JP7237978B2 - Resin composition, cured film, laminate, method for producing cured film, and semiconductor device - Google Patents

Description

The present invention relates to a resin composition containing a polyimide 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 polymer precursor.

Polyimide resins are used in various applications because of their excellent heat resistance and insulating properties. Its use is not particularly limited, but in the case of semiconductor devices for mounting, it can be used as a material for insulating films and sealing materials, or as a protective film (see Non-Patent Documents 1 and 2, etc.). It is also used as a base film or coverlay for flexible substrates.
On the other hand, polyimide resins generally have low solubility in solvents. Therefore, a method of dissolving the polymer precursor before the cyclization reaction, specifically the polyimide precursor, in a solvent is often used. As a result, it is possible to realize excellent handleability, and it is possible to apply and process various forms on a substrate or the like when manufacturing each product as described above. Heating can then be applied to cyclize the polyimide precursor and form a cured product. In addition to the high performance possessed by polyimide resins and the like, from the viewpoint of such excellent manufacturing adaptability, there are increasing expectations for the development of industrial applications.

In Patent Document 1, (A) a polyamide having a photopolymerizable unsaturated bond: 100 parts by mass, (B) a monomer having a photopolymerizable unsaturated double bond: 1 to 50 parts by mass, (C) light A photosensitive resin composition containing 1 to 20 parts by mass of a polymerization initiator and (D) a 5 to 30 parts by mass of a thermal cross-linking agent is described.

Patent Document 2 discloses (A) a polyimide precursor having a polymerizable unsaturated bond, (B) a polymerizable monomer having an aliphatic cyclic skeleton, (C) a photopolymerization initiator, and (D) a thermal cross-linking agent. A containing photosensitive resin composition is described.

JP 2003-287889 A JP 2014-201695 A

Science & Technology Co., Ltd. "High Functionality and Application Technology of Polyimide" April 2008 Masaaki Kakimoto/supervisor, CMC Technical Library "Fundamentals and Development of Polyimide Materials" Published November 2011

In recent years, it has been studied to cyclize a polyimide precursor at a low temperature to obtain a cured product. In addition, further improvements in properties such as elongation at break and chemical resistance are desired for cured products obtained by cyclizing polyimide precursors at low temperatures.

Accordingly, 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 capable of forming a cured film having excellent elongation at break and chemical resistance. .

The inventor of the present invention has extensively studied a resin composition containing at least one polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors. The inventors have found that a cured film having excellent chemical resistance can be formed, and have completed the present invention. The present invention provides the following.

