienyl) bis [2,6-difluoro-3- (N-cyclohexylmethylbenzoylamino) phenyl] titanium, bis Ropentadienyl) bis [2,6-difluoro-3- (N-cyclohexylmethyl- (4-tolyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- ( 2-Ethylhexyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isopropylbenzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2, 6-Difluoro-3- (N- (3-phenylpropyl) -2,2-dimethylpentanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-) [Hexylbenzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- ( N-Cyclohexylmethyl-2,2-dimethylpentanoyl) amino) phenyl) titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butylbenzoylamino) phenyl] titanium, bis (cyclo) Pentadienyl) bis [2,6-difluoro-3- (N- (2-ethylhexyl) -2,2-dimethylpentanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6- Difluoro-3- (N-hexyl-2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isopropyl-2,2-dimethylpenta) Noylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-fe) (Propyl) pivaloylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl-2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) Bis [2,6-difluoro-3- (N- (2-methoxyethyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-benzylbenzoylamino) Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-benzyl- (4-tolyl) amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (2-methoxyethyl)-(4-tolyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 -Difluoro-3- (N- (4-methylphenylmethyl) -2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- ( 2-Methoxyethyl) -2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexylmethyl- (2-ethyl-2-methyl) Heptanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl- (4-chlorobenzoyl)] Mino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl- (2-ethyl-2-methylbutanoyl) amino) phenyl] titanium, bis (cyclopentadiethyl) Enyl) bis [2,6-difluoro-3- (N-cyclohexyl-2,2-dimethylpentanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N -(Oxorani-2-ylmethyl) -2,2-dimethylpentanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexyl- (4-chlorobenzoyl) ) Amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexyl- (2-) (Lorobenzoyl) amino) phenyl) titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3,3-dimethyl-2-azetidinnon-1-yl) phenyl] titanium, bis (cyclopentadienyl) phenyl Enyl) bis [2,6-difluoro-3-isocyanatophenyl) titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethyl- (4-tolylsulfonyl) amino) phenyl] Titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl- (4-tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro -3- (N-Butyl- (4-tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-di] Fluoro-3- (N-isobutyl- (4-tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl- (2,2-dimethyl-) 3-Chloropropanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-phenylpropanoyl) -2,2-dimethyl-3-chloroprop Noyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexylmethyl- (2,2-dimethyl-3-chloropropanoyl) amino) phenyl] titanium, Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isobutyl- (2,2-dimethyl-3-chloropropanoyl) fe] [Le] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl- (2-chloromethyl-2-methyl-3-chloropropanoyl) amino) phenyl] titanium, bis ( Cyclopentadienyl) bis [2,6-difluoro-3- (butylthiocarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (phenylthiocarbonylamino) phenyl] Titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-isocyanatophenyl) titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethyl- (4-) Tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl-) 4-tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl- (4-tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) Enyl) bis [2,6-difluoro-3- (N-isobutyl- (4-tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl) -(2,2-dimethyl-3-chloropropanoyl) amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-phenylpropanoyl) -2,2-dimethyl-3-chloropropanoyl) amino) phenyl] titanium, bis (cyclopenta) Dienyl) bis [2,6-difluoro-3- (N-cyclohexylmethyl- (2,2-dimethyl-3-chloropropanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 -Difluoro-3- (N-isobutyl- (2,2-dimethyl-3-chloropropanoyl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl- ( 2-Chloromethyl-2-methyl-3-chloropropanoyl) amino) phenyl] 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-dimethylbutanoyl) amino) phenyl] titanium, bis (methylcyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl-2,2 -Dimethylpentanoylamino) phenyl] titanium, bis (methylcyclopentadienyl) bis [2,6-difluoro-3- (N-ethylacetylamino) phenyl] titanium, bis (methylcyclopentadienyl) bis [2 , 6-Difluoro-3- (N-ethylpropionylamino) phenyl] titanium, bis (trimethyl) Lylpentadienyl) bis [2,6-difluoro-3- (N-butyl-2,2-dimethylpropanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (2-methoxyethyl) -trimethylsilylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butylhexyldimethylsilylamino) phenyl] titanium, bis (cyclo) Pentadienyl) bis [2,6-difluoro-3- (N-ethyl- (1,1,2-trimethylpropyl) dimethylsilylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 -Difluoro-3- (3-ethoxymethyl-3-methyl-2-azethiodininon-1-yl) phenyl] titanium, bis (cyclo) Pentadienyl) bis [2,6-difluoro-3- (3-allyloxymethyl-3-methyl-2-azetidinnon-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro- 3- (3-Chloromethyl-3-methyl-2-azetidinoni-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-benzyl-2,2-] Dimethylpropanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (5,5-dimethyl-2-pyrrolidinnon-1-yl) phenyl] titanium, bis (cyclopentadienyl) (Enyl) bis [2,6-difluoro-3- (6,6-diphenyl-2-piperidin-2-yl) phenyl] titanium, bis (cyclopentadiene)ビス) bis [2,6-difluoro-3- (N- (2,3-dihydro-1,2-benzisothiazolo-3-one (1,1-dioxide) -2-yl) phenyl] titanium, bis (cyclo) Pentadienyl) bis [2,6-difluoro-3- (N-hexyl- (4-chlorobenzoyl) amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl- (2-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3 -(N-isopropyl- (4-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (4-methylphenylmethyl)-(4-chloro) Benzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (4-methylphenylmethyl)-(2-chlorobenzoyl) amino) phenyl] titanium, bis ( Cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl- (4-chlorobenzoyl) amino) phenyl] titanium, bis Cyclopentadienyl) bis [2,6-difluoro-3- (N-benzyl-2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (2-ethylhexyl) -4-tolyl-sulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-oxaheptyl) benzoylamino) Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3,6-dioxadecyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2, 6 -Difluoro-3- (trifluoromethylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 Difluoro-3- (trifluoroacetylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) Bis [2,6-difluoro-3- (4-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3,6-dioxadecyl)- 2,2-Dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3,7-dimethyl-7-methoxyoctyl) benzoylamino) phenyl] Titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexylbenzoylamino) phenyl [Phenyl] titanium etc. can also be used.

