WO2020080217A1

WO2020080217A1 - Resin composition, cured film, laminate body, cured film production method, and semiconductor device

Info

Publication number: WO2020080217A1
Application number: PCT/JP2019/039779
Authority: WO
Inventors: 慶福原; 健太山▲ざき▼
Original assignee: 富士フイルム株式会社
Priority date: 2018-10-19
Filing date: 2019-10-09
Publication date: 2020-04-23
Also published as: JPWO2020080217A1; JP7078744B2; TWI824035B; TW202028304A

Abstract

This resin composition contains at least one type of resin selected from the group consisting of a polyimide precursor, polyimide, a polybenzoxazole precursor and polybenzoxazole, and a compound B with a pKa of greater than or equal to 5 and containing a group that generates a basic group by heating, and a group represented by formula (b1). Formula (b1): -M(R^1)(R2)(R3) M represents Si, etc., R^{1-R3 independently represent Rb1 or ORb1, and Rb1 represents a hydrocarbon group with 1-10 hydrogens. A cured film using said resin composition, a laminate body, a cured film production method and a semiconductor device are also provided.}

Description

Resin composition, cured film, laminate, method for producing cured film, and semiconductor device

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

Since resins such as polyimide and polybenzoxazole have excellent heat resistance and insulating properties, they are used in the insulating layers of electronic devices. Further, since polyimide and polybenzoxazole have low solubility in a solvent, they are applied to a support or the like in the state of a precursor (polyimide precursor or polybenzoxazole precursor) before the cyclization reaction, and then heated. It is also practiced to cyclize a polyimide precursor or a polybenzoxazole precursor to form a cured film.

Patent Document 1 describes an invention relating to a resin composition containing a polymer precursor such as a polyimide precursor or a polybenzoxazole precursor, and a thermal base generator.

International Publication No. 2015/199219

With the technique of Patent Document 1 described above, the storage stability of a resin composition containing a polymer precursor such as a polyimide precursor or a polybenzoxazole precursor can be improved.
On the other hand, further research and development is required to meet the recent diversified required properties required for resin compositions containing these polymer precursors and the like. For example, it is desired to further improve the storage stability of the resin composition and the adhesion and reliability of the cured film obtained with a metal or the like.

Therefore, an object of the present invention is to provide a resin composition, a cured film, a laminate, a method for producing a cured film, and a semiconductor device which have good storage stability and can form a cured film having excellent adhesion and reliability. The purpose is to

The present inventor has made diligent studies on a resin composition containing at least one resin selected from the group consisting of a polyimide precursor, a polyimide, a polybenzoxazole precursor and a polybenzoxazole, and a predetermined compound described below. The inventors have found that the above object can be achieved by further adding, and have completed the present invention. The present invention provides the following.

<1> at least one resin selected from the group consisting of a polyimide precursor, a polyimide, a polybenzoxazole precursor and a polybenzoxazole,
A compound B having a Pka of 5 or more, each containing a group which forms a basic group when heated and a group represented by the following formula (b1),
A resin composition containing:
-M ¹ (R ¹ ) (R ² ) (R ³ ) ... (b1)
In formula (b1), M ¹ represents Si, Ti or Zr, R ¹ to R ³ each independently represent Rb ¹ or ORb ¹ , and Rb ¹ is a hydrocarbon having 1 to 10 carbon atoms. Represents a group.
<2> The resin composition according to <1>, wherein R ¹ to R ³ of formula (b1) each independently represent ORb ¹ , and Rb ¹ represents a hydrocarbon group having 1 to 10 carbon atoms. ..
<3> The resin composition according to <1> or <2>, wherein M ^{1 in the} formula (b1) represents Si.
<4> The resin composition according to any one of <1> to <3>, in which the basic group generation temperature of the compound B is 160 ° C. or higher.
<5> The group generated by heating to form a basic group is at least one selected from a heterocyclic group containing a nitrogen atom, an amide group, a urea group, an isocyanate group, a urethane group, an alohanate group, a buret group and an imide group. The resin composition according to any one of <1> to <4>, which contains the group of.
<6> The group which a basic group forms by heating contains a heterocyclic group containing a nitrogen atom and at least one group selected from —OCO— and COO—, or an amide group, The resin composition according to any one of <1> to <4>, containing at least one group selected from a urea group, an isocyanate group, a urethane group, an alohanate group, a buret group, and an imide group.
<7> Compound B is a resin composition according to any one of <1> to <6>, which is a compound represented by the following formula (I):

In formula (I), A ¹ represents a group generated by heating to generate a basic group, L ¹ represents a single bond or a divalent linking group, M ¹ represents Si, Ti or Zr, and R 1 ¹ to R ³ each independently represent Rb ¹ or ORb ¹ , and Rb ¹ represents a hydrocarbon group having 1 to 10 carbon atoms.
<8> The resin composition according to any one of <1> to <7>, which contains the compound B in an amount of 0.01 to 5% by mass based on the total solid content of the resin composition.
<9> The resin composition according to any one of <1> to <8>, in which the resin contains at least one selected from a polyimide precursor and a polybenzoxazole precursor.
<10> The resin composition according to any one of <1> to <9>, which further contains a photoradical polymerization initiator.
<11> The resin composition according to <10>, wherein the radical photopolymerization initiator contains an oxime compound.
<12> The resin composition according to any one of <1> to <11>, which is used for forming an interlayer insulating film for a redistribution layer.
<13> A cured film obtained by curing the resin composition according to any one of <1> to <12>.
<14> A laminate having two or more cured films according to <13> and having a metal layer between the two cured films.
<15> A method for producing a cured film, which includes a film forming step of forming a film by applying the resin composition according to any one of <1> to <12> to a substrate.
<16> The method for producing a cured film according to <15>, which includes an exposure step of exposing the film and a development step of developing the film.
<17> The method for producing a cured film according to <15> or <16>, which includes a step of heating the film at 80 to 450 ° C.
<18> A semiconductor device having the cured film according to <13> or the laminate according to <14>.

According to the present invention, it is possible to provide a resin composition, a cured film, a laminate, a method for producing a cured film, and a semiconductor device, which can form a cured film having good storage stability and excellent adhesion and reliability.

The details of the present invention will be described below. In the present specification, “to” is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value.

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

[Resin composition]
The resin composition of the present invention,
At least one resin selected from the group consisting of a polyimide precursor, a polyimide, a polybenzoxazole precursor and a polybenzoxazole;
A compound B having a Pka of 5 or more, each containing a group which forms a basic group when heated and a group represented by the formula (b1) described later;
It is characterized by containing.

By containing the compound B in the resin composition of the present invention, a cured film having good storage stability and excellent adhesion and reliability can be formed. Since this compound B has a pKa of 5 or more, it is possible to suppress the progress of the reaction of the resin during storage of the resin composition, and as a result, a resin composition having excellent storage stability can be obtained. In addition, this compound contains a group (hereinafter, also referred to as a specific functional group) which is formed by heating to form a basic group and a group represented by the formula (b1) described later, thereby closely adhering to a substrate or the like. It is possible to form a cured film having excellent properties and reliability. That is, the group represented by the formula (b1) contained in the compound B interacts with the substrate and the like by the heating at the time of forming the cured film to perform the coupling reaction, and the specific functional group contained in the compound B is also generated. It is presumed that the basic group generated from the above interacts with the resin to form a bond, and as a result, a cured film having excellent adhesiveness can be formed. Furthermore, when a polyimide precursor or polybenzoxazole precursor is used as the resin, it is presumed that the basic group generated from the compound B can accelerate the cyclization reaction of these precursors. Therefore, the adhesiveness with the substrate can be significantly improved, and the excellent adhesiveness is maintained even after the reliability test such as exposing the cured film formed on the substrate to a high temperature and high humidity environment for a long time. It is also possible to significantly improve the reliability of the cured film. Furthermore, mechanical properties such as elongation of the cured film can be improved.

Since the resin composition of the present invention can form a cured film having excellent adhesion and reliability, it can be preferably used as a resin composition for forming an interlayer insulating film for a rewiring layer.

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

<Resin>
The resin composition in the present invention contains at least one resin selected from the group consisting of a polyimide precursor, a polyimide, a polybenzoxazole precursor and a polybenzoxazole. The resin used in the resin composition of the present invention preferably contains at least one selected from a polyimide precursor and a polybenzoxazole precursor, and more preferably contains a polyimide precursor. Hereinafter, the polyimide precursor and the polybenzoxazole precursor are collectively referred to as a polymer precursor.

The resin composition containing the polymer precursor tends to undergo a reaction such as cyclization of the polymer precursor during storage to easily change the viscosity of the resin composition. By using the compound B, excellent storage stability can be obtained even when a resin containing a polymer precursor is used. Therefore, when a polyimide precursor or a polybenzoxazole precursor is used as the resin, the effect of the present invention can be remarkably obtained. Especially, when a polyimide precursor is used as the resin, the effect of the present invention is more easily obtained.