式（１）中、Ａ¹およびＡ²は、それぞれ独立に酸素原子またはＮＨを表し、Ｒ¹¹¹は、２価の有機基を表し、Ｒ¹¹⁵は、４価の有機基を表し、Ｒ¹¹³およびＲ¹¹⁴は、それぞれ独立に、水素原子または１価の有機基を表す。
＜１０＞ 式（１）におけるＲ¹¹³およびＲ¹¹⁴の少なくとも一方がラジカル重合性基を含む、＜９＞に記載の樹脂組成物。
＜１１＞ 更に、光重合開始剤を含む＜８＞または＜１０＞に記載の樹脂組成物。
＜１２＞ 再配線層用層間絶縁膜の形成に用いられる、＜１＞～＜１１＞のいずれか１つに記載の樹脂組成物。
＜１３＞ ＜１＞～＜１２＞のいずれか１つに記載の樹脂組成物を硬化して得られる硬化膜。
＜１４＞ ＜１３＞に記載の硬化膜を２層以上有し、２層の硬化膜の間に金属層を有する、積層体。
＜１５＞ ＜１＞～＜１２＞のいずれか１つに記載の樹脂組成物を基板に適用して膜を形成する膜形成工程を含む、硬化膜の製造方法。
＜１６＞ 膜を露光する露光工程および膜を現像する現像工程を有する、＜１５＞に記載の硬化膜の製造方法。
＜１７＞ 膜を８０～４５０℃で加熱する工程を含む、＜１６＞に記載の硬化膜の製造方法。
＜１８＞ ＜１３＞に記載の硬化膜または＜１４＞に記載の積層体を有する、半導体デバイス。<1> a polyimide precursor,
a thermal base generator;
a thermosetting compound having a plurality of functional groups selected from the group consisting of epoxy groups, oxetanyl groups, methylol groups, alkoxymethyl groups, phenol groups, maleimide groups, cyanate groups and blocked isocyanate groups;
A resin composition comprising:
<2> The resin composition according to <1>, wherein the thermosetting compound is a compound represented by the following formula (TC1);
^X1- ( ^Y1 ) _n ...(TC1)
In formula (TC1), X ¹ represents an n-valent linking group, Y ¹ represents an epoxy group, oxetanyl group, methylol group, alkoxymethyl group, phenol group, maleimide group, cyanate group or blocked isocyanate group, and n represents Represents an integer of 2 or greater.
<3> The resin composition according to <2>, wherein X ¹ in formula (TC1) contains a cyclic structure.
<4> The resin composition according to any one of <1> to <3>, wherein the thermosetting compound is a compound having a plurality of alkoxymethyl groups.
<5> The resin composition according to any one of <1> to <3>, wherein the thermosetting compound is a compound having a plurality of methoxymethyl groups.
<6> The resin composition according to any one of <1> to <5>, wherein the base generation temperature of the thermal base generator is lower than the curing start temperature of the thermosetting compound.
<7> The resin composition according to any one of <1> to <6>, wherein the content of the polymerizable monomer having a plurality of (meth)acryloyl groups is 20% by mass or less in the total solid content of the resin composition. thing.
<8> The resin composition according to any one of <1> to <7>, wherein the polyimide precursor contains a radically polymerizable group.
<9> The resin composition according to any one of <1> to <8>, wherein the polyimide precursor has a structural unit represented by the following formula (1);

In formula (1), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, R ¹¹³ and Each R ¹¹⁴ independently represents a hydrogen atom or a monovalent organic group.
<10> The resin composition according to <9>, wherein at least one of R ¹¹³ and R ¹¹⁴ in formula (1) contains a radically polymerizable group.
<11> The resin composition according to <8> or <10>, further comprising a photopolymerization initiator.
<12> The resin composition according to any one of <1> to <11>, which is used for forming an interlayer insulating film for a rewiring 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 layers of the cured film according to <13> and having a metal layer between the two layers of the cured film.
<15> A method for producing a cured film, comprising a film forming step of applying the resin composition according to any one of <1> to <12> to a substrate to form a film.
<16> The method for producing a cured film according to <15>, comprising 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 <16>, comprising the step of heating the film at 80 to 450°C.
<18> A semiconductor device comprising the cured film according to <13> or the laminate according to <14>.

INDUSTRIAL APPLICABILITY 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 capable of forming a cured film having excellent elongation at break and chemical resistance.

The contents of the present invention will be described in detail below. In this specification, the term "~" is used to mean that the numerical values before and after it are included as the lower limit and the upper limit.

The description of the constituent elements of the present invention described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.
In the description of a group (atomic group) in the present specification, a description that does not describe substitution or unsubstituted includes not only those without substituents but also those with substituents. For example, an "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).
As used herein, the term "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Light used for exposure generally includes actinic rays or radiation such as emission line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
As used herein, "(meth)acrylate" represents both or either of "acrylate" and "methacrylate", and "(meth)acrylic" represents both "acrylic" and "methacrylic", or Either is represented, and "(meth)acryloyl" represents both or either of "acryloyl" and "methacryloyl".
As used herein, the term "process" includes not only an independent process, but also when the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. .
Unless otherwise specified, physical property values in the present invention are values at a temperature of 23° C. and an atmospheric pressure of 101,325 Pa.
As used herein, the weight average molecular weight (Mw) and number average molecular weight (Mn) are measured by gel permeation chromatography (GPC measurement) and defined as polystyrene equivalents, unless otherwise specified. In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), guard column HZ-L, TSKgel Super HZM-M, TSKgel It can be obtained by using Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). In this measurement, THF (tetrahydrofuran) is used as the eluent unless otherwise specified. In addition, unless otherwise specified, a UV ray (ultraviolet) wavelength detector of 254 nm is used for detection.