Further, among organic titanium compounds and the like, as organic compounds containing a zirconium atom and compounds containing a hafnium atom, (cyclopentadienyl) trimethylzirconium, (cyclopentadienyl) triphenylzirconium, (cyclopentadienyl) tril Benzylzirconium, (cyclopentadienyl) trichlorozirconium, (cyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) dimethyl (methoxy) zirconium, cyclopentadienylmethyldichlorozirconium, (methylcyclopentadienyl) trimethyl Zirconium, (Methyl cyclopentadienyl) triphenyl zirconium, (Methyl cyclopentadienyl) tribenzyl zirconium, (Methyl cyclopentadienyl) trichlorosil (Methylcyclopentadienyl) dimethyl (methoxy) zirconium, (dimethylcyclopentadienyl) trimethylzirconium, (trimethylcyclopentadienyl) trimethylzirconium, (trimethylsilylcyclopentadienyl) trimethylzirconium, (tetramethylcyclopenta) Dienyl) trimethylzirconium, (pentamethylcyclopentadienyl) trimethylzirconium, (pentamethylcyclopentadienyl) triphenylzirconium, (pentamethylcyclopentadienyl) tribenzylzirconium, (pentamethylcyclopentadienyl) trichloro Zirconium, (pentamethylcyclopentadienyl) trimethoxyzirconium, (pentamethylcyclopentadienyl) dimethyl ( X) zirconium, (cyclopentadienyl) triethyl zirconium, (cyclopentadienyl) tripropyl zirconium, (cyclopentadienyl) trineopentyl zirconium, (cyclopentadienyl) tri (diphenylmethyl) zirconium, (cyclopenta) Dienyl) dimethylhydridozirconium, (cyclopentadienyl) triethoxyzirconium, (cyclopentadienyl) triisopropoxyzirconium, (cyclopentadienyl) triphenoxyzirconium, (cyclopentadienyl) dimethylisopropoxyzirconium, ( Cyclopentadienyl) diphenylisopropoxyzirconium, (cyclopentadienyl) dimethoxychlorozirconium, (cyclopentadienyl) methoxydichlorozil Conium, (cyclopentadienyl) diphenoxychlorozirconium, (cyclopentadienyl) phenoxydichlorozirconium, (cyclopentadienyl) tri (phenyldimethylsilyl) zirconium, (n-butylcyclopentadienyl) dimethyl-n- Butoxy zirconium, (benzyl cyclopentadienyl) di-m-tolyl methyl zirconium, (trifluoromethyl cyclopentadienyl) tribenzyl zirconium, (diphenyl cyclopentadienyl) dinorbornyl methyl zirconium, (tetraethyl cyclopentadi (Enyl) tribenzyl zirconium, (pentatrimethylsilyl cyclopentadienyl) tribenzyl zirconium, (pentamethylcyclopentadienyl) trineopentyl zirconium, ( Tamethylcyclopentadienyl) methyldichlorozirconium, (pentamethylcyclopentadienyl) triethoxyzirconium, (pentamethylcyclopentadienyl) triphenoxyzirconium, (pentamethylcyclopentadienyl) methoxydichlorozirconium, (pentamethyl) Cyclopentadienyl) diphenoxychlorozirconium, (pentamethylcyclopentadienyl) phenoxydichlorozirconium, (indenyl) trimethylzirconium, (indenyl) tribenzylzirconium, (indenyl) trichlorozirconium, (indenyl) trimethoxyzirconium,

(Indenyl) triethoxy zirconium, bis (cyclopentadienyl) dimethyl zirconium, bis (cyclopentadienyl) diphenyl zirconium, bis (cyclopentadienyl) diethyl zirconium, bis (cyclopentadienyl) dibenzyl zirconium, bis ( Cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) dichlorozirconium (bis (cyclopentadienyl) zirconium dichloride), bis (cyclopentadienyl) dihydridozirconium, bis (cyclopentadienyl) chlorohydridozirconium Bis (methylcyclopentadienyl) dimethylzirconium, bis (methylcyclopentadienyl) dibenzylzirconium, bis (methylcyclopentadienyl) dichlorodi Conium, bis (pentamethylcyclopentadienyl) dimethylzirconium, bis (pentamethylcyclopentadienyl) dibenzylzirconium, bis (pentamethylcyclopentadienyl) dichlorozirconium, bis (pentamethylcyclopentadienyl) chloromethyl Zirconium, bis (pentamethylcyclopentadienyl) hydridomethylzirconium, (cyclopentadienyl) (pentamethylcyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) dineopentyl zirconium, bis (cyclopentadienyl) ) Di-m-tolyl zirconium, bis (cyclopentadienyl) di p-tolyl zirconium, bis (cyclopentadienyl) bis (diphenylmethyl) zirconium, bis (cyclopenta) Enyl) dibromozirconium, bis (cyclopentadienyl) methylchlorozirconium, bis (cyclopentadienyl) ethylchlorozirconium, bis (cyclopentadienyl) cyclohexylchlorozirconium, bis (cyclopentadienyl) phenylchlorozirconium, bis (Cyclopentadienyl) benzylchlorozirconium, bis (cyclopentadienyl) hydridomethylzirconium, bis (cyclopentadienyl) methoxychlorozirconium,

Bis (cyclopentadienyl) ethoxychlorozirconium, bis (cyclopentadienyl) (trimethylsilyl) methylzirconium, bis (cyclopentadienyl) bis (trimethylsilyl) zirconium, bis (cyclopentadienyl) (triphenylsilyl) methyl Zirconium, bis (cyclopentadienyl) (tris (dimethylsilyl) silyl) methylzirconium, bis (cyclopentadienyl) (trimethylsilyl) (trimethylsilylmethyl) zirconium, bis (methylcyclopentadienyl) diphenylzirconium, bis (ethyl) Cyclopentadienyl) dimethylzirconium, bis (ethylcyclopentadienyl) dichlorozirconium, bis (propylcyclopentadienyl) dimethylzirconium, bis Pill cyclopentadienyl) dichlorozirconium, bis (n-butylcyclopentadienyl) dichlorozirconium, bis (t-butylcyclopentadienyl) bis (trimethylsilyl) zirconium, bis (hexylcyclopentadienyl) dichlorozirconium, bis (Cyclohexylcyclopentadienyl) dimethylzirconium, bis (dimethylcyclopentadienyl) dimethylzirconium, bis (dimethylcyclopentadienyl) dichlorozirconium, bis (dimethylcyclopentadienyl) ethoxychlorozirconium, bis (ethylmethylcyclopenta) Dienyl) dichlorozirconium, bis (propylmethylcyclopentadienyl) dichlorozirconium, bis (butylmethylcyclopentadienyl) dichlorozyl , Bis (trimethylcyclopentadienyl) dichlorozirconium, bis (tetramethylcyclopentadienyl) dichlorozirconium, bis (cyclohexylmethylcyclopentadienyl) dibenzylzirconium, bis (trimethylsilylcyclopentadienyl) dimethylzirconium, bis (Trimethylsilylcyclopentadienyl) dichlorozirconium, bis (trimethylgermylcyclopentadienyl) dimethylzirconium, bis (trimethylgermylcyclopentadienyl) diphenylzirconium, bis (trimethylstannylcyclopentadienyl) dimethylzirconium, bis (Trimethylstannylcyclopentadienyl) dibenzylzirconium, bis (trifluoromethylcyclopentadienyl) dimethy Zirconium, bis (trifluoromethylcyclopentadienyl) dinorbornylzirconium, bis (indenyl) dibenzylzirconium, bis (indenyl) dichlorozirconium, bis (indenyl) dibromozirconium, bis (tetrahydroindenyl) dichlorozirconium, Bis (fluorenyl) dichloro zirconium, (propyl cyclopentadienyl) (cyclopentadienyl) dimethyl zirconium, (cyclohexylmethyl cyclopentadienyl) (cyclopentadienyl) dibenzyl zirconium, (pentatrimethylsilyl cyclopentadienyl) ( Cyclopentadienyl) dimethylzirconium, (trifluoromethylcyclopentadienyl) (cyclopentadienyl) dimethylzirconium, ethylenebi (Indenyl) dimethyl zirconium, ethylene bis (indenyl) dichloro zirconium, ethylene bis (tetrahydro indenyl) dimethyl zirconium, ethylene bis (tetrahydro indenyl) dichloro zirconium, dimethyl silylene bis (cyclopentadienyl) dimethyl zirconium, dimethyl silylene bis ( Cyclopentadienyl) dichlorozirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) dimethylzirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) dichlorozirconium, [phenyl (methyl) methylene] (9- Fluorenyl) (cyclopentadienyl) dimethylzirconium, diphenylmethylene (cyclopentadienyl) (9-fluorenyl) dimethy Zirconium, ethylene (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclohexylidene (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclopentylidene (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium Cyclobutylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylene bis (2,3,5-trimethylcyclopentadienyl) Dimethylzirconium, dimethylsilylene bis (2,3,5-trimethylcyclopentadienyl) dichlorozirconium, dimethylsilylene bis (indenyl) dichlorozirconium, methylene bis Cyclopentadienyl) dimethylzirconium, methylenebis (cyclopentadienyl) di (trimethylsilyl) zirconium,

Methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) dimethyl zirconium, methylene (cyclopentadienyl) (fluorenyl) dimethyl zirconium, ethylene bis (cyclopentadienyl) dimethyl zirconium, ethylene bis (cyclopentadienyl) Dibenzyl zirconium, ethylene bis (cyclopentadienyl) dihydrido zirconium, ethylene bis (indenyl) diphenyl zirconium, ethylene bis (indenyl) methyl chloro zirconium, ethylene bis (tetrahydro indenyl) di benzyl zirconium, isopropylidene Enyl) (methylcyclopentadienyl) dichlorozirconium, isopropylidene (cyclopentadienyl) (octahydrofluorenyl) dihydric Lido zirconium, dimethyl silylene bis (cyclopentadienyl) dineopentyl zirconium, dimethyl silylene bis (cyclopentadienyl) dihydrido zirconium, dimethyl silylene bis (methyl cyclopentadienyl) dichloro zirconium, dimethyl silylene bis (dimethyl cyclopenta) Dienyl) dichlorozirconium, dimethylsilylene bis (tetrahydroindenyl) dichlorozirconium, dimethylsilylene (cyclopentadienyl) (fluorenyl) dichlorozirconium, dimethylsilylene (cyclopentadienyl) (fluorenyl) dihydridozirconium, dimethylsilylene (methyl) Cyclopentadienyl) (fluorenyl) dihydridozirconium, dimethylsilylene bis (3-trimethylsilylcyclo) Ntajieniru) dihydride zirconium, dimethylsilylene bis (indenyl) dimethyl zirconium, diphenylsilylene bis (indenyl) dichlorozirconium, it may be mentioned phenylmethyl (indenyl) dichlorozirconium. Moreover, the compound etc. which substituted the zirconium atom of these compounds by the hafnium atom can also be used.

The content of the organic titanium compound or the like is preferably 0.1 to 30% by mass with respect to the total solid content of the composition of the present invention. The lower limit is more preferably 1.0% by mass or more, further 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, further preferably 15% by mass or less, still more preferably 10% by mass or less, and particularly preferably 5% by mass or less.
One or two or more organic titanium compounds can be used. When using 2 or more types, it is preferable that a total amount is the said range.
In the composition of the present invention, the mass ratio of the content of the organic titanium compound etc. to the content of the thermal base generator is preferably 100: 1 to 1: 100, and 90:10 to 10:90. The ratio is more preferably 40:60 to 20:80. Such a range makes it possible to achieve higher ring closure rates at low temperatures of the polymer precursor and higher glass transition temperatures.

In the composition of the present invention, incorporation of an organic titanium compound or the like makes it possible to achieve a higher ring closure rate at a low temperature of the heterocycle-containing polymer precursor and a higher glass transition temperature. An especially high effect can be acquired by making this compounding quantity into said range.

<Other additives>
The thermosetting resin composition of the present invention may contain various additives, for example, thermal acid generators, sensitizing dyes, chain transfer agents, surfactants, if necessary, as long as the effects of the present invention are not impaired. Higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet light absorbers, aggregation inhibitors, etc. can be blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the composition.

<< Thermal acid generator >>
The thermosetting resin composition of the present invention may contain a thermal acid generator. The thermal acid generator generates an acid upon heating, promotes cyclization of the polymer precursor and further improves the mechanical properties of the cured film. Examples of the thermal acid generator include compounds described in paragraph 0059 of JP-A-2013-167742.

0.01 mass part or more is preferable with respect to 100 mass parts of polymer precursors, and, as for content of a thermal acid generator, 0.1 mass part or more is more preferable. By containing 0.01 mass part or more of thermal acid generators, since a crosslinking reaction and cyclization of a polymer precursor are accelerated | stimulated, the mechanical property and chemical resistance of a cured film can be improved more. In addition, 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 from the viewpoint of the electrical insulation of the cured film.
The thermal acid generator may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes said range.

<< sensitizing dye >>
The thermosetting resin composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs specific actinic radiation to be in an electronically excited state. The sensitizing dye in the electronically excited state is brought into contact with a heat curing accelerator, a thermal radical polymerization initiator, a photo radical polymerization initiator and the like to produce actions such as electron transfer, energy transfer, heat generation and the like. As a result, the heat curing accelerator, the thermal radical polymerization initiator, and the photo radical polymerization initiator undergo a chemical change and decompose to form a radical, an acid or a base. The details of the sensitizing dye can be referred to the description of paragraphs 0161 to 0163 of JP-A-2016-027357, the contents of which are incorporated herein.

When the thermosetting resin composition of the present invention contains a sensitizing dye, the content of the sensitizing dye is 0.01 to 20% by mass based on the total solid content of the thermosetting resin composition of the present invention. Is preferably 0.1 to 15% by mass, and more preferably 0.5 to 10% by mass. The sensitizing dyes may be used alone or in combination of two or more.

<< chain transfer agent >>
The thermosetting resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in Polymer Dictionary Third Edition (edited by the Polymer Society of Japan, 2005), pp. 683-684. As a chain transfer agent, for example, a compound group having SH, PH, SiH, and GeH in the molecule is used. These can donate hydrogen to a low activity radical to form a radical or be oxidized and then deprotonated to form a radical. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazole, etc.) can be preferably used.

When the thermosetting resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the thermosetting resin composition of the present invention. Part is preferable, 1 to 10 parts by mass is more preferable, and 1 to 5 parts by mass is more preferable. The chain transfer agent may be used alone or in combination of two or more. When two or more chain transfer agents are used, the total is preferably in the above range.

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

When the thermosetting resin composition of the present invention has a surfactant, the content of the surfactant is 0.001 to 2.0 mass with respect to the total solid content of the thermosetting resin composition of the present invention %, Preferably 0.005 to 1.0% by mass. The surfactant may be used alone or in combination of two or more. When two or more surfactants are used, the total is preferably in the above range.

<< Higher fatty acid derivatives >>
In the thermosetting resin composition of the present invention, a higher fatty acid derivative such as behenic acid or behenic acid amide is added to prevent polymerization inhibition caused by oxygen, and the composition is dried in the process of drying after coating. It may be unevenly distributed on the surface.
When the thermosetting resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is 0.1 to 10% by mass with respect to the total solid content of the thermosetting resin composition of the present invention Is preferred. The higher fatty acid derivative may be used alone or in combination of two or more. When two or more higher fatty acid derivatives are used, the total is preferably in the above range.

<Restrictions on other contained substances>
From the viewpoint of coated surface properties, the water 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 particularly preferably less than 0.6% by mass.