<< polyimide precursor >>
The polyimide precursor is preferably a polyimide precursor containing a constitutional unit represented by the following formula (1). By using such a polyimide precursor, a resin composition having more excellent film strength can be obtained.

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

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

<<<< R ¹¹¹ >>>>
R ¹¹¹ represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, a heteroaromatic group, or a group consisting of a combination thereof, which has 2 to 20 carbon atoms. A straight-chain aliphatic group, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group composed of a combination thereof An aromatic group having 6 to 20 carbon atoms is more preferable.
R ¹¹¹ is preferably derived from a diamine. Examples of the diamine used for producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamine. Only one diamine may be used, or two or more diamines may be used.
Specifically, the diamine is a straight-chain 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. And a diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable. The following are mentioned as an example of an aromatic group.

In the formula, A is 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—, —S A group selected from (═O) ₂ —, —NHCO—, and a combination thereof is preferable, and a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, and —O— , —C (═O) —, —S— and —SO ₂ — are more preferred, and —CH ₂ —, —O—, —S—, —SO ₂ —, —C ( It is more preferably a divalent group selected from the group consisting of CF ₃ ) ₂ — and —C (CH ₃ ) ₂ —.

Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1 , 3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4- Aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; meta and paraphenylenediamine, diaminotoluene, 4,4'- and 3 , 3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether 4,4'- and 3,3'-diaminodiphenylmethane, 4,4'- and 3,3'-diaminodiphenyl sulfone, 4,4'- and 3,3'-diaminodiphenyl sulfide, 4,4 ' -And 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl (4,4'-diamino-2,2 '-Dimethylbiphenyl), 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4-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- Sus (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino -3-hydroxyphenyl) sulfone, 4,4'-diaminoparaterphenyl, 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-diaminoanthraquinone, 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- (3 ', 5'-diaminobenzoyloxy) ethyl methacrylate, 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-diaminonaphtha Amine, diaminobenzotrifluoride, 1,3-bis (4-aminophenyl) hexafluoropropane, 1,4-bis (4-aminophenyl) octafluorobutane, 1,5-bis (4-aminophenyl) decafluoro Pentane, 1,7-bis (4-aminophenyl) tetradecafluoroheptane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (2-amino Phenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3 , 5-Bis (trifluoromethyl) phenyl] hexafluoropropane, parabis (4-amino-2-trifluorome Tylphenoxy) benzene, 4,4′-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4′-bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4,4′- Bis (4-amino-2-trifluoromethylphenoxy) diphenyl sulfone, 4,4′-bis (3-amino-5-trifluoromethylphenoxy) diphenyl sulfone, 2,2-bis [4- (4-amino- 3-trifluoromethylphenoxy) phenyl] hexafluoropropane, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminobiphenyl, 4,4′-diamino-2,2′-bis (trifluoro From methyl) biphenyl, 2,2 ', 5,5', 6,6'-hexafluorotolidine and 4,4'-diaminoquaterphenyl It includes at least one diamine barrel.

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

In addition, diamines having at least two or more alkylene glycol units in the main chain are also preferred examples. Diamines containing one or both of ethylene glycol chains and propylene glycol chains in one molecule in combination of two or more, and more preferably diamines containing no aromatic ring are preferred. Specific examples include Jeffamine (registered trademark) KH-511, Jeffarmin (registered trademark) ED-600, Jeffermin (registered trademark) ED-900, Jeffermin (registered trademark) ED-2003, Jeffermin (registered trademark) ) EDR-148, Jeffamine (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (manufactured by HUNTSMAN), 1- (2- (2- (2-aminopropoxy)) Examples include, but are not limited to, ethoxy) propoxy) propan-2-amine, 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propan-2-amine, and the like.
Jeffarmin® KH-511, Jeffarmin® ED-600, Jeffarmin® ED-900, Jeffarmin® ED-2003, Jeffarmin® EDR-148, The structure of Jeffamine® EDR-176 is shown below.

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

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

From the viewpoint of i-ray transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, the divalent organic group represented by the formula (61) is more preferable from the viewpoints of i-ray transmittance and availability.

R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group, or It is a trifluoromethyl group.
The monovalent organic group represented by R ⁵⁰ to R ⁵⁷ is an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluorine atom having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Alkyl groups and the like.

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

Examples of the diamine compound giving the structure of formula (51) or (61) include dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 2,2 Examples thereof include'-bis (fluoro) -4,4'-diaminobiphenyl and 4,4'-diaminooctafluorobiphenyl. You may use these 1 type or may use it in combination of 2 or more type.

<<<< R ¹¹⁵ >>>>
R ¹¹⁵ in the formula (1) represents a tetravalent organic group. The tetravalent organic group is preferably a group containing an aromatic ring, and more preferably a group represented by the following formula (5) or formula (6).

R ¹¹² has the same meaning as A and the preferred range is also the same.

Specific examples of the tetravalent organic group represented by R ¹¹⁵ in the formula (1) include a tetracarboxylic acid residue remaining after the acid dianhydride group is removed from the tetracarboxylic dianhydride. The tetracarboxylic dianhydride may be used alone or in combination of two or more. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).

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

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

Further, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below are also preferred examples.

<<<< R ¹¹³ and R ¹¹⁴ >>>>
R ¹¹³ and R ¹¹⁴ in formula (1) each independently represent a hydrogen atom or a monovalent organic group. It is preferable that at least one of R ¹¹³ and R ¹¹⁴ contains a radical polymerizable group, and it is more preferable that both contain a radical polymerizable group. The radically polymerizable group is a group capable of undergoing a crosslinking reaction by the action of a radical, and a preferable example thereof is a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth) acryloyl group and a group represented by the following formula (III).

In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and a methyl group is more preferable.
In the formula (III), R ²⁰¹ is an alkylene group having 2 to 12 carbon atoms, —CH ₂ CH (OH) CH ₂ — or a (poly) oxyalkylene group having 4 to 30 carbon atoms (the alkylene group has 1 carbon atoms. The number of repetitions is preferably 1 to 12, more preferably 1 to 6, and most preferably 1 to 3). The (poly) oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.
Examples of suitable R ²⁰¹ include ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butanediyl group, 1,3-butanediyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group. , —CH ₂ CH (OH) CH ₂ —, and an ethylene group, a propylene group, a trimethylene group, 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.

As a preferred embodiment of the polyimide precursor in the present invention, an aliphatic group, an aromatic group and an aryl having 1, 2 or 3, preferably 1 acid group as the monovalent organic group of R ¹¹³ or R ^114. An alkyl group etc. are mentioned. Specific examples thereof include an aromatic group having 6 to 20 carbon atoms having an acid group and an arylalkyl group having 7 to 25 carbon atoms having an acid group. More specific examples include a phenyl group having an acid group and a benzyl group having an acid group. The acid group is preferably a hydroxyl group. That is, R ¹¹³ or R ¹¹⁴ is preferably a group having a hydroxyl group.
As the monovalent organic group represented by R ¹¹³ or R ^114, a substituent that improves the solubility of the 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 an organic solvent, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group or an aromatic group, more preferably an alkyl group substituted with an aromatic group.
The alkyl group preferably has 1 to 30 carbon atoms (3 or more in the case of a cyclic group). The alkyl group may be linear, branched or cyclic. Examples of the linear or branched alkyl group include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, octadecyl group. , Isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, and 2-ethylhexyl group. The cyclic alkyl group may be either a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Examples of the polycyclic cyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a camphenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group and a pinenyl group. Is mentioned. As the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described below is preferable.

Specific examples of the aromatic group include a substituted or unsubstituted aromatic hydrocarbon group (the cyclic structure constituting the group includes a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an indene ring, and azulene. Ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene ring, triphenylene ring, etc.) or substituted or unsubstituted aromatic heterocyclic group (group The cyclic structure constituting the fluorene 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, quinolidi Ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, phenothiazine ring Or phenazine ring).

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

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

The constitutional unit represented by the formula (1) is preferably a constitutional unit represented by the formula (1-A) or (1-B).

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 a hydrogen atom or a monovalent group. It represents an organic group, and at least one of R ¹¹³ and R ¹¹⁴ is preferably a group containing a radically polymerizable group, and more preferably a radically polymerizable group.

A ¹¹ , A ¹² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ each independently have a preferable range which is the same as the preferable range of A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ^{114 in} the formula (1). ..
A preferred range of R ¹¹² has the same meaning as ^{R 112} in formula (5), and more preferably among others oxygen atoms.
The bonding position of the carbonyl group in the formula to the benzene ring is preferably 4,5,3 ′, 4 ′ in the formula (1-A). In the formula (1-B), 1,2,4,5 are preferable.

In the polyimide precursor, the constitutional unit represented by the formula (1) may be one type or two or more types. Further, the structural unit represented by the formula (1) may contain a structural isomer. Further, the polyimide precursor may include other types of structural units in addition to the structural units of the above formula (1).