[Resin composition]
The resin composition of the present invention comprises a polyimide precursor,
a thermal base generator;
a thermosetting compound having a plurality of functional groups selected from the group consisting of epoxy groups, oxetanyl groups, methylol groups, alkoxymethyl groups, phenol groups, maleimide groups, cyanate groups and blocked isocyanates;
including.

The resin composition of the present invention can form a cured film having excellent elongation at break and chemical resistance. In particular, even if the curing treatment is performed at a low temperature of 200° C. or less, a cured film having excellent elongation at break and chemical resistance can be formed.

In the resin composition of the present invention, the base generation temperature of the thermal base generator is preferably lower than the curing initiation temperature of the thermosetting compound. By using such a thermal base generator and a thermosetting compound in combination, the effects of the present invention can be obtained more remarkably.

In the resin composition of the present invention, it is also preferable that the content of the polymerizable monomer having multiple (meth)acryloyl groups is 20% by mass or less in the total solid content of the resin composition. Also by this aspect, the effects of the present invention can be obtained more remarkably. The lower limit can be greater than 0% by mass.

Each component of the resin composition of the present invention will be described in detail below.

<Polyimide precursor>
The resin composition of the present invention contains a polyimide precursor.

The polyimide precursor used in the present invention preferably contains a radically polymerizable group. The radically polymerizable group is a group capable of undergoing a cross-linking reaction by the action of a radical, and preferred examples thereof include groups having an ethylenically unsaturated bond. Examples of groups having an ethylenically unsaturated bond include vinyl groups, allyl groups, (meth)acryloyl groups, groups represented by formula (III) described below, and the like. When a polyimide precursor containing a radically polymerizable group is used, a cured film having better properties is likely to be obtained. Moreover, when the resin composition of the present invention contains a radical photopolymerization initiator, it can be a resin composition having excellent pattern formability in photolithography.

Ａ¹およびＡ²は、それぞれ独立に酸素原子またはＮＨを表し、Ｒ¹¹¹は、２価の有機基を表し、Ｒ¹¹⁵は、４価の有機基を表し、Ｒ¹¹³およびＲ¹¹⁴は、それぞれ独立に、水素原子または１価の有機基を表す。The polyimide precursor preferably contains a structural unit represented by the following formula (1). With such a structure, 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, 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, preferably an oxygen atom.

<<<R ¹¹¹ >>>
R ¹¹¹ represents a divalent organic group. Examples of divalent organic groups include linear or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or groups consisting of combinations thereof, and those having 2 to 20 carbon atoms. A linear aliphatic group, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group consisting of a combination thereof Preferred are aromatic groups having 6 to 20 carbon atoms.
R ¹¹¹ is preferably derived from a diamine. Diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, or two or more types may be used.
Specifically, the diamine is a linear aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof. A diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable. Examples of aromatic groups include:

In the formula, A is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms optionally substituted with a fluorine atom, -O-, -C (= O) -, -S-, -S (=O) ₂ -, -NHCO- and a group selected from a combination thereof, preferably a single bond, an optionally fluorine-substituted alkylene group having 1 to 3 carbon atoms, -O- , -C(=O)-, -S- and -SO ₂ - are more preferred, and -CH ₂ -, -O-, -S-, -SO ₂ -, -C( More preferably, it is a divalent group selected from the group consisting of CF ₃ ) ₂ -- and --C(CH ₃ ) ₂ --.

Diamines are specifically 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-amino phenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl ) hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxy phenyl)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'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)be 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, esters of diaminobenzoic acid, 1,5 -diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl) Decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2 -aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy) -3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, parabis(4-amino-2-trifluoromethyl) lufenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'- Bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone, 4,4′-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 2,2-bis[4-(4-amino- 3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3′,5,5′-tetramethyl-4,4′-diaminobiphenyl, 4,4′-diamino-2,2′-bis(trifluoro methyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolysine and at least one diamine selected from 4,4'-diaminoquaterphenyl.