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, except for the above-mentioned Group 4 metal. More preferably, less than 0.5 mass ppm is particularly preferred. Metals to be inhibited include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are included, the total of these metals is preferably in the above range.
Moreover, as a method of reducing the metal impurities contained unintentionally in the thermosetting resin composition of this invention, the raw material with few metal contents is selected as a raw material which comprises the thermosetting resin composition of this invention Filtering the raw material constituting the thermosetting resin composition of the present invention, lining the inside of the apparatus with polytetrafluoroethylene or the like, and performing distillation under conditions that minimize contamination as much as possible I can mention the method.

The thermosetting resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, from the viewpoint of wiring corrosion, in consideration of the use as a semiconductor material. Particularly preferred is less than mass ppm. Among them, those less than 5 mass ppm are preferable, those less than 1 mass ppm are more preferable, and less than 0.5 mass ppm is more preferable. The halogen atom includes a chlorine atom and a bromine atom. It is preferable that the sum total of a chlorine atom and a bromine atom, or a chloride ion and a bromide ion is respectively in the above range.

A conventionally known storage container can be used as a storage container of the thermosetting resin composition of the present invention. In addition, as the storage container, in order to suppress the mixing of impurities into the raw materials and the composition, the inner wall of the container is made of a multilayer bottle consisting of 6 kinds of resin and 6 layers of resin, and 6 kinds of resin with 7 layers structure It is also preferred to use a bottle which has been As such a container, for example, the container described in JP-A-2015-123351 can be mentioned.

<Preparation of composition>
The thermosetting resin composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited, and can be carried out by a conventionally known method.
The thermosetting resin composition of the present invention comprises a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, an amine compound, an acidic compound, and a solvent, and the pKa of the conjugate acid of the amine compound and the acidic compound It is exemplified that it includes mixing so that pKa of and the range of Formula 1 become.
Further, the thermoplastic resin of the present invention comprises a polymer precursor selected from 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 It is exemplified that the method includes mixing such that the pKa of the conjugate acid of the amine compound and the pKa of the acidic compound are in the range of Formula 1.
Moreover, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and particles in the composition. 1 micrometer or less is preferable, 0.5 micrometer or less is more preferable, and 0.1 micrometer or less is further more preferable. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be one previously washed with an organic solvent. In the filter filtration step, a plurality of filters may be connected in series or in parallel. When multiple types of filters are used, filters with different pore sizes and / or different materials may be used in combination. In addition, various materials may be filtered multiple times. In the case of multiple filtration, circulation filtration may be used. Moreover, you may pressurize and filter. When pressurizing and filtering, the pressure applied is preferably 0.05 MPa or more and 0.3 MPa or less.
In addition to filtration using a filter, removal of impurities using an adsorbent may be performed. Filter filtration may be combined with impurity removal treatment using an adsorbent. A known adsorbent can be used as the adsorbent. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

Cured Film, Laminate, Semiconductor Device, and Method of Manufacturing the Same
Next, a cured film, a laminate, a semiconductor device, and a method of manufacturing them will be described.
The cured film of the present invention is formed by curing the thermosetting resin composition of the present invention. The film thickness of the cured film of the present invention can be, for example, 0.5 μm or more, and can be 1 μm or more. Moreover, as an upper limit, it can be 100 micrometers or less, and can also be 30 micrometers or less.

Two or more layers of the cured film of the present invention may be laminated to form a laminate. The embodiment having a metal layer between the cured films is preferable for the laminate having two or more layers of the cured film of the present invention. Such a metal layer is preferably used as a metal wiring such as a rewiring layer.

As an applicable field | area of the cured film of this invention, the insulating film of a semiconductor device, the interlayer insulation film for rewiring layers, a stress buffer film etc. are mentioned. In addition, forming a pattern by etching a sealing film, a substrate material (a base film or a cover lay of a flexible printed substrate, an interlayer insulating film), or an insulating film for mounting application as described above may be mentioned. For these applications, for example, Science & Technology Co., Ltd. “High Polyimide Function and Applied Technology” April 2008, Masaaki Enomoto / Supervised, CMC Technical Library “Basic and Development of Polyimide Material” November 2001, etc. You can refer to it.

The cured film according to the invention can also be used for the production of printing plates, such as offset printing plates or screen printing plates, for use in the etching of molded parts, for the production of protective lacquers and dielectric layers in electronics, in particular in microelectronics.

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 heating the layer-formed thermosetting resin composition at 50 to 500 ° C. . When photosensitivity is imparted to the thermosetting resin composition, preferably, an exposure step of exposing after the layer forming step and an exposing step of exposing the thermosetting resin composition layer (resin layer) are performed. And a development process step of performing development processing. After this development, the exposed resin layer can be further cured by heating preferably at 50 to 500 ° C. (more preferably, 150 to 400 ° C.). In addition, when using the thermosetting resin composition which provided photosensitivity as mentioned above, a composition is hardened by exposure beforehand, desired processing (for example, following lamination) is given as needed after that. And can be further cured by heating.

The method for producing a laminate of the present invention includes the method for producing a cured film of the present invention. According to the method for producing a laminate of the present invention, after the formation of the cured film, the layer forming step and the heating step of the thermosetting resin composition or the photosensitivity is given again after the formation of the cured film. In such a case, it is preferable to perform the layer formation step, the exposure step, and the development treatment step (additional heating step, if necessary) again in the order described above. In particular, it is preferable to carry out each of the above steps two to five times sequentially (ie, three to six times in total). By laminating the cured film in this manner, a laminate can be obtained. In the present invention, in particular, it is preferable to provide a metal layer on the portion where the cured film is provided.
Details of these will be described below.

<< layer formation process >>
The manufacturing method according to a preferred embodiment of the present invention includes a layer forming step of applying a thermosetting resin composition to a substrate to form a layer.
The type of substrate can be appropriately determined depending on the application, but a semiconductor production substrate such as silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, quartz, glass, optical film, ceramic material, vapor deposited film, magnetic film No particular limitation is imposed on a reflection film, a metal substrate such as Ni, Cu, Cr, or Fe, paper, an SOG (Spin On Glass), a TFT (thin film transistor) array substrate, an electrode plate of a plasma display panel (PDP), or the like. In the present invention, in particular, a semiconductor production substrate is preferable, and a silicon substrate is more preferable.
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 is a substrate.
As a means to apply a thermosetting resin composition to a board | substrate, application is preferable.
Specifically, as means for application, dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spray coating method, spin coating method, slit coating method, And an inkjet method. From the viewpoint of the uniformity of the thickness of the thermosetting resin composition layer, the spin coating method, the slit coating method, the spray coating method, and the inkjet method are more preferable. A resin layer having a desired thickness can be obtained by adjusting the solid content concentration and application conditions appropriately according to the method. Also, the coating method can be appropriately selected depending on the shape of the substrate, and if it is a circular substrate such as a wafer, spin coating method, spray coating method, ink jet method etc. are preferable, and if it is a rectangular substrate, slit coating method, spray coating method, ink jet The law is preferred. In the case of the spin coating method, for example, it can be applied at a rotational speed of 500 to 2000 rpm for about 10 seconds to 1 minute.

<< Drying process >>
The manufacturing method of this invention may include the process of drying in order to remove a solvent after layer-forming process, after forming a thermosetting resin composition layer. The preferred drying temperature is 50 to 150 ° C., more preferably 70 ° C. to 130 ° C., and still more preferably 90 ° C. to 110 ° C. The drying time is, for example, 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 3 to 7 minutes.