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

The weight average molecular weight (Mw) of the polyimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and further preferably 10,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2000 to 50000, and further preferably 4000 to 25000.
The molecular weight dispersity of the polyimide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.

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

It is preferable that a step of depositing a solid is included in the production of the polyimide precursor. Specifically, solid precipitation can be performed by precipitating the polyimide precursor in the reaction solution in water and dissolving the polyimide precursor in a solvent in which the polyimide precursor is soluble.

<< Polybenzoxazole precursor >>
The polybenzoxazole precursor is preferably a polybenzoxazole precursor containing a structural unit represented by the following formula (2).

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

R ¹²¹ represents a divalent organic group. As the divalent organic group, 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 (preferably having 6 to 22 carbon atoms, 6 to 14 carbon atoms) Is more preferable, and 6 to 12 is particularly preferable). Examples of the aromatic group forming R ¹²¹ include the examples of R ^{111 in} the above formula (1). As the aliphatic group, a linear aliphatic group is preferable. R ¹²¹ is preferably derived from 4,4′-oxydibenzoyl chloride.
In the formula (2), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same meaning as R ¹¹⁵ in the above formula (1), and the preferred range is also the same. R ¹²² is preferably derived from 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group, have the same meaning as R ¹¹³ and R ¹¹⁴ in the above formula (1), and the preferred ranges are also the same.

The polybenzoxazole precursor may contain other types of constitutional units in addition to the constitutional units of the above formula (2).
It is preferable that the polybenzoxazole precursor contains a diamine residue represented by the following formula (SL) as another type of structural unit from the viewpoint of suppressing the occurrence of warpage of the cured film due to ring closure.

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

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

When the precursor contains a diamine residue represented by the formula (SL) as another type of structural unit, it further improves alkali solubility, and further removes an acid dianhydride group from the tetracarboxylic dianhydride. It is preferable to include a tetracarboxylic acid residue remaining afterwards as a constituent unit. Examples of such a tetracarboxylic acid residue include the example of R ¹¹⁵ in the formula (1).

The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and further preferably 10,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2000 to 50000, and further preferably 4000 to 25000.
The polybenzoxazole precursor has a molecular weight dispersity of preferably from 1.5 to 3.5, more preferably from 2 to 3.

<< Polyimide >>
The polyimide is not particularly limited as long as it is a polymer compound having an imide ring, but is preferably a compound represented by the following formula (4), and a compound represented by the following formula (4) More preferably, it is a compound having a radically polymerizable group. Examples of the radically polymerizable group include the radically polymerizable group described in the above section of the polyimide precursor, and the preferable range is also the same.
Formula (4)

In the formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group.

When the polyimide has a radical polymerizable group, the radical polymerizable group may be introduced into at least one of R ¹³¹ and R ¹³² , or the radical polymerizable group may be introduced into the terminal of the polyimide.

Examples of the divalent organic group represented by R ¹³¹ include the same groups as R ¹¹¹ in the formula (1) of the polyimide precursor described above, and the preferred ranges are also the same. Examples of the tetravalent organic group represented by R ¹³² include the same groups as R ¹¹⁵ in the formula (1) of the polyimide precursor described above, and the preferred ranges are also the same.

The imidization ratio of the polyimide is preferably 85% or more, more preferably 90% or more. When the imidization ratio is 85% or more, the film shrinkage due to ring closure that occurs when imidized by heating is reduced, and the occurrence of warpage can be suppressed.

<< polybenzoxazole >>
The polybenzoxazole may be a compound having a benzoxazole ring and is not particularly limited, but is preferably a compound having a repeating unit represented by the following formula (X), represented by the following formula (X). More preferably, it is a compound having a radically polymerizable group. Examples of the radically polymerizable group include the radically polymerizable group described in the above polyimide precursor, and the preferable range is also the same.

In the formula (X), R ¹³³ represents a divalent organic group, and R ¹³⁴ represents a tetravalent organic group.

When the polybenzoxazole has a radical polymerizable group, a radical polymerizable group may be introduced into at least one of R ¹³³ and R ¹³⁴ , or a radical polymerizable group may be introduced into the end of the polybenzoxazole. .

^Examples of the divalent organic group represented by R ¹³³ include an aliphatic or aromatic group. Specific examples include the groups described for R ¹²¹ in the formula (2) of the polybenzoxazole precursor, and the preferred range is also the same. ^Examples of the tetravalent organic group represented by R ¹³⁴ include the groups described for R ¹²² in the formula (2) of the polybenzoxazole precursor, and the preferable range is also the same.

The content of the resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and 40% by mass or more based on the total solid content of the resin composition. More preferably, it is more preferably 50 mass% or more, still more preferably 60 mass% or more, still more preferably 70 mass% or more. The content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, and more preferably 98% by mass or less based on the total solid content of the resin composition. The content is more preferably not more than mass%, and even more preferably not more than 95 mass%.
Further, the content of the polymer precursor (preferably the polyimide precursor) in the resin composition of the present invention is preferably 20% by mass or more and 30% by mass or more based on the total solid content of the resin composition. More preferably, it is more preferably 40 mass% or more, still more preferably 50 mass% or more, even more preferably 60 mass% or more, and even more preferably 70 mass% or more. . Further, the content of the polymer precursor in the resin composition of the present invention is preferably 99.5% by mass or less, and more preferably 99% by mass or less, based on the total solid content of the resin composition. , 98% by mass or less is more preferable, 95% by mass or less is more preferable, and 95% by mass or less is even more preferable.
The resin composition of the present invention may contain only one type of resin, or may contain two or more types of resin. When two or more kinds are contained, the total amount is preferably within the above range.

<Compound B>
The resin composition of the present invention includes a compound B having a pKa of 5 or more, each of which contains a group which forms a basic group when heated and a group which is represented by the formula (b1). Hereinafter, a group which a basic group produces by heating is also referred to as a specific functional group. The group represented by the formula (b1) is also referred to as a group (b1).
-M ¹ (R ¹ ) (R ² ) (R ³ ) ... (b1)
Wherein (b1), ^{M 1} is, Si, represents Ti or ^Zr, R 1 to ^{R 3} each independently represents a Rb ¹ or ORb ^1, Rb ¹ is carbon independently 1 to Represents 10 hydrocarbon groups.

The pKa of the compound B is 5 or more, preferably 8 or more, more preferably 10 or more, further preferably 12 or more, even more preferably 12.5 or more, and 13 or more. Is even more preferable. The upper limit is preferably 20 or less, more preferably 18 or less, still more preferably 15 or less. The pKa of compound B is the value in water at 23 ° C.

The molecular weight of compound B is preferably 100 to 2000. The upper limit is preferably 1900 or less, more preferably 1500 or less, and further preferably 500 or less. The lower limit is preferably 150 or more, more preferably 200 or more, and further preferably 250 or more.

The amine value of compound B is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and further preferably 300 mgKOH / g or less.

The basic group generation temperature of compound B is preferably 160 ° C. or higher, more preferably 170 ° C., and further preferably 180 ° C. or higher. The upper limit of the basic group generation temperature is preferably 300 ° C or lower, more preferably 280 ° C or lower, and further preferably 250 ° C or lower. According to this aspect, since the basic group can be efficiently generated during formation of the cured film, it is possible to form a cured film having excellent adhesion and reliability while maintaining the storage stability of the resin composition. You can That is, the specific functional group contained in the compound B is preferably a group that decomposes at a temperature of 160 ° C. or higher to form a basic group, and a group that decomposes at a temperature of 170 ° C. or higher to form a basic group. Is more preferable, and a group that is decomposed at a temperature of 180 ° C. or higher to form a basic group is further preferable. The upper limit of the temperature is preferably 300 ° C or lower, more preferably 280 ° C or lower, and further preferably 250 ° C or lower.

The specific functional group (group which a basic group is generated by heating) of the compound B is a heterocyclic group containing a nitrogen atom, an amide group, a urea group, an isocyanate group, a urethane group, an alohanate group, a buret group and an imide group. It is preferable that it contains at least one group selected from Examples of the heterocyclic group containing a nitrogen atom include an azole ring group, a pyrrole ring group, an indole ring group, a pyridine ring group, a pyrazole ring group, a diazine ring group, and a benzodiazine ring group.
Preferred embodiments of the specific functional group include the following (1) and (2). Among them, the following embodiment (2) is preferable from the viewpoint of storage stability in a liquid, and more preferably an embodiment containing at least an isocyanate group.
(1) A mode including a heterocyclic group containing a nitrogen atom and at least one group selected from —OCO— and COO—.
(2) An embodiment containing at least one group selected from an amide group, a urea group, an isocyanate group, a urethane group, an alohanate group, a buret group and an imide group.

Next, the group (b1) contained in the compound B will be described.