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

Diamines having two or more alkylene glycol units in the main chain are also preferred examples. Diamines containing two or more ethylene glycol chains or propylene glycol chains in one molecule are preferred, and diamines containing no aromatic ring are more preferred. Specific examples include Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, Jeffamine (registered trademark) ED-900, Jeffamine (registered trademark) ED-2003, Jeffamine (registered trademark) ) EDR-148, Jeffamine (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy) ethoxy)propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, and the like.
Jeffamine® KH-511, Jeffamine® ED-600, Jeffamine® ED-900, Jeffamine® ED-2003, Jeffamine® EDR-148, The structure of Jeffamine® EDR-176 is shown below.

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

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

Ｒ⁵⁰～Ｒ⁵⁷は、それぞれ独立に水素原子、フッ素原子または１価の有機基であり、Ｒ⁵⁰～Ｒ⁵⁷の少なくとも１つはフッ素原子、メチル基、フルオロメチル基、ジフルオロメチル基、または、トリフルオロメチル基である。
Ｒ⁵⁰～Ｒ⁵⁷の１価の有機基として、炭素数１～１０（好ましくは炭素数１～６）の無置換のアルキル基、炭素数１～１０（好ましくは炭素数１～６）のフッ化アルキル基等が挙げられる。

Ｒ⁵⁸およびＲ⁵⁹は、それぞれ独立にフッ素原子、フルオロメチル基、ジフルオロメチル基、または、トリフルオロメチル基である。From the viewpoint of i-line transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or (61). In particular, from the viewpoint of i-line transmittance and availability, a divalent organic group represented by formula (61) is more preferable.

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

^R58 and ^R59 are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group.

Diamine compounds that give the structure of formula (51) or (61) include dimethyl-4,4′-diaminobiphenyl, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 2,2 '-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like. One of these may be used, or two or more may be used in combination.

Ｒ¹¹²は、Ａと同義であり、好ましい範囲も同じである。<<<R ¹¹⁵ >>>
R ¹¹⁵ in formula (1) represents a tetravalent organic group. The tetravalent organic group is preferably a group containing an aromatic ring, more preferably a group represented by the following formula (5) or (6).

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

Ｒ¹¹⁵は、４価の有機基を表す。Ｒ¹¹⁵は式（１）のＲ¹¹⁵と同義である。Specific examples of the tetravalent organic group represented by R ¹¹⁵ in formula (1) include a tetracarboxylic acid residue remaining after removal of the acid dianhydride group from the tetracarboxylic dianhydride. Only one kind of tetracarboxylic dianhydride may be used, or two or more kinds thereof may be used. Tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).

R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ has the same definition as R ¹¹⁵ in formula (1).

Specific examples of tetracarboxylic dianhydrides include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 3,3′,4 ,4′-diphenylsulfidetetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′,4,4′-diphenylmethanetetracarboxylic dianhydride, 2,2′,3,3′-diphenylmethanetetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic acid dianhydride, 2,3,3′,4′-benzophenonetetracarboxylic 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 di anhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1, 4,5,6-naphthalenetetracarboxylic dianhydride, 2,2′,3,3′-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1, 2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1- bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and at least one selected from alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

In addition, the following tetracarboxylic dianhydrides (DAA-1) to (DAA-5) 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. At least one of R ¹¹³ and R ¹¹⁴ preferably contains a radically polymerizable group, more preferably both contain a radically polymerizable group. The radically polymerizable group is a group capable of undergoing a cross-linking reaction by the action of a radical, and preferred examples thereof include groups having an ethylenically unsaturated bond. Examples of groups having an ethylenically unsaturated bond include vinyl groups, allyl groups, (meth)acryloyl groups, groups represented by the following formula (III), and the like.

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

Preferred embodiments of polyimide precursors in the present invention include aliphatic groups, aromatic groups and aryl groups having 1, 2 or 3, preferably 1 acid group as monovalent organic groups for R ¹¹³ or R ¹¹⁴ . An alkyl group and the like can be mentioned. Specific examples include an acidic group-containing aromatic group having 6 to 20 carbon atoms and an acid group-containing arylalkyl group having 7 to 25 carbon atoms. More specific examples include a phenyl group having an acid group and a benzyl group having an acid group. The acid groups are preferably hydroxyl groups. 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 solubility in a developer is preferably used.
More preferably, R ¹¹³ or R ¹¹⁴ is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl or 4-hydroxybenzyl from the viewpoint of solubility in an aqueous developer.