<< exposure step >>
The production method of the present invention may include an exposure step of exposing the thermosetting resin composition layer. The exposure dose is not particularly limited as long as the thermosetting resin composition can be cured, but for example, irradiation with 100 to 10000 mJ / cm ² is preferable in terms of exposure energy at a wavelength of 365 nm, and 200 to 8000 mJ / cm ² irradiation It is more preferable to do.
The exposure wavelength can be appropriately determined in the range of 190 to 1000 nm, preferably 240 to 550 nm.
The exposure wavelength is (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g line (wavelength 436 nm), h Line (wavelength 405 nm), i line (365 nm wavelength), broad (3 wavelengths of g, h, i line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer Laser (wavelength: 157 nm), (5) extreme ultraviolet light; EUV (wavelength: 13.6 nm), (6) electron beam, etc. may be mentioned. For the thermosetting resin composition of the present invention, in particular, exposure with a high pressure mercury lamp is preferable, and in particular, exposure with i-ray is preferable. Thereby, particularly high exposure sensitivity can be obtained.

<< Development processing process >>
The manufacturing method of the present invention may include a development treatment step of developing the exposed thermosetting resin composition layer. By performing development, in the case of the negative type, the non-exposed portion (non-exposed portion) is removed, and in the case of the positive type, the exposed portion (exposed portion) is removed. The development method is not particularly limited as long as it can form a desired pattern, and, for example, development methods such as paddle, spray, immersion, and ultrasonic waves can be employed.
Development is performed using a developer. The developer can be used without particular limitation as long as the unexposed area (non-exposed area) is removed. The developer preferably contains an organic solvent. In the present invention, the developer preferably contains an organic solvent having a ClogP of −1 to 5, and more preferably an organic solvent having a ClogP of 0 to 3. ClogP can be obtained as a calculated value by inputting a structural formula in ChemBioDraw.
The organic solvent is, for example, esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone Ε-caprolactone, δ-valerolactone, alkyl alkyl oxyacetate (eg methyl alkyl oxyacetate, ethyl alkyl oxy acetate, butyl alkyl oxy acetate (eg methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, Ethyl ethoxyacetate etc.), 3-alkyloxypropionic acid alkyl esters (eg methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate etc etc. (eg methyl 3-methoxypropionate, 3-methoxypropionate) Ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate etc.), 2-alkyloxypropionic acid alkyl esters (eg: methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2 2-Propyl alkyl oxypropionate etc. (eg methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate etc.), 2- Methyl alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate etc.), pyruvate Methyl, pyruvine Ethyl, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether Methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. As ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene Dimethyl sulfoxide is preferably mentioned as the sulfoxides.
In the present invention, cyclopentanone and γ-butyrolactone are particularly preferable, and cyclopentanone is more preferable.
The developer preferably has 50% by mass or more of the organic solvent, more preferably 70% by mass or more of the organic solvent, and still more preferably 90% by mass or more of the organic solvent. Further, 100% by mass of the developer may be an organic solvent.

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

<< Heating process >>
The production method of the present invention preferably includes a step of heating after the layer forming step, the drying step, or the developing step. In the heating step, the cyclization reaction of the polymer precursor proceeds. In addition, although the composition of the present invention may contain a radically polymerizable compound other than the polymer precursor, curing of the radically polymerizable compound other than the unreacted polymer precursor can be advanced at this step. The heating temperature (maximum heating temperature) in the heating step is 50 to 500 ° C., preferably 50 to 450 ° C., more preferably 140 to 400 ° C., and still more preferably 160 to 350 ° C.
The heating is preferably performed at a temperature rising rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, still more preferably 3 to 10 ° C./min. By setting the temperature rising rate to 2 ° C./min or more, excessive volatilization of the amine can be prevented while securing the productivity, and by setting the temperature rising rate to 12 ° C./min or less, the cured film Residual stress can be relieved.
The temperature at the start of heating is preferably 20 ° C. to 150 ° C., more preferably 20 ° C. to 130 ° C., and still more preferably 25 ° C. to 120 ° C. The temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature is started. For example, when the thermosetting resin composition is applied onto a substrate and then dried, the temperature is the temperature after drying, for example, 30 to 200 ° C. than the boiling point of the solvent contained in the thermosetting resin composition. It is preferable to raise the temperature gradually from a low temperature.
The heating time (heating time at the maximum 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, the heating temperature is preferably 180 ° C. to 320 ° C., and more preferably 180 ° C. to 260 ° C., from the viewpoint of adhesion between the layers of the cured film. The reason is not clear, but at this temperature, it is considered that the ethynyl groups of the polymer precursor between layers proceed with the crosslinking reaction.

The heating may be performed stepwise. As an example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min, held at 180 ° C. for 60 minutes, raised from 180 ° C. to 200 ° C. at 2 ° C./min, held at 200 ° C. for 120 minutes And the like may be performed. 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 the pretreatment step, it is also preferable to conduct the treatment while irradiating with ultraviolet light as described in U.S. Pat. No. 9,159,547. It is possible to improve the characteristics of the film by such a pretreatment process. The pretreatment step may be performed for a short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps, for example, the pretreatment step 1 may be performed in the range of 100 to 150 ° C., and then the pretreatment step 2 may be performed in the range of 150 to 200 ° C.
Furthermore, it may be cooled after heating, and in this case, the cooling rate is preferably 1 to 5 ° C./minute.

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

<< metal layer formation process >>
The production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the thermosetting resin composition layer after development processing.
As the metal layer, existing metal species can be used without particular limitation, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified, copper and aluminum are more preferable, copper is more preferable. More preferable.
The formation method of a metal layer does not have a limitation in particular, The existing method can be applied. For example, the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and methods combining these may be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electrolytic plating may be mentioned.
The thickness of the metal layer is preferably 0.1 to 50 μm, and more preferably 1 to 10 μm at the thickest part.

<< lamination process >>
The production method of the present invention preferably further includes a lamination step.
In the laminating step, the layer forming step and the heating step, or when the photosensitivity is imparted to the thermosetting resin composition, the layer forming step, the exposure step, and the development processing step are the same. It is a series of steps including performing in order. It goes without saying that the laminating step may further include the above-mentioned drying step, heating step and the like.
When the lamination step is further performed after the lamination step, the surface activation treatment step may be further performed after the heating step, after the exposure step, or after the metal layer forming step. Plasma treatment is exemplified as the surface activation treatment.
The lamination step is preferably performed 2 to 5 times, and more preferably 3 to 5 times.
For example, a configuration having three or more and seven or less resin layers such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer is preferable, and three or more and five or less layers are more preferable.
That is, in the present invention, in particular, after the metal layer is provided, the layer forming process and the heating process of the thermosetting resin composition, or the thermosetting resin composition is photosensitive so as to cover the metal layer. It is preferable to perform the layer formation step, the exposure step, and the development treatment step (additional heating step, if necessary) in the above order when applying. By alternately performing the laminating step of laminating the thermosetting resin composition layer (resin) and the metal layer forming step, the thermosetting resin composition layer (resin layer) and the metal layer can be alternately laminated. .

The present invention also discloses a semiconductor device having the cured film or laminate of the present invention. As a specific example of a semiconductor device using the thermosetting resin composition of the present invention for formation of an interlayer insulating film for rewiring layer, the description of paragraphs 0213 to 0218 of JP-A-2016-027357 and the description of FIG. The contents of which are incorporated herein by reference.