In the formula (b1), in the formula (b1), M ¹ represents Si, Ti or Zr, and is preferably Si. When M ¹ is Si, the storage stability of the resin composition can be further improved, and the adhesion and reliability of the obtained cured film can be further improved. It is also preferable that M ¹ is Ti or Zr. Preferably, mechanical properties such as elongation of the obtained cured film can be further improved.

In formula (b1), R ¹ to R ³ each independently represent Rb ¹ or ORb ¹ , and Rb ¹ represents a hydrocarbon group having 1 to 10 carbon atoms. Examples of the hydrocarbon group represented by Rb ¹ include an aliphatic saturated hydrocarbon group, an aliphatic unsaturated hydrocarbon group and an aromatic hydrocarbon group. The aliphatic saturated hydrocarbon group and the aliphatic unsaturated hydrocarbon group may be linear, branched or cyclic. As the hydrocarbon group represented by Rb ¹ , an aliphatic saturated hydrocarbon group and an aliphatic unsaturated hydrocarbon group are preferable, and an aliphatic saturated hydrocarbon group is more preferable. The number of carbon atoms in the aliphatic saturated hydrocarbon group is preferably 1-6, more preferably 1-3.

In formula (b1), at least one of R ¹ to R ³ is preferably ORb ¹ . Among them, it is more preferable that R ¹ to R ³ are each independently ORb ¹ because a cured film having more excellent adhesion and reliability can be easily obtained.

The type of bond between M ¹ and R ¹ to R ³ in formula (b1) is not particularly limited, and may be a covalent bond, an ionic bond, or a coordinate bond. Among them, the covalent bond is preferable because a cured film having more excellent adhesion and reliability can be easily obtained.

The compound B used in the present invention is preferably a compound represented by the following formula (I).

In formula (I), A ¹ represents a group generated by heating to generate a basic group, L ¹ represents a single bond or a divalent linking group, M ¹ represents Si, Ti or Zr, and R 1 ¹ to R ³ each independently represent Rb ¹ or ORb ¹ , and Rb ¹ represents a hydrocarbon group having 1 to 10 carbon atoms.

The preferable ranges of M ¹ , R ¹ to R ³ and Rb ¹ of the formula (I) are the same as the above-mentioned ranges.
A ¹ of the formula (I) represents a group which a basic group forms by heating. The preferable range of A ¹ is synonymous with the specific functional group described above. L ^{1 in} formula (I) represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, an alkenylene group, an arylene group, —O—, and a group composed of a combination thereof.

Specific examples of the compound B include compounds having the following structures.

The content of the compound B is preferably 0.01 to 5% by mass based on the total solid content of the resin composition. The upper limit is preferably 4% by mass or less, more preferably 3% by mass or less, further preferably 2% by mass or less, and particularly preferably 1.5% by mass or less. The lower limit is preferably 0.05% by mass or more.
Further, the content of the compound B is preferably 0.02 to 15 parts by mass with respect to 100 parts by mass of the resin. The upper limit is preferably 11 parts by mass or less, more preferably 8 parts by mass or less, and further preferably 6 parts by mass or less. The lower limit is preferably 0.05 part by mass or more, more preferably 0.5 part by mass or more, still more preferably 1 part by mass or more. The compound B may be only one kind or two or more kinds. When two or more kinds are used, the total is preferably within the above range.

<Thermal base generator>
The resin composition of the present invention may further contain a thermal base generator as a component other than the compound B described above. The type of the thermal base generator is not particularly limited, but it is selected from an acidic compound that generates a base when heated to 40 ° C. or higher, and an ammonium salt having an anion having a pKa of 0 to 4 and an ammonium cation. It is preferable to include a thermal base generator containing at least one of
By compounding such a compound, the cyclization reaction of the polymer precursor or the like can be carried out at a low temperature. Further, since the thermal base generator does not generate a base unless heated, it can suppress cyclization of the polymer precursor during storage even when it is made to coexist with the polymer precursor, and has excellent storage stability.

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

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

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

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

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

In the present embodiment, the ammonium salt means a salt of an ammonium cation represented by the following formula (101) or formula (102) and an anion. The anion may be bound to any part of the ammonium cation through a covalent bond and may be present outside the ammonium cation molecule, but may be present outside the ammonium cation molecule. preferable. In addition, that the anion has outside the molecule of the ammonium cation means that the ammonium cation and the anion are not bonded via a covalent bond. Hereinafter, the anion outside the molecule of the cation portion is also referred to as a counter anion.
Expression (101) Expression (102)

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

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

In formulas (Y1-1) to (Y1-5), R ¹⁰¹ represents an n-valent organic group, and R ¹ and R ⁷ have the same meaning as in formula (101) or formula (102).
In formulas (Y1-1) to (Y1-5), Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group, n represents an integer of 1 or more, and m represents an integer of 0 to 5. .

In the present embodiment, the ammonium salt preferably has an anion having a pKa of 0 to 4 and an ammonium cation. The upper limit of the pKa of the anion is more preferably 3.5 or less and even more preferably 3.2 or less. The lower limit is preferably 0.5 or more, more preferably 1.0 or more. When the pKa of the anion is within the above range, the polymer precursor can be cyclized at a lower temperature, and the stability of the resin composition can be improved. When the pKa is 4 or less, the stability of the thermal base generator is good, the generation of base without heating can be suppressed, and the stability of the resin composition is good. When the pKa is 0 or more, the generated base is difficult to neutralize, and the cyclization efficiency of the polymer precursor is good.
The type of anion is preferably one selected from a carboxylate anion, a phenol anion, a phosphate anion and a sulfate anion, and a carboxylate anion is more preferable because the stability of the salt and the thermal decomposability can be compatible. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion.
The carboxylic acid anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxyl groups, and more preferably a divalent carboxylic acid anion. According to this aspect, it is possible to provide a thermal base generator capable of further improving the stability, curability and developability of the resin composition. In particular, the stability, curability and developability of the resin composition can be further improved by using the anion of divalent carboxylic acid.
In the present embodiment, the carboxylic acid anion is preferably an anion of a carboxylic acid having a pKa of 4 or less. The pKa is more preferably 3.5 or less and even more preferably 3.2 or less. According to this aspect, the stability of the resin composition can be further improved.
Here, pKa represents the logarithm of the reciprocal of the dissociation constant of the proton of an acid, and is known as Determination of Organic Structures by Physical Methods (author: Brown, H. C., McDaniel, D. H., Haf Nager, O. Nafliger, O. Hafliger. F. C .; Compilation: Braude, E. A., Nachod, F. C .; Academic Press, New York, 1955), and Data for Biochemical Research (author: Dawson, R. M. R. M. , Clarendon Press, 1959). For compounds not described in these documents, the value calculated from the structural formula using software of ACD / pKa (manufactured by ACD / Labs) is used.

The carboxylate anion is preferably represented by the following formula (X1).

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

In the present embodiment, the electron-withdrawing group means that the Hammett's substituent constant σm exhibits a positive value. Here, σm is as described in Yuho Tsuno, Review of Organic Synthetic Chemistry, Vol. 23, No. 8 (1965) p. 631-642. The electron-withdrawing group in the present embodiment is not limited to the substituents described in the above documents.
Examples of the substituent having a positive σm value include CF ₃ group (σm = 0.43), CF ₃ CO group (σm = 0.63), HC≡C group (σm = 0.21), CH ₂ = CH group (σm = 0.06), Ac group (σm = 0.38), MeOCO group (σm = 0.37), MeCOCH = CH group (σm = 0.21), PhCO group (σm = 0) .34), H ₂ NCOCH ₂ group (σm = 0.06), and the like. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group.

EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).

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

In this embodiment, the carboxylate anion is preferably represented by the following formula (XA).
Formula (XA)

In formula (XA), L ¹⁰ represents a single bond or a divalent linking group selected from an alkylene group, an alkenylene group, an aromatic group, —NR ^X — and a combination thereof, and R ^X represents a hydrogen atom. Represents an alkyl group, an alkenyl group or an aryl group.

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

The following compounds may be mentioned as specific examples of the thermal base generator.

The content of the thermal base generator is preferably 0.1 to 50% by mass based on the total solid content of the resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, still more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less. The thermal base generator can use 1 type (s) or 2 or more types. When two or more kinds are used, the total amount is preferably within the above range.

<Photosensitizer>
The resin composition of the present invention preferably contains a photosensitizer. Examples of the photosensitizer include a photopolymerization initiator, and may further include, for example, a photocuring accelerator.

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

As the radical photopolymerization initiator, any known compound can be used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives, etc. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone compounds, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. Is mentioned. For details of these, the descriptions in paragraphs 0165 to 0182 of JP-A-2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219 can be referred to, and the contents thereof are incorporated herein.