From the viewpoint of solubility in organic solvents, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. The monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and more preferably an alkyl group substituted with an aromatic group.
The number of carbon atoms in the alkyl group is preferably 1 to 30 (3 or more in the case of cyclic). Alkyl groups may be linear, branched or cyclic. Linear or branched alkyl groups 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 and octadecyl group. , isopropyl, isobutyl, sec-butyl, t-butyl, 1-ethylpentyl, and 2-ethylhexyl groups. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Monocyclic cyclic alkyl groups include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups. Examples of polycyclic cyclic alkyl groups include adamantyl group, norbornyl group, bornyl group, camphenyl group, decahydronaphthyl group, tricyclodecanyl group, tetracyclodecanyl group, campholoyl group, dicyclohexyl group and pinenyl group. are mentioned. Moreover, 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 aromatic groups include substituted or unsubstituted aromatic hydrocarbon groups (cyclic structures constituting the group include benzene ring, naphthalene ring, biphenyl ring, fluorene ring, pentalene ring, indene ring, azulene ring, 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 constituent cyclic structures include 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, quinolidine 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 ring, phenoxathiin ring, phenothiazine ring or phenazine ring).

Moreover, the polyimide precursor preferably has a fluorine atom in its constitutional unit. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less. Although there is no particular upper limit, 50% by mass or less is practical.

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

Ａ¹¹およびＡ¹²は、酸素原子またはＮＨを表し、Ｒ¹¹¹およびＲ¹¹²は、それぞれ独立に、２価の有機基を表し、Ｒ¹¹³およびＲ¹¹⁴は、それぞれ独立に、水素原子または１価の有機基を表し、Ｒ¹¹³およびＲ¹¹⁴の少なくとも一方は、ラジカル重合性基を含む基であることが好ましく、ラジカル重合性基であることがより好ましい。The structural unit represented by formula (1) is preferably a structural unit represented by formula (1-A) or (1-B).

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

A ¹¹ , A ¹² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ each independently have the same preferred ranges as the preferred ranges of A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (1) .
The preferred range of R ¹¹² has the same meaning as R ¹¹² in formula (5), and more preferably an oxygen atom.
The bonding positions of the carbonyl group to the benzene ring in the formula are preferably 4, 5, 3' and 4' in formula (1-A). In formula (1-B), 1, 2, 4 and 5 are preferred.

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

As one embodiment of the polyimide precursor in the present invention, 50 mol% or more, further 70 mol% or more, particularly 90 mol% or more of all structural units is a polyimide precursor whose structural unit is represented by formula (1). are exemplified. A practical upper limit is 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, still more preferably 10,000 to 50,000. Also, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, still more preferably 4,000 to 25,000.
The polyimide precursor preferably has a molecular weight distribution of 1.5 to 3.5, more preferably 2 to 3.

A polyimide precursor can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative using a halogenating agent and then reacting it with a diamine.
In the method for producing a polyimide precursor, it is preferable to use an organic solvent in the reaction. One type of organic solvent may be used, or two or more types may be used.
Examples of the organic solvent include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone, although they can be appropriately determined depending on the raw material.

The production of the polyimide precursor preferably includes a step of depositing a solid. Specifically, the polyimide precursor in the reaction solution is precipitated in water, and dissolved in a solvent such as tetrahydrofuran in which the polyimide precursor is soluble, whereby solid deposition can be performed.

The content of the polyimide precursor 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 with respect to the total solid content of the resin composition. is more preferably 50% by mass or more, even more preferably 60% by mass or more, and even more preferably 70% by mass or more. Further, the content of the polyimide precursor in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, relative to the total solid content of the resin composition. , more preferably 98% by mass or less, and even more preferably 95% by mass or less.
The resin composition of the present invention may contain only one type of polyimide precursor, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<Thermal base generator>
The resin composition of the present invention contains a thermal base generator. The type of the thermal base generator is not particularly specified, but it is selected from acidic compounds that generate a base when heated to 40° C. or higher, and ammonium salts having an anion with a pKa1 of 0 to 4 and an ammonium cation. It is preferable to include a thermal base generator containing at least one of Here, pKa1 represents the logarithm (-Log ₁₀ Ka) of the dissociation constant (Ka) of the first proton of the acid, details of which will be described later.
By blending such a compound, the cyclization reaction of the polyimide precursor can be carried out at a low temperature. Moreover, since the thermal base generator does not generate a base unless it is heated, even if it is coexisted with the polymer precursor, it can suppress cyclization of the polymer precursor during storage and has excellent storage stability.