Hereinafter, the present invention will be more specifically described by way of examples. The materials, amounts used, proportions, treatment contents, treatment procedures and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, 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 from pyromellitic dianhydride, 4,4′-diaminodiphenyl ether and 3-hydroxybenzyl alcohol]
14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C. for 12 hours) and 16.33 g (131.58 mmol) of 3-hydroxybenzyl alcohol in 50 mL of N-methylpyrrolidone And dried over molecular sieves. The suspension was heated to 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. The reaction mixture was then cooled to -10.degree. C. and 16.12 g (135.5 mmol) of thionyl chloride was added over 10 minutes, keeping the temperature at -10. +-. 4.degree. The viscosity increased during the addition of thionyl chloride. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, a solution of 11.08 g (58.7 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture over 20 minutes at 20-23 ° C. The reaction mixture was then stirred at room temperature overnight. The polyimide precursor resin was then precipitated in 5 liters of water and the water-polyimide precursor resin mixture was stirred at a speed of 5000 rpm for 15 minutes. The polyimide precursor resin was filtered off, stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor resin was dried at 45 ° C. for 3 days under reduced pressure. The polyimide precursor had Mw = 22800 and Mn = 8100.

(Composition example 2)
[Synthesis of polyimide precursor resin A-2 from oxydiphthalic acid dianhydride, 2-hydroxyethyl methacrylate and 4,4′-diaminodiphenyl ether]
20.0 g (64.5 millimoles) of oxydiphthalic acid dianhydride was suspended in 140 mL of diglyme while removing water in a dry reactor equipped with a stirrer, a condenser and a flat bottom joint fitted with an internal thermometer . 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone and 10.7 g (135 mmol) of pyridine were subsequently added and stirred at a temperature of 60 ° C. for 18 hours. Then, the mixture was cooled to −20 ° C., and 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. The mixture was then warmed to room temperature and after stirring for 2 hours, 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to obtain a clear solution. Next, to the obtained transparent liquid, 11.8 g (58.7 mmol) of 4,4′-diaminodiphenyl ether dissolved in 100 mL of NMP was added dropwise over 1 hour. The viscosity increased during the addition of 4,4'-diaminodiphenyl ether. Then, 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added and the mixture was stirred for 2 hours. The polyimide precursor resin was then precipitated in 4 liters of water and the water-polyimide precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes. The polyimide precursor resin was filtered off, stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor resin was dried at 45 ° C. for 3 days under reduced pressure. The polyimide precursor had Mw = 23500 and Mn = 8800.

(Composition example 3)
[Synthesis of polyimide precursor resin A-3 from oxydiphthalic acid dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic acid dianhydride, 2-hydroxyethyl methacrylate and 4,4′-diaminodiphenyl ether]
10.0 g (32.2 mmol) oxydiphthalic acid dianhydride and 3,3 ', 4,4 while removing water in a dry reactor equipped with a stirrer, a condenser and a flat bottom joint fitted with an internal thermometer. 9.47 g (32.3 mmol) of '-biphenyltetracarboxylic acid 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 subsequently added and stirred at a temperature of 60 ° C. for 18 hours. Then, the mixture was cooled to −20 ° C., and 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. The mixture was then warmed to room temperature and after stirring for 2 hours, 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to obtain a clear solution. Next, to the obtained transparent liquid, 11.8 g (58.7 mmol) of 4,4′-diaminodiphenyl ether dissolved in 100 mL of NMP was added dropwise over 1 hour. The viscosity increased during the addition of 4,4'-diaminodiphenyl ether. Then, 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added and the mixture was stirred for 2 hours. The polyimide precursor resin was then precipitated in 4 liters of water and the water-polyimide precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes. The polyimide precursor resin was filtered off, stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor resin was dried at 45 ° C. for 3 days under reduced pressure. The polyimide precursor had Mw = 24300 and Mn = 9500.

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

(Composition 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-dicyclohexylmethylamine was added dropwise over 10 minutes. The resulting solution was concentrated at 35 ° C. under reduced pressure to obtain a salt of N, N-dicyclohexylmethylamine and maleic acid.

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

<Measuring method of molecular weight>
The molecular weight (weight-average molecular weight, number-average molecular weight) of the above-mentioned polymer precursor was defined as a polystyrene conversion value according to gel permeation chromatography (GPC measurement). Specifically, HLC-8220 (trade name: manufactured by Tosoh Corp.) is used, and a guard column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ 3000, and TSKgel Super HZ 2000 (trade names) as columns. : Determined by using Tosoh Co., Ltd.). The eluent was measured using THF (tetrahydrofuran).

<How to determine pKa>
<< Acid compound >>
The pKa of the acidic compound is as follows: 50 mg of the acidic compound is added to 50 mL of water, and 0.01 N aqueous solution of sodium hydroxide is used as a titration solution, using Kyoto Electric Industry Co., Ltd. AT-420 (trade name) potentiometric automatic titrator. It was measured at 25 ° C. The pH at which half the amount of the aqueous sodium hydroxide solution required to neutralize the acid group was added was taken as the pKa of the acidic compound.
<< Amine compound >>
The pKa of the conjugate acid of the amine compound is as follows: 50 mg of the amine compound is added to 50 mL of water, and 0.01 N hydrochloric acid is used as a titration solution, using Kyoto Electric Industry Co., Ltd. AT-420 (trade name) potentiometric automatic titrator. It was measured at 25 ° C. The pH at which half of the amount of hydrochloric acid required to neutralize the amino group was added was designated pKb. The value obtained by subtracting the value of pK [b] from 14 is taken as the pKa of the conjugate acid of the amine value.
<< sulfonic acid compounds etc. >>
Although basically measured by the above method, the pKa of the strong acid sulfonic acid may not be determined by this method. In such a case, literature values measured in water (Angew. Chem. Int. Ed. 2016, 55, 350-354) were adopted.

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

<Preparation of Thermosetting Resin Composition>
Each component described in the following table was blended, pressure filtration was conducted at a pressure of 3.0 MPa through a filter having a pore width of 0.8 μm, to obtain a thermosetting resin composition. In Examples 1 to 62, 70 to 85, and Comparative Examples 4, 5, 9 and 10, the salts synthesized according to the above synthesis examples are added, and in Examples 63 to 69, an amine compound and an acidic compound are added and compared. Examples 2, 3, 7 and 8 added an amine compound or an acidic compound.