Examples of the ketone compound include the compounds described in paragraph 0087 of JP-A-2005-087611, the contents of which are incorporated herein. In the commercially available product, Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

As the photoradical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, 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 the hydroxyacetophenone initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127 (trade name: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, the compound described in JP-A 2009-191179 in which the absorption maximum wavelength is matched with a wavelength light source of 365 nm or 405 nm can also be used. Examples of the acylphosphine-based initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. In addition, commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: all manufactured by BASF) can be used. Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF).

An oxime compound is more preferred as the photo-radical polymerization initiator. By using the oxime compound, the exposure latitude can be more effectively improved. Oxime compounds are particularly preferable because they have a wide exposure latitude (exposure margin) and also act as a photocuring accelerator. As specific examples of oxime compounds, the compounds described in JP 2001-233842 A, the compounds described in JP 2000-080068 A, and the compounds described in JP 2006-342166 A can be used. Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, and 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. In the resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as the photoradical polymerization initiator. The oxime-based photopolymerization initiator is a compound having 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), Adeka Optimer N-1919 (manufactured by ADEKA, Inc., JP 2012-014052 A) The radical polymerization initiator 2) is also preferably used. Further, TR-PBG-304 (manufactured by Changzhou Power Electronics New Materials Co., Ltd.), ADEKA ARCRUZ NCI-831 and ADEKA ARCRUZ NCI-930 (manufactured by ADEKA Corporation) can also be used. In addition, DFI-091 (manufactured by Daito Chemix Co., Ltd.) can be used.
Furthermore, it is also possible to use an oxime compound having a fluorine atom. Specific examples of such oxime compounds include the compounds described in JP 2010-262028 A, compounds 24, 36 to 40 described in paragraph 0345 of JP-A-2014-500852, and JP 2013-2013 A. The compound (C-3) described in paragraph 0101 of JP-A-164471 can be mentioned.
The most preferable oxime compound includes oxime compounds having a specific substituent described in JP-A 2007-269779 and oxime compounds having a thioaryl group described in JP-A 2009-191061.

The photoradical polymerization initiator is a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triaryl, from the viewpoint of exposure sensitivity. Selected from the group consisting of imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complexes and their salts, halomethyloxadiazole compounds, 3-aryl substituted coumarin compounds. Compounds are preferred. More preferred photoradical polymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, acetophenone compounds, At least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferable, metallocene compounds or oxime compounds are even more preferable, and oxime compounds are more preferable. Are even more preferred.

The photo-radical polymerization initiators are benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone) and other N, N'-tetraalkyl-4,4'-diaminobenzophenones, 2-benzyl. Aromatic ketones such as -2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1 and alkylanthraquinones It is also possible to use quinones condensed with the aromatic ring, a benzoin ether compound such as benzoin alkyl ether, a benzoin compound such as benzoin and alkylbenzoin, and a benzyl derivative such as benzyldimethylketal. Moreover, the compound represented by the following formula (I) can also be used.

In formula (I), R ^I00 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 alkoxyl group having 1 to 12 carbon atoms, a phenyl group, C1-C20 alkyl group, C1-C12 alkoxyl group, halogen atom, cyclopentyl group, cyclohexyl group, C2-C12 alkenyl group, C2-C interrupted by one or more oxygen atoms 18 alkyl group and at least one substituted phenyl group of the alkyl group having 1 to 4 carbon atoms or a biphenyl,, R ^I01 is a group represented by formula (II), the same as R ^I00 R ^I02 to R ^I04 each independently represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or halogen.

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

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

When the photopolymerization initiator is contained, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. %, More preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. The photopolymerization initiator may contain only one type, or may contain two or more types. When two or more photopolymerization initiators are contained, the total amount is preferably within the above range.

<Thermal radical polymerization initiator>
The resin composition of the present invention may contain a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates a radical by the energy of heat and initiates or accelerates the polymerization reaction of the polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the polymer precursor can be progressed together with the cyclization of the polymer precursor, so that higher heat resistance can be achieved. Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP 2008-063554 A.

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

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

The number of radically polymerizable groups contained in the radically polymerizable compound may be 1 or 2 or more, but the radically polymerizable compound preferably has 2 or more radically polymerizable groups, and preferably 3 or more. More preferable. The upper limit is preferably 15 or less, more preferably 10 or less, and further preferably 8 or less.

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

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

Specific examples of the radically polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters thereof, and amides thereof, and preferably, They are esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyhydric amine compounds. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a sulfanyl group with a monofunctional or polyfunctional isocyanate or an epoxy, or a monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines, thiols, and halogen groups. Substitution products of unsaturated carboxylic acid esters or amides having a leaving substituent such as or tosyloxy group with monofunctional or polyfunctional alcohols, amines, and thiols are also suitable. Further, as another example, it is also possible to use a compound group in which unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like is substituted for the above unsaturated carboxylic acid. As specific examples, the descriptions in paragraphs 0113 to 0122 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated in the present specification.

The radical polymerizable compound is also preferably a compound having a boiling point of 100 ° C. or higher under normal pressure. Examples thereof include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol. Poly (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin, trimethylolethane, etc. A compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then converting it into (meth) acrylate, JP-B-48-0417 No. 8, JP-B-50-006034, JP-A-51-37193, urethane (meth) acrylates as described in JP-A-48-64183 and JP-B-49-43191. , Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof, which are described in JP-B-52-30490. You can Further, the compounds described in paragraphs 0254 to 0257 of JP-A 2008-292970 are also suitable. Further, a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated bond can also be mentioned.
In addition, as preferable radically polymerizable compounds other than the above, there are ethylenically unsaturated bonds having a fluorene ring, which are described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, and the like. It is also possible to use a compound having two or more groups having a or a cardo resin.
Further, as other examples, specific unsaturated compounds described in JP-B-46-043946, JP-B-01-040337, and JP-B-01-040336, and JP-A-02-025493 are described. The vinyl phosphonic acid-based compounds can also be used. Further, the compounds containing a perfluoroalkyl group described in JP-A No. 61-022048 can also be used. Furthermore, the Japan Adhesive Association magazine, vol. 20, No. The compounds introduced as photopolymerizable monomers and oligomers on pages 7, 300 to 308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP-A-2005-034964 and the compounds described in paragraphs 0087 to 0131 of WO 2015/199219 can also be preferably used, and the contents thereof are described in the present specification. Incorporated into the book.

Further, compounds described in JP-A-10-062986 as formulas (1) and (2) together with specific examples thereof, which are (meth) acrylated after addition of ethylene oxide or propylene oxide to a polyfunctional alcohol, It can be used as a radically polymerizable compound.

Furthermore, the compounds described in paragraphs 0104 to 0131 of JP-A-2015-18721 can also be used as other radically polymerizable compounds, and the contents thereof are incorporated in the present specification.

As the radically polymerizable compound, dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nippon Kayaku (Nippon Kayaku) Ltd., A-TMMT: Shin-Nakamura Chemical Co., Ltd., dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meta). Acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.), and these (meth) acryloyl groups are mediated by ethylene glycol residues or propylene glycol residues. A bonded structure is preferred. These oligomer types can also be used.

Examples of commercially available radically polymerizable compounds include SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, and SR-209, which is a bifunctional methacrylate having four ethyleneoxy chains, manufactured by Sartomer. 231, 239, DPCA-60, which is a hexafunctional acrylate having 6 pentyleneoxy chains, manufactured by Nippon Kayaku Co., Ltd., TPA-330, which is a trifunctional acrylate having 3 isobutyleneoxy chains, and 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.), UA-306H, UA-306T, UA-306 , AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF Corporation) and the like.

Examples of the radically polymerizable compound include urethane acrylates such as those described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, and JP-B-02-016765. The urethane compounds having an ethylene oxide skeleton described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417 and JP-B-62-039418 are also suitable. Furthermore, as the radically polymerizable compound, compounds having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909 and JP-A-01-105238, 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 and 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 hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to produce an acid. A radically polymerizable compound having a group is more preferable. Particularly preferably, in the radically polymerizable compound in which an unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to have an acid group, the aliphatic polyhydroxy compound is pentaerythritol or dipenta A compound that is erythritol. Examples of commercially available products include polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd. such as M-510 and M-520.
The acid value of the radically polymerizable compound having an acid group is preferably 0.1 to 40 mgKOH / g, particularly preferably 5 to 30 mgKOH / g. When the acid value of the radically polymerizable compound is within the above range, the production and handling properties are excellent, and further, the developability is excellent. Also, the polymerizability is good.

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

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

<<< Compound Having Hydroxymethyl Group, Alkoxymethyl Group or 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).

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

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

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

Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-. PTBP, DML-34X, DML-EP, DML-POP, dimethyltylBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (Sanwa Chemical Co., Ltd.) Manufactured by K.K.), 2,6-dimethyloxymethyl-4-t-butylphenol, 2,6-dimethyloxymethyl-p-cresol, 2,6-diacetyloxymethyl-p-cresol and the like.