The thermal base generator includes an acidic compound (A1) that generates a base when heated to 40° C. or higher, an ammonium salt (A2) having an anion with a pKa1 of 0 to 4 and an ammonium cation, and a nonionic thermal base generator (A3 ), more preferably a nonionic thermal base generator (A3). Since these compounds generate bases when heated, the bases generated from these compounds can promote the cyclization reaction of the polyimide precursor, and the cyclization of the polyimide precursor can be carried out at a low temperature. In this specification, an acidic compound means that 1 g of a compound is collected in a container, 50 mL of a mixed solution of ion-exchanged water and tetrahydrofuran (mass ratio is water/tetrahydrofuran=1/4) is added, and the mixture is stirred at room temperature for 1 hour. It means a compound whose value is less than 7 when the solution obtained by stirring is 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, and even more preferably 165°C or lower. The base generation temperature is determined, for example, by using differential scanning calorimetry, heating the compound in a pressure-resistant capsule at 5°C/min up to 250°C, reading the peak temperature of the exothermic peak with the lowest temperature, and measuring the peak temperature as the base generation temperature. can do.

Moreover, the base generation temperature of the thermal base generator used in the present invention is preferably lower than the curing initiation temperature of the thermosetting compound described above.

The base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, more preferably a tertiary amine. Since tertiary amines are highly basic, they can lower the cyclization temperature of the polyimide precursor. 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 even more preferably 140°C or higher. Further, the molecular weight of the generated base is preferably 80-2000. The lower limit is more preferably 100 or more. The upper limit is more preferably 500 or less. The molecular weight value 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 formula (101) or (102) described below.

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.), ), except for acidic compounds that generate a base when heated to .

式（１０１）および式（１０２）中、Ｒ¹～Ｒ⁶は、それぞれ独立に、水素原子または炭化水素基を表し、Ｒ⁷は炭化水素基を表す。式（１０１）および式（１０２）におけるＲ¹とＲ²、Ｒ³とＲ⁴、Ｒ⁵とＲ⁶、Ｒ⁵とＲ⁷はそれぞれ結合して環を形成してもよい。In this embodiment, an 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 via a covalent bond, or may be present outside the molecule of the ammonium cation, but may be present outside the molecule of the ammonium cation. preferable. In addition, having the anion outside the molecule of the ammonium cation means that the ammonium cation and the anion are not bonded via a covalent bond. Hereinafter, the extramolecular anion of the cation moiety is also referred to as a counter anion.
Equation (101) Equation (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 combine to form a ring.

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

In formulas (Y1-1) to (Y1-5), R ¹⁰¹ represents an n-valent organic group, and R ¹ and R ⁷ have the same meanings as in formula (101) or (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 this embodiment, the ammonium salt preferably has an anion with a pKa1 of 0 to 4 and an ammonium cation. The upper limit of the pKa1 of the anion is more preferably 3.5 or less, even more preferably 3.2 or less. The lower limit is preferably 0.5 or more, more preferably 1.0 or more. When the pKa1 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 pKa1 is 4 or less, the stability of the thermal base generator is good, the generation of a base can be suppressed without heating, and the stability of the resin composition is good. When the pKa1 is 0 or more, the generated base is less likely to be neutralized, and the cyclization efficiency of the polymer precursor is good.
The kind of anion is preferably one selected from carboxylate anions, phenol anions, phosphate anions and sulfate anions, and carboxylate anions are more preferable because both salt stability and thermal decomposability can be achieved. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion.
The carboxylate anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxyl groups, more preferably an anion of a divalent carboxylic acid. According to this aspect, the thermal base generator can further improve the stability, curability and developability of the resin composition. In particular, by using a divalent carboxylic acid anion, the stability, curability and developability of the resin composition can be further improved.
In the present embodiment, the carboxylic acid anion is preferably an anion of a carboxylic acid having a pKa1 of 4 or less. The pKa1 is more preferably 3.5 or less, even more preferably 3.2 or less. According to this aspect, the stability of the resin composition can be further improved.
Here, pKa1 represents the logarithm of the reciprocal of the dissociation constant of the first proton of the acid, and is described in Determination of Organic Structures by Physical Methods (authors: Brown, HC, McDaniel, DH, Hafliger, OH). Academic Press, New York, 1955) and Data for Biochemical Research (authors: Dawson, RMC et al.). al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, values calculated from structural formulas using software ACD/pKa (manufactured by ACD/Labs) are used.