<Film thickness change>
<< The film thickness before aging >>
Each thermosetting resin composition described in the following table was applied on a silicon wafer by a spin coating method to form a thermosetting resin composition layer. The silicon wafer to which the obtained thermosetting resin composition layer is applied is dried at 100 ° C. for 5 minutes on a hot plate to obtain a uniform thermosetting resin composition layer of about 15 μm thickness on the silicon wafer. The This value was taken as the film thickness before aging.
<< The film thickness after aging >>
Each thermosetting resin composition described in the following table is put in a glass container, sealed, allowed to stand in an environment of 25 ° C. for 14 days, and spind using the same rotation number as when the film thickness before aging was determined. It was applied on a silicon wafer by a coating method to form a thermosetting resin composition layer. The silicon wafer to which the obtained thermosetting resin composition layer was applied was dried at 100 ° C. for 5 minutes on a hot plate to obtain a uniform thermosetting resin composition layer on the silicon wafer. The film thickness of the resulting thermosetting resin composition layer was measured in the same manner as described above, and this value was taken as the film thickness after aging.
<< Thickness change rate >>
The film thickness change rate was calculated by the following equation.
Change in film thickness [%] = | film thickness before aging-film thickness after aging | film thickness before aging * 100
Thickness change rate
A less than 10%
B 10% or more and less than 15% C 15% or more and less than 20% D 20% or more

<Film strength>
Each thermosetting resin composition described in the following table was applied on a silicon wafer by a spin coating method to form a thermosetting resin composition layer. The silicon wafer to which the obtained thermosetting resin composition layer is applied is dried at 100 ° C. for 5 minutes on a hot plate to obtain a uniform thermosetting resin composition layer of about 15 μm thickness on the silicon wafer. The The obtained thermosetting resin composition layer (resin layer) was heated at a temperature rising rate of 10 ° C./min under a nitrogen atmosphere, and after reaching 250 ° C., it was heated for 3 hours. The cured resin layer (cured film) was immersed in a 4.9% hydrofluoric acid solution to peel the cured film from the silicon wafer. The peeled cured film was punched using a punching machine to prepare a test piece having a width of 3 mm and a sample length of 30 mm. Using the tensile tester (Tensileon), the obtained test piece is JIS-K6251 in an environment of 25 ° C and 65% RH (relative humidity) in the longitudinal direction of the film at a crosshead speed of 300 mm / min. It measured according to. The evaluation was carried out five times each, and the average value of the elongation at break (break elongation) when the film was broken was used.
A 60% or more B 55% or more less than 60% C 50% or more less than 55% D less than 50%

<Adhesiveness>
Each thermosetting resin composition described in the following table was applied on a copper wafer by a spin coating method to form a thermosetting resin composition layer. The copper wafer to which the obtained thermosetting resin composition layer is applied is dried at 100 ° C. for 5 minutes on a hot plate to obtain a uniform thermosetting resin composition layer having a thickness of about 15 μm on the copper wafer. The The temperature of the obtained thermosetting resin composition layer is raised at a heating rate of 10 ° C./min under a nitrogen atmosphere, and after reaching 250 ° C., the cured film is formed on a copper wafer by heating for 3 hours. It formed. On this substrate, a cross cut test was carried out by cutting slits at intervals of 1 mm according to JIS K5600-5-6: 1999, and the adhesion between the cured film and the copper wafer was evaluated.
A Total area of cured film peeled off from copper wafer is less than 2% B Total area of cured film peeled off from copper wafer is 2% to less than 5% C Total area of cured film peeled off from copper wafer is 5% to 10% Less than D Total area of cured film peeled off from copper wafer is 10% or more

<Corrosion (Cu corrosion)>
Each thermosetting resin composition described in the following table was applied on a copper wafer by a spin coating method to form a thermosetting resin composition layer. The copper wafer to which the obtained thermosetting resin composition layer is applied is dried at 100 ° C. for 5 minutes on a hot plate to obtain a uniform thermosetting resin composition layer having a thickness of about 15 μm on the copper wafer. The The temperature of the obtained thermosetting resin composition layer is raised at a heating rate of 10 ° C./min under a nitrogen atmosphere, and after reaching 250 ° C., the cured film is formed on a copper wafer by heating for 3 hours. It formed. This substrate is introduced into a constant temperature and humidity layer for 24 hours at a temperature of 85 ° C. and a humidity of 85%, and the corrosion occurrence location is observed with an optical microscope, and the corrosion occurrence location with respect to the area of the surface of the copper wafer on which the cured film is provided. It was determined what percentage of the area was.
A 5% less B 5% more than 10% C 10% more than 20% D 20% more

<Resolution>
Among the respective thermosetting resin compositions described in the following table, one containing a photo radical polymerization initiator (photosensitive resin composition) is applied on a copper wafer by a spin coating method to form a thermosetting resin composition layer did. The silicon wafer to which the obtained thermosetting resin composition layer is applied is dried at 100 ° C. for 5 minutes on a hot plate to obtain a uniform thermosetting resin composition layer of about 15 μm thickness on the silicon wafer. The
The thermosetting resin composition layer was exposed using a aligner (Karl-Suss MA150 [trade name]) through a mask having a line and space pattern (step: 5 to 20 μm). The exposure was performed with a high pressure mercury lamp, and was irradiated at 500 mJ / cm ^{2 in} terms of exposure energy at a wavelength of 365 nm.
The thermosetting resin composition layer after exposure was dissolved in cyclopentanone for 75 seconds and paddle development was performed. The line width of the developed site was evaluated according to the following criteria. If the exposure width of the base substrate after development is within ± 10% of the mask size, it is judged that the corresponding line width has been resolved, and the smaller the resolved line width, the smaller the light irradiation portion and the light This represents that the difference in solubility in the developing solution from the non-irradiated part is large, which is a preferable result.
A line width that can be resolved is 5 μm or more and less than 10 μm
B-resolved line width is 10 μm or more and less than 15 μm
C The resolved line width is more than 15μm or no image appears

<Glass transition temperature (Tg)>
Each thermosetting resin composition was pressure-filtered through a filter with a pore width of 0.8 μm at a pressure of 0.3 MPa, and then 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 uniform thermosetting resin composition layer with a film thickness of 10 μm on the silicon wafer. The thermosetting resin composition layer on the silicon wafer was exposed on the entire surface with an exposure energy of 400 mJ / cm ² using a stepper (Nikon NSR 2005 i9C) to obtain a resin layer. However, when the thermosetting resin composition which does not contain a radical photopolymerization initiator was used, exposure was not performed. Furthermore, the resin layer was heated at 200 ° C. for 3 hours, and then 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). 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 becomes maximum. The temperature of the resin layer is raised from 0 ° C. to 350 ° C. with a temperature increase rate of 5 ° C./min, strain at a strain angle of 0.1 degree is applied to the resin layer in a cycle of 100 Hz, and Tg is measured The following criteria were evaluated.
A: 270 ° C. or more B: 260 ° C. or more 270 ° C. C: 250 ° C. or more 260 ° C. or less D: 240 ° C. or more 250 ° C. or less E: 230 ° C. or more 240 ° C. or less F: 220 ° C. or more 230 ° C. or less G: 220 ° C.

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

(B) Amine Compounds The respective amine compounds listed in the table were adopted.

(C) Acidic compounds Each acid compound listed in the table was adopted

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

(E) Photo radical polymerization initiator (all are trade names)
OXE-1: IRGACURE OXE 01 (manufactured by BASF)
OXE-2: IRGACURE OXE 02 (manufactured by BASF)
NCI-831: NCI-831 (made by ADEKA Corporation)

(F) Radically polymerizable compound (all are trade names)
SR-209: SR-209 (made by Sartmar Inc.)
SR-231: SR-231 (made by Sartmar Inc.)
SR-239: SR-239 (made by Sartmar Inc.)

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

(H) Metal Adhesion Improver H-1: Following Compound H-2: Following Compound H-3: Following Compound

Et represents an ethyl group.

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

(J) Curing accelerator J-1: the following compound J-2: the following compound J-3: the following compound

(K) Organic compound organics TC-100 containing a group 4 element, manufactured by Matsumoto Fine Chemical Co., Ltd. titanium diisopropoxy bis (acetylacetonate)

Organics TC-401, titanium tetraacetylacetonate manufactured by Matsumoto Fine Chemical Co., Ltd.