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

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

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

Examples of the epoxy compound include bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resin such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether; polymethyl (glycidyl Examples include, but are not limited to, epoxy group-containing silicones such as loxypropyl) siloxane. 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, Epicron (registered trademark) EXA-4710, epicuron (registered trademark) HP-4770, epiclon (registered trademark) EXA-859CRP, epiclon (registered trademark) EXA-1514, epiclon (registered trademark) EXA-4880, epiclon (registered trademark) EXA-4850-150, Epiclon EXA-4850-1000, Epiclon (registered trademark) EXA-4816, Epicron (registered trademark) EXA-4822 (manufactured by DIC Corporation), Licaresin (registered trademark) BEO-60E (Nippon Rika) Ltd.), EP-4003S, EP-4 And the like 00S ((Ltd.) ADEKA). Among these, an epoxy resin containing a polyethylene oxide group is preferable in terms of suppression of warpage and excellent heat resistance. For example, Epiclon (registered trademark) EXA-4880, Epiclon (registered trademark) EXA-4822, and Lycaledin (registered trademark) BEO-60E are preferable because they contain a polyethylene oxide group.

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

<<<< benzoxazine compound (compound having benzoxazolyl group) >>>>
The benzoxazine compound is preferable because it does not generate degas during curing because it is a cross-linking reaction derived from a ring-opening addition reaction and further suppresses thermal contraction to suppress warpage.

Preferred examples of the benzoxazine compound include Ba type benzoxazine, Bm type benzoxazine (manufactured by Shikoku Chemicals Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, and phenol novolac type dihydrobenzoxazine compound. . These may be used alone or in combination of two or more.

When the polymerizable compound is contained, its content is preferably more than 0% by mass and 60% by mass or less based on the total solid content of the resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.
When the radical polymerizable compound is contained, its content is preferably more than 0% by mass and 60% by mass or less based on the total solid content of the resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.
The polymerizable compounds may be used alone or in combination of two or more. When two or more kinds are used in combination, the total amount is preferably within the above range.

<Solvent>
The resin composition of the present invention preferably contains a solvent. Any known solvent can be used as the solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides and amides.
Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone. , Δ-valerolactone, alkyl alkyloxyacetate (eg methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate etc. )), 3-alkyloxypropionic acid alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, 3-methoxypropionate) Acid ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionic acid alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2 -Propyl alkyloxypropionate and the like (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 , Pyruvic acid Chill, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like as preferred.
Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol. Suitable examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.
Preferable examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like.
Examples of suitable aromatic hydrocarbons include toluene, xylene, anisole, and limonene.
Examples of suitable sulfoxides include dimethyl sulfoxide.
Preferred amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like.

From the viewpoint of improving the properties of the coated surface, the solvent is preferably a mixture of two or more kinds.
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- One solvent selected from butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, or composed of two or more solvents Mixed solvents are preferred. The combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

From the viewpoint of coating properties, the content of the solvent is preferably such that the total solid content concentration of the resin composition of the present invention is 5 to 80% by mass, and preferably 5 to 75% by mass. The amount is more preferably 10 to 70% by mass, still more preferably 40 to 70% by mass. The solvent content may be adjusted according to the desired thickness and coating method.
The solvent may contain only 1 type, and may contain 2 or more types. When two or more kinds of solvents are contained, the total amount is preferably within the above range.

<Migration inhibitor>
The resin composition of the present invention preferably further contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress the migration of metal ions derived from the metal layer (metal wiring) into the resin composition layer.
The migration inhibitor is not particularly limited, but a heterocycle (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 sulfanyl groups, hindered phenol compounds , Salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole and benzotriazole can be preferably used, and tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole.

Also, an ion trap agent that traps anions such as halogen ions can be used.

Other migration inhibitors include rust preventives described in paragraph 0094 of JP2013-015701A, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-059656A. The compounds described in Paragraph 0052, the compounds described in Paragraphs 0114, 0116 and 0118 of JP 2012-194520 A, the compounds described in Paragraph 0166 of WO 2015/199219 and the like can be used.

Specific examples of the migration inhibitor include the following compounds.

When the resin composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass% with respect to the total solid content of the resin composition, and 0.05 to 2 It is more preferably 0.0% by mass, and further preferably 0.1 to 1.0% by mass. Only one type of migration inhibitor may be used, or two or more types may be used. When two or more migration inhibitors are used, it is preferable that the total amount thereof is within the above range.

<Polymerization inhibitor>
The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4 ′. -Thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine , N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1 -Nitroso 2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, bis (4 -Hydroxy-3,5-tert-butyl) phenylmethane and the like are preferably used. Further, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compounds described in paragraphs 0031 to 0046 of WO 2015/125469 can also be used. Further, the following compounds can be used (Me is a methyl group).

When the resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5 mass% with respect to the total solid content of the resin composition of the present invention, and 0 The content is more preferably 0.02 to 3% by mass, further preferably 0.05 to 2.5% by mass. Only one type of polymerization inhibitor may be used, or two or more types may be used. When two or more polymerization inhibitors are used, the total is preferably within the above range.

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

<< thermal acid generator >>
The resin composition of the present invention may contain a thermal acid generator. The content of the thermal acid generator is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the resin. By including 0.01 part by mass or more of the thermal acid generator, the crosslinking reaction and the cyclization of the polymer precursor are promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved. 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 even more preferably 10 parts by mass or less, from the viewpoint of electric insulation of the cured film. Only one thermal acid generator may be used, or two or more thermal acid generators may be used. When two or more kinds are used, the total amount is preferably within the above range.

<< sensitizing dye >>
The 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 electron-excited sensitizing dye is brought into contact with a thermal curing accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, and the like, and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the thermosetting accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo a chemical change and decompose to generate a radical, an acid, or a base. For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated herein.

When the resin composition of the present invention contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01 to 20 mass% with respect to the total solid content of the resin composition of the present invention, The amount is more preferably 1 to 15% by mass, further 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 resin composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in Polymer Dictionary, Third Edition (edited by The Polymer Society of Japan, 2005), pages 683-684. As the 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 generate a radical, or can generate a radical by being deprotonated after being oxidized. Particularly, a thiol compound can be preferably used.
Further, as the chain transfer agent, the compounds described in paragraphs 0152 to 0153 of WO 2015/199219 can also be used.

When the resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the resin composition of the present invention, and 1 to 10 parts by mass is more preferable, and 1 to 5 parts by mass is further preferable. Only one type of chain transfer agent may be used, or two or more types may be used. When two or more chain transfer agents are used, it is preferable that the total thereof is within the above range.

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

Further, as the surfactant, the compounds described in paragraphs 0159 to 0165 of WO 2015/199219 can also be used.

When the resin composition of the present invention has a surfactant, the content of the surfactant is preferably 0.001 to 2.0 mass% with respect to the total solid content of the resin composition of the present invention. , And more preferably 0.005 to 1.0 mass%. The surfactant may be only one kind or two or more kinds. When two or more kinds of surfactants are used, it is preferable that the total amount is within the above range.

<< Higher fatty acid derivative >>
The resin composition of the present invention is added with a higher fatty acid derivative such as behenic acid or behenic acid amide in order to prevent polymerization inhibition due to oxygen, and is unevenly distributed on the surface of the composition during the drying process after coating. You may let me.
Further, as the higher fatty acid derivative, the compound described in paragraph 0155 of WO 2015/199219 can also be used.
When the resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10 mass% with respect to the total solid content of the resin composition of the present invention. Only one type of higher fatty acid derivative may be used, or two or more types may be used. When two or more higher fatty acid derivatives are used, the total of them is preferably within the above range.

<Restrictions on other contained substances>
The water content of the resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass from the viewpoint of the properties of the coated surface.

Considering the use as a semiconductor material, the resin composition of the present invention has a halogen atom content of preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and less than 200 mass ppm from the viewpoint of wiring corrosivity. Is more preferable. Among them, those existing in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of the halogen atom include chlorine atom and bromine atom. It is preferable that the total of chlorine atom and bromine atom, or the total of chlorine ion and bromine ion be in the above ranges.

A conventionally known container can be used as a container for the resin composition of the present invention. In addition, as the container, a multi-layer bottle in which the inner wall of the container is composed of 6 kinds of 6 layers of resin, or 6 kinds of resin of 7 layers structure is used for the purpose of suppressing the mixing of impurities into raw materials and compositions. It is also preferable to use a bottle. As such a container, for example, the container described in JP-A-2015-123351 can be mentioned.

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

[Cured Film, Laminated Body, Semiconductor Device, and Manufacturing Method Thereof]
Next, a cured film, a laminated body, a semiconductor device, and a method for manufacturing them will be described.
The cured film of the present invention is obtained by curing the resin composition of the present invention. The thickness of the cured film of the present invention can be, for example, 0.5 μm or more, and can be 1 μm or more. Further, the upper limit value may be 100 μm or less, and may be 30 μm or less. The thickness of the cured film of the present invention is preferably 1 to 30 μm.