式（Ｘ１）において、ＥＷＧは、電子求引性基を表す。The carboxylate anion is preferably represented by the following formula (X1).

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

In the present embodiment, the electron-withdrawing group means a group having a positive Hammett's substituent constant σm. Here, σm is described in Yuho Tsuno Review, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965) p. 631-642. In addition, the electron-withdrawing group in the present embodiment is not limited to the substituents described in the above literature.
Examples of substituents with positive σm include _CF3 group (σm=0.43), _CF3CO 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 groups (σm=0.06), and the like. Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group.

式（ＥＷＧ－１）～（ＥＷＧ－６）中、Ｒ^x1～Ｒ^x3は、それぞれ独立に、水素原子、アルキル基、アルケニル基、アリール基、ヒドロキシル基またはカルボキシル基を表し、Ａｒは芳香族基を表す。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 represent 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

式（ＸＡ）において、Ｌ¹⁰は、単結合、または、アルキレン基、アルケニレン基、芳香族基、－ＮＲ^X－およびこれらの組み合わせから選ばれる２価の連結基を表し、Ｒ^Xは、水素原子、アルキル基、アルケニル基またはアリール基を表す。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 is a hydrogen atom. , represents an alkyl group, an alkenyl group or an aryl group.

Specific examples of carboxylate anions include maleate, phthalate, N-phenyliminodiacetate and oxalate anions. These can be preferably used.

<Specific thermal base generator>
Examples of the nonionic thermal base generator (A3) include compounds represented by formula (B1) or formula (B2).

In formulas (B1) and (B2), Rb ¹ , Rb ² and Rb ³ are each independently an organic group having no tertiary amine structure, a halogen atom or a hydrogen atom. However, Rb ¹ and Rb ² are not hydrogen atoms at the same time. Also, Rb ¹ , Rb ² and Rb ³ do not have a carboxyl group. In this specification, the tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to hydrocarbon-based carbon atoms. Therefore, when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when forming an amide group together with the nitrogen atom, this is not the case.

In formulas (B1) and (B2), at least one of Rb ¹ , Rb ² and Rb ³ preferably contains a cyclic structure, more preferably at least two of them contain a cyclic structure. The cyclic structure may be either a single ring or a condensed ring, preferably a single ring or a condensed ring in which two single rings are condensed. The monocyclic ring is preferably a 5- or 6-membered ring, preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring and a benzene ring, more preferably a cyclohexane ring.

More specifically, Rb ¹ and Rb ² are hydrogen atoms, alkyl groups (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, even more preferably 3 to 12 carbon atoms), alkenyl groups (preferably 2 to 24 carbon atoms). , more preferably 2 to 18, more preferably 3 to 12), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, even more preferably 6 to 10), or an arylalkyl group (7 carbon atoms to 25 are preferred, 7 to 19 are more preferred, and 7 to 12 are even more preferred). These groups may have a substituent as long as the effects of the present invention are exhibited. Rb ¹ and Rb ² may combine with each other to form a ring. The ring to be formed is preferably a 4- to 7-membered nitrogen-containing heterocyclic ring. Rb ¹ and Rb ² are particularly linear, branched or cyclic alkyl groups (having preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms) which may have a substituent. is preferably a cycloalkyl group optionally having a substituent (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, more preferably 3 to 12 carbon atoms), and more preferably a cycloalkyl group having a substituent A cyclohexyl group, which may be

Rb ³ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 10 are more preferred), alkenyl groups (preferably 2 to 24 carbon atoms, more preferably 2 to 12, more preferably 2 to 6), arylalkyl groups (preferably 7 to 23 carbon atoms, more preferably 7 to 19 preferably 7 to 12), arylalkenyl groups (preferably 8 to 24 carbon atoms, more preferably 8 to 20, more preferably 8 to 16), alkoxyl groups (preferably 1 to 24 carbon atoms, 2 to 18 is more preferred, and 3 to 12 are more preferred), an aryloxy group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12), or an arylalkyloxy group (preferably 7 to 12 carbon atoms). 23 is preferred, 7 to 19 are more preferred, and 7 to 12 are even more preferred). Among them, a cycloalkyl group (having preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferred. Rb ³ may further have a substituent as long as the effects of the present invention are exhibited.

The compound represented by formula (B1) is preferably a compound represented by formula (B1-1) or formula (B1-2) below.

In the formula, Rb ¹¹ and Rb ¹² and Rb ³¹ and Rb ³² are the same as Rb ¹ and Rb ² in formula (B1) respectively.
Rb ¹³ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19, 7 to 12 are more preferable), and may have a substituent within the range in which the effects of the present invention are exhibited. Among them, Rb ¹³ is preferably an arylalkyl group.

Rb ³³ and Rb ³⁴ each independently represent a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms). , more preferably 2 to 8, more preferably 2 to 3), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 10), an arylalkyl group (7 to 23 is preferred, 7 to 19 are more preferred, and 7 to 11 are even more preferred), and a hydrogen atom is preferred.

Rb ³⁵ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 3 to 8 carbon atoms), aryl groups (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 12), arylalkyl groups (preferably 7 to 23 carbon atoms, more preferably 7 to 19, more preferably 7 to 12 ), with aryl groups being preferred.

The compound represented by formula (B1-1) is also preferably the compound represented by formula (B1-1a).

Rb ¹¹ and Rb ¹² are synonymous with Rb ¹¹ and Rb ¹² in formula (B1-1).
Rb ¹⁵ and Rb ¹⁶ are hydrogen atoms, alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), alkenyl groups (preferably 2 to 12 carbon atoms, 2 to 6 more preferably 2 to 3), aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, even more preferably 6 to 10), arylalkyl group (preferably 7 to 23 carbon atoms, 7 to 19 are more preferred, and 7 to 11 are even more preferred), and a hydrogen atom or a methyl group is preferred.
Rb ¹⁷ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 3 to 8 carbon atoms), an aryl group; (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms), arylalkyl groups (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, more preferably 7 to 12 carbon atoms) and an aryl group is particularly preferred.

The molecular weight of the nonionic thermal base generator (A3) is preferably 800 or less, more preferably 600 or less, even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

Specific examples of the thermal base generator include the following compounds.

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, and even more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and even more preferably 20% by mass or less. One or two or more thermal base generators can be used. When two or more kinds are used, the total amount is preferably within the above range.

<Thermosetting compound>
The resin composition of the present invention comprises a thermosetting compound having a plurality of functional groups selected from the group consisting of epoxy groups, oxetanyl groups, methylol groups, alkoxymethyl groups, phenol groups, maleimide groups, cyanate groups and blocked isocyanate groups. contains. In the present invention, a thermosetting compound means a compound that is cured by heating. A blocked isocyanate group is a group capable of generating an isocyanate group by heat. For example, a group obtained by reacting a blocking agent with an isocyanate group to protect the isocyanate group can be preferably exemplified.

The molecular weight of the thermosetting compound (weight average molecular weight in the case of polymers) is preferably 100-10,000. The lower limit is preferably 150 or more, more preferably 200 or more. The upper limit is preferably 1000 or less, more preferably 500 or less.

The curing initiation temperature of the thermosetting compound is preferably 100 to 350°C. The lower limit is preferably 110°C or higher, more preferably 120°C or higher. The upper limit is preferably 200° C. or lower, more preferably 180° C. or lower. In the present invention, the curing initiation temperature of a thermosetting compound is measured by differential scanning calorimetry by heating 1 mg of a sample (thermosetting compound) from a state of 25 ° C. at a temperature rising rate of 5 ° C./min. is the temperature at which the exothermic reaction of the thermosetting compound begins, measured by performing The temperature at which the exothermic reaction