Organics TC-710, manufactured by Matsumoto Fine Chemical Co., Ltd. Titanium diisopropoxy bis (ethyl acetoacetate)

Organics TC-201, manufactured by Matsumoto Fine Chemical Co., Ltd. Titanium di-2-ethylhexoxybis (2-ethyl-3-hydroxyhexoxide)

Organics TC-245, manufactured by Matsumoto Fine Chemical Co., Ltd. Titanium octylene glycolate

Organics TC-150, manufactured by Matsumoto Fine Chemical Co., Ltd. Zirconium tetraacetylacetonate

Bis (cyclopentadienyl) titanium dichloride

Bis (cyclopentadienyl) titanium dimethyl

Bis (cyclopentadienyl) zirconium dichloride

Bis (cyclopentadienyl) hafnium dichloride

IRGACURE 784

As apparent from the results in the above table, using an amine compound and an acidic compound, one half (A-pKa) of the sum of the pKa of the conjugate acid of the amine compound and the pKa of the acidic compound is 3.5 to 7.1. It was found that the thermosetting resin composition in the range of (1) was excellent in suppressing film thickness change, and that the strength of the cured film was high (Examples 1 to 85). In addition, all the samples of the examples were able to satisfy the requirements for use with respect to adhesion, corrosion resistance of copper, and resolution when photosensitivity was imparted.
On the other hand, those containing neither an amine compound nor an acidic compound (Comparative Examples 1 to 3 and 6 to 8) and A pKa less than 3.5 (Comparative Examples 4 and 9), 7.1 even if both of them are included With the super (Comparative Examples 5 and 10), the suppression of film thickness change and the film strength become inferior.

Example 100
The thermosetting resin composition of Example 48 was applied to a silicon wafer by spin coating. The silicon wafer coated with the thermosetting resin composition layer was dried at 100 ° C. for 5 minutes on a hot plate to form a uniform thermosetting resin composition layer of 15 μm thickness 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 is exposed to an exposure energy of 500 mJ / cm ² through a mask having a hole of 10 μm in diameter. Exposed. The resin layer was developed with cyclopentanone for 60 seconds to form holes with a diameter of 10 μm. Next, the temperature was raised at a temperature rising rate of 10 ° C./min under a nitrogen atmosphere, and after reaching 250 ° C., heating was performed for 3 hours to obtain a cured film (final cured film). After cooling to room temperature, a copper foil layer (metal layer) with a thickness of 2 μm was formed on the surface of the cured film by vapor deposition so as to cover the hole portion, and unnecessary portions of the copper foil layer were removed by dry etching. . Furthermore, from the filtration of the thermosetting resin composition to the heating of the patterned film for 3 hours in the same manner as above, using the same kind of thermosetting resin composition again on the surface of the metal layer and the cured film The procedure was carried out again, and as shown in FIG. 1, a laminate of 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 denote a cured film, 301 to 303 denote a metal layer, 401 to 403 denote a groove formed between the cured film and the cured film, and 500 denotes a laminate.
Moreover, when the semiconductor device was manufactured using this interlayer insulation film for rewiring layers, it confirmed that it operate | moveed without a problem.

201-204: Cured film 301-303: Metal layer 401-403: Groove 500: Laminate

Claims

A polymer precursor selected from 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,
Containing solvent and
A thermosetting resin composition in which the pKa of the conjugate acid of the amine compound and the pKa of the acidic compound are in the range of Formula 1 below;
3.5 ≦ (pKa of conjugate acid of amine compound + pKa of acidic compound) /2≦7.1 (Equation 1).
The thermosetting resin composition according to claim 1, wherein the amount of the acid group of the acidic compound is 0.9 to 3.0 equivalents relative to the amount of the amino group of the amine compound.
The thermosetting resin composition according to claim 1 or 2, wherein the molecular weight of the amine compound is 120 to 1000.
The thermosetting resin composition according to any one of claims 1 to 3, wherein the amine compound is represented by the following formula (B1):

R B1 to R B3 each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms, and may be linked to each other to form a ring; provided that all of R B1 to R B3 are hydrogen atoms There is no such thing.
R B1 and R B2 in the above formula (B1) are each independently a linear or branched alkyl group having 1 to 6 carbon atoms, a cyclopentyl group or a cyclohexyl group; R B3 is a hydrogen atom or a carbon number of 1 The thermosetting resin composition according to claim 4, which is a linear or branched alkyl group of -6, a cyclopentyl group, a cyclohexyl group or a pyridyl group.
The heat according to any one of claims 1 to 5, wherein in the amine compound, the number of atoms connecting the nitrogen atom and the carbon atom of the carbon atom farthest from the nitrogen atom is 2 to 5, Curable resin composition.
The thermosetting resin composition according to any one of claims 1 to 6, wherein the pKa of the acidic compound is 2 or less.
The thermosetting resin composition according to any one of claims 1 to 7, wherein the acidic compound is represented by any one of the following formulas (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 any one of claims 1 to 8, wherein the molecular weight of the acidic compound is 60 to 500.
The thermosetting resin composition according to any one of claims 1 to 9, wherein the polyimide precursor has a repeating unit represented by the 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, and 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 any one of claims 1 to 11, further comprising a photo radical polymerization initiator.
The thermosetting resin composition according to claim 12, wherein the photo radical polymerization initiator is an oxime compound.
The thermosetting resin composition according to any one of claims 1 to 13, further comprising a radically polymerizable compound.
The thermosetting resin composition according to any one of claims 1 to 14, further comprising an organic compound containing a Group 4 element.
The thermosetting resin composition according to claim 15, wherein the group 4 element is at least one element selected from the group consisting of titanium, zirconium and hafnium.
The thermosetting resin composition according to claim 15 or 16, 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 any one of claims 1 to 17, which is for forming an interlayer insulating film for rewiring layer.
A cured film formed from the thermosetting resin composition according to any one of claims 1 to 18.
A laminate comprising two or more layers of the cured film according to claim 19.
The laminate according to claim 20, having 3 to 7 layers of the cured film.
The layered product according to claim 20 which has a metal layer between said hardening films.
A layer forming step of applying a thermosetting resin composition according to any one of claims 1 to 18 to a substrate to form a layer, and a temperature of 50 to 500 ° C. of the layer formed thermosetting resin composition. And a heating step of heating the film.
A layer forming step of applying a thermosetting resin composition according to any one of claims 1 to 18 to a substrate to form a layer, an exposure step of exposing the layer-formed thermosetting resin composition, and A cured film comprising: a development processing step of developing the exposed thermosetting resin composition; and a heating step of heating the exposed thermosetting resin composition at a temperature of 50 to 500 ° C. Production method.
A laminate comprising a step of forming a cured film according to the method for producing a cured film according to claim 23 or 24 and then forming a cured film according to the method for producing a cured film according to claim 23 or 24 Production method.
A semiconductor device comprising the cured film according to claim 19 or the laminate according to any one of claims 20 to 22.
A method of manufacturing a semiconductor device, wherein the cured film according to claim 19 or the laminated body according to any one of claims 20 to 22 is processed into a semiconductor device.
A polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, an amine compound, an acidic compound, and a solvent The pKa of the conjugate acid of the amine compound and the pKa of the acidic compound are in the range of Formula 1 below A method of producing a thermosetting resin composition comprising mixing to become
3.5 ≦ (pKa of conjugate acid of amine compound + pKa of acidic compound) /2≦7.1 (Equation 1).