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

The fields to which the cured film of the present invention can be applied include insulating films of semiconductor devices, interlayer insulating films for rewiring layers, stress buffer films, and the like. In addition, a sealing film, a substrate material (a base film or a coverlay of a flexible printed board, an interlayer insulating film), or an insulating film for mounting as described above may be patterned by etching. Regarding these applications, for example, Science & Technology Co., Ltd., “High-performance and applied technology of polyimide” April 2008, Masaaki Kakimoto / supervised, CMC Technical Library “Basic and development of polyimide materials”, published November 2011 , "Polyimide Aromatic Polymer Research Society / Edited," Latest Polyimide Basics and Applications, "NTS, August 2010, etc. can be referred to.

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

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

The method for producing a laminate according to a preferred embodiment of the present invention includes the method for producing a cured film of the present invention. According to the method for producing a laminated body of the present embodiment, after the cured film is formed according to the above-described method for producing a cured film, the step (a) or the steps (a) to (c) or (a) is performed again. )-(D) are performed. In particular, it is preferable to perform each of the above steps a plurality of times, for example, 2 to 5 times (ie, 3 to 6 times in total). By laminating the cured films in this manner, a laminated body can be obtained. In the present invention, it is particularly preferable to provide a metal layer on the portion where the cured film is provided, between the cured films, or both. In the production of the laminate, it is not necessary to repeat all the steps (a) to (d), and as described above, at least (a), preferably (a) to (c) or (a) to (d). A laminated body of cured films can be obtained by performing the step (1) a plurality of times.

<Film forming step (layer forming step)>
A manufacturing method according to a preferred embodiment of the present invention includes a film forming step (layer forming step) of applying a resin composition to a substrate to form a film (layer).
The type of substrate can be appropriately determined according to the application, but semiconductor production substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films , A reflective film, a metal substrate of Ni, Cu, Cr, Fe or the like, paper, SOG (Spin On Glass), a TFT (thin film transistor) array substrate, an electrode plate of a plasma display panel (PDP), etc. are not particularly limited. In the present invention, a semiconductor manufacturing substrate is particularly preferable, and a silicon substrate is more preferable. It is also preferable that the substrate is a substrate capable of forming a covalent bond with the compound B by a chemical reaction.
When the resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer serves as the substrate.
As a means for applying the resin composition to the substrate, coating is preferable.
Specifically, as the applying means, a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, a slit coating method, And the inkjet method and the like. From the viewpoint of the uniformity of the thickness of the 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 an appropriate solid content concentration and coating conditions according to the method. In addition, the coating method can be appropriately selected depending on the shape of the substrate. For circular substrates such as wafers, the spin coating method, spray coating method, inkjet method, etc. are preferable, and for rectangular substrates, the slit coating method, spray coating method, inkjet method, etc. The method is preferred. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 2000 rpm for about 10 seconds to 1 minute.

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

<Exposure process>
The production method of the present invention may include an exposure step of exposing the resin composition layer. The exposure amount is not particularly limited as long as the resin composition can be cured, but, for example, 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 is preferable. More preferable.
The exposure wavelength can be appropriately set within the range of 190 to 1000 nm, and is 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 (wavelength 365 nm), broad (3 wavelengths of g, h and i lines), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer Laser (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), (6) electron beam and the like can be mentioned. For the resin composition of the present invention, exposure with a high pressure mercury lamp is particularly preferable, and exposure with i-line is particularly preferable. Thereby, a particularly high exposure sensitivity can be obtained.

<Development process>
The production method of the present invention may include a development treatment step of performing development treatment on the exposed resin composition layer. By developing, the unexposed portion (non-exposed portion) is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and for example, a developing method such as paddle, spray, dipping, ultrasonic wave, etc. can be adopted.
Development is performed using a developer. The developer can be used without particular limitation as long as the unexposed portion (non-exposed portion) is removed. The developer preferably contains an organic solvent, and more preferably the developer contains 90% or more of the organic solvent. In the present invention, the developing solution preferably contains an organic solvent having a ClogP value of -1 to 5, and more preferably an organic solvent having a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting a structural formula in ChemBioDraw.
Examples of the organic solvent include 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 alkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, Ethyl acetate, etc.)), 3-alkyloxypropionic acid alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, 3-methoxypropionate, etc. Ethyl pionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionic acid alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2 -Propyl alkyloxypropionate and the like (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 , Pyruvic acid Cyl, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like 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, and the like, and Examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and aromatic hydrocarbons such as toluene, xylene, anisole and limonene. Preferred examples of the sulfoxides include dimethyl sulfoxide.
In the present invention, cyclopentanone and γ-butyrolactone are particularly preferable, and cyclopentanone is more preferable.
50% by mass or more of the developer is preferably an organic solvent, more preferably 70% by mass or more of the organic solvent, and further preferably 90% by mass or more of the organic solvent. Further, the developing solution may be 100% by mass of an organic solvent.

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

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

The heating may be performed in stages. 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, and held at 200 ° C for 120 minutes. A pretreatment step such as, may be performed. The heating temperature in the pretreatment step is preferably 100 to 200 ° C, more preferably 110 to 190 ° C, and further preferably 120 to 185 ° C. In this pretreatment step, it is also preferable to perform treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547. The characteristics of the film can be improved by such a pretreatment process. The pretreatment step may be performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps. For example, the pretreatment step 1 may be performed in the range of 100 to 150 ° C., and then the pretreatment step 2 may be performed in the range of 150 to 200 ° C.
Further, it may be cooled after heating, and the cooling rate in this case is preferably 1 to 5 ° C./minute.

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

<Metal layer forming step>
The production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the resin composition layer after the development treatment.
The metal layer is not particularly limited, it is possible to use existing metal species, copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified, more preferably copper and aluminum, copper is More preferable.
The method for forming the metal layer is not particularly limited, and an existing method can be applied. For example, the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501 and JP-A-2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a method combining these can be considered. More specifically, a patterning method that combines sputtering, photolithography and etching, and a patterning method that combines photolithography and electrolytic plating can be mentioned.
The thickness of the metal layer is preferably 0.1 to 50 μm, and more preferably 1 to 10 μm in the thickest part.

<Lamination process>
The manufacturing method of the present invention preferably further includes a laminating step.
The laminating step means, on the surface of the cured film (resin layer) or the metal layer, again (a) a film forming step (layer forming step), (b) exposure step, (c) development processing step, (d) heating step. Is carried out in this order. However, the mode may be such that only the film forming step of (a) is repeated. In addition, the heating step (d) may be collectively performed at the end or the middle of the lamination. That is, the steps of (a) to (c) may be repeated a predetermined number of times, and then the heating of (d) may be performed to collectively cure the laminated resin composition layers. Further, (c) the developing step may include (e) the metal layer forming step, and even at this time, even if the heating (d) is performed each time, after the layers are laminated a predetermined number of times, the steps (d) are collectively performed. You may heat. It goes without saying that the laminating step may further include the above-mentioned drying step, heating step and the like as appropriate.
When the laminating step is further performed after the laminating step, a surface activation treatment step may be further performed after the heating step, the exposure step, or the metal layer forming step. A plasma treatment is exemplified as the surface activation treatment.
The laminating step is preferably performed 2 to 5 times, more preferably 3 to 5 times.
For example, it is preferable that the resin layer has 3 or more and 7 or less layers such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, and more preferably 3 or more and 5 layers or less.
In the present invention, it is particularly preferable that after the metal layer is provided, a cured film (resin layer) of the resin composition is further formed so as to cover the metal layer. Specifically, a mode in which (a) film forming step, (b) exposure step, (c) developing step, (e) metal layer forming step, (d) heating step is repeated in this order, or (a) film forming A mode in which the steps, (b) exposure step, (c) development step, (e) metal layer formation step are repeated in this order, and (d) heating step is collectively provided at the end or in the middle is mentioned. By alternately performing the laminating step of laminating the resin composition layer (resin) and the metal layer forming step, the resin composition layer (resin layer) and the metal layer can be laminated alternately.

The present invention also discloses a semiconductor device having the cured film or laminate of the present invention. As specific examples of the semiconductor device in which the resin composition of the present invention is used for forming the interlayer insulating film for the redistribution layer, the description in paragraphs 0213 to 0218 of JP-A-2016-027357 and the description in FIG. 1 can be referred to. These contents are incorporated herein.

The present invention will be described more specifically with reference to the following examples. Materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. "Parts" and "%" are based on mass unless otherwise specified.

<Preparation of resin composition>
The components shown in the following table were mixed to obtain a resin composition.

The raw materials described in the above table are as follows.
(resin)
A-1: Polyimide precursor having the following structure (Mw = 25000)

A-2: Benzoxazole precursor having the above structure (Mw = 25000)

(Coupling agent)
B-1: Compound having the following structure (pKa = 14.45)
B-2: Compound having the following structure (pKa = 12.33)
B-3: Compound having the following structure (pKa = 13.06)
B-4: Compound having the following structure (pKa = 12.96)
B-5: Compound having the following structure (pKa = 14.27)
B-6: Compound having the following structure (pKa = 12.68)
B-7: Compound having the following structure (pKa = 5.99)
B-101: compound having the following structure (pKa = 12.47)
B-102: compound having the following structure (pKa = 14.75)
B-103: compound having the following structure (pKa = 13.22)
B-1 to B-7 are compounds containing a group which forms a basic group when heated. The basic group generation temperature of B-1 to B-7 is 160 ° C or higher.
B-101 to B-103 are compounds that do not contain a group that is heated to generate a basic group.

(Initiator)
C-1: IRGACURE OXE 01 (manufactured by BASF)
C-2: IRGACURE OXE 02 (manufactured by BASF)
C-3: IRGACURE 784 (manufactured by BASF)
C-4: NCI-831 (manufactured by ADEKA Corporation)

(Migration inhibitor)
D-1: 1,2,4-triazole D-2: 1H-tetrazole

(solvent)
E-1: N-methylpyrrolidone E-2: Ethyl lactate E-3: γ-butyrolactone E-4: Dimethyl sulfoxide

(Polymerizable monomer)
F-1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
F-2: SR-209 (manufactured by Arkema)

(Other additives)
G-1: 4-methoxyphenol (polymerization inhibitor)
G-2: 1,4-benzoquinone (polymerization inhibitor)
G-3: Compound of the following structure (thermal base generator)

<Evaluation>
<< Storage stability >>
Immediately after the production, 10 g of the resin composition was sealed in a container (container material: light-shielding glass, capacity: 100 mL), and allowed to stand for 2 weeks in an environment of 25 ° C. and relative humidity of 65%. The viscosity of the resin composition before and after standing was measured with an E-type viscometer (TV-25, Toki Sangyo Co., Ltd.), and the viscosity variation rate was calculated from the following formula. The lower the viscosity variation rate, the higher the storage stability.
Viscosity fluctuation rate (%) = | 100 × {1- (viscosity of resin composition after standing for 2 weeks / viscosity of resin composition before standing)} |
The viscosity was measured at 25 ° C., and other conditions were determined according to JIS Z 8803: 2011.
A: Viscosity variation is less than 1% B: Viscosity variation is 1% or more and less than 3% C: Viscosity variation is 3% or more and less than 5% D: Viscosity variation is 5% or more

<< Adhesion >>
The resin composition was applied in layers by a spin coating method on a copper substrate to form a resin composition layer. The copper substrate to which the obtained resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to form a resin composition layer having a thickness of 20 μm on the copper substrate. This resin composition layer was exposed using a stepper (Nikon NSR 2005 i9C) with an exposure energy of 500 mJ / cm ² using a 100 μm square photomask, and then developed with cyclopentanone for 60 seconds to obtain 100 μm. A tetragonal resin layer was obtained. Furthermore, in a nitrogen atmosphere, the temperature was raised at a temperature rising rate of 10 ° C./min, and after reaching 250 ° C., this temperature was maintained for 3 hours to obtain a cured film.
For a 100 μm square cured film on a copper substrate, at a temperature of 25 ° C. and 65% relative humidity (RH), a bond tester (XYZTEC, Condor Sigma) is used to separate the copper substrate and the cured film. The force was measured. The measurement conditions were a peeling rate of 10 μm / S using a 200 μm needle, and a distance of 2 μm between the copper substrate and the needle.
A: Peeling force is 60 gf or more B: Peeling force is 50 gf or more and less than 60 gf C: Peeling force is 40 gf or more and less than 50 gf D: Peeling force is 40 gf or less

<< Reliability >>
A cured film was formed by the same method as the evaluation of adhesion. The obtained cured film was left to stand in an environment of 121 ° C. and 100% relative humidity (RH) for 1000 hours using a high-acceleration life tester (PC-422R8D, Hirayama Seisakusho) to perform a reliability test. For a 100 μm square cured film on the copper substrate before and after the reliability test, the peeling force between the copper substrate and the cured film was measured using a bond tester (CondorSigma, manufactured by XYZTEC). As the measurement conditions, a 200 μm needle was used and the peeling speed was 10 μm / S, and the distance between the copper substrate and the needle was 2 μm.
The adhesion reduction rate was calculated from the following formula.
Adhesion force reduction rate (%) = 100 × {1- (Peeling force of cured film after reliability test / Peeling force of cured film before reliability test)}
A: Adhesion reduction rate is less than 1% B: Adhesion reduction rate is 1% or more and less than 3% C: Adhesion reduction rate is 3% or more and less than 10% D: Adhesion reduction rate is 10% or more

<< Evaluation of mechanical properties (elongation) >>
A resin composition was spin-coated on a silicon wafer or the like so that the film thickness after curing was about 10 μm, dried, and then heated using a temperature-programmed curing furnace (VF-2000 type, manufactured by Koyo Lindbergh). A cured film was obtained by heating at 180 ° C. for 2 hours in a nitrogen atmosphere. The obtained cured film was cut into a strip having a width of 3 mm using a dicing saw (DAD3350 type, manufactured by DISCO), and then stripped from the silicon wafer using 46% hydrofluoric acid. The elongation of the cured film was measured in accordance with ASTM D882-09 using a tensile tester (UTM-II-20 type, manufactured by Orientec Co., Ltd.). The elongation was judged as follows.
A: Elongation is 60% or more B: Elongation is 50% or more and less than 60% C: Elongation is 40 or more and less than 50% D: Elongation is less than 40%

As shown in the above table, the examples were evaluated for storage stability, adhesion and reliability.

Claims

At least one resin selected from the group consisting of a polyimide precursor, a polyimide, a polybenzoxazole precursor and a polybenzoxazole;
A compound B having a Pka of 5 or more, each containing a group which forms a basic group when heated and a group represented by the following formula (b1),
A resin composition containing:
-M 1 (R 1 ) (R 2 ) (R 3 ) ... (b1)
In formula (b1), M 1 represents Si, Ti or Zr, R 1 to R 3 each independently represent Rb 1 or ORb 1 , and Rb 1 is a hydrocarbon having 1 to 10 carbon atoms. Represents a group.
The resin composition according to claim 1, wherein R 1 to R 3 in the formula (b1) each independently represent ORb 1 , and Rb 1 represents a hydrocarbon group having 1 to 10 carbon atoms.
The resin composition according to claim 1, wherein M 1 in the formula (b1) represents Si.
The resin composition according to any one of claims 1 to 3, wherein the compound B has a basic group generation temperature of 160 ° C or higher.
The group generated by heating the basic group is at least one group selected from a heterocyclic group containing a nitrogen atom, an amide group, a urea group, an isocyanate group, a urethane group, an alohanate group, a buret group and an imide group. The resin composition according to any one of claims 1 to 4, which comprises:
The group which a basic group forms by heating includes a heterocyclic group containing a nitrogen atom and at least one group selected from —OCO— and COO—, or an amide group or a urea group. The resin composition according to any one of claims 1 to 4, containing at least one group selected from an isocyanate group, a urethane group, an alohanate group, a buret group and an imide group.
The resin composition according to any one of claims 1 to 6, wherein the compound B is a compound represented by the following formula (I):

In formula (I), A 1 represents a group generated by heating to generate a basic group, L 1 represents a single bond or a divalent linking group, M 1 represents Si, Ti or Zr, and R 1 1 to R 3 each independently represent Rb 1 or ORb 1 , and Rb 1 represents a hydrocarbon group having 1 to 10 carbon atoms.
The resin composition according to any one of claims 1 to 7, wherein the compound B is contained in an amount of 0.01 to 5% by mass based on the total solid content of the resin composition.
The resin composition according to any one of claims 1 to 8, wherein the resin contains at least one selected from a polyimide precursor and a polybenzoxazole precursor.
The resin composition according to any one of claims 1 to 9, which further comprises a photoradical polymerization initiator.
The resin composition according to claim 10, wherein the photoradical polymerization initiator contains an oxime compound.
The resin composition according to any one of claims 1 to 11, which is used for forming an interlayer insulating film for a redistribution layer.
A cured film obtained by curing the resin composition according to any one of claims 1 to 12.
A laminate having two or more layers of the cured film according to claim 13 and a metal layer between the two layers of the cured film.
A method for producing a cured film, comprising a film forming step of forming a film by applying the resin composition according to any one of claims 1 to 12 to a substrate.
The method for producing a cured film according to claim 15, comprising an exposing step of exposing the film and a developing step of developing the film.
The method for producing a cured film according to claim 15 or 16, including the step of heating the film at 80 to 450 ° C.
A semiconductor device having the cured film according to claim 13 or the laminate according to claim 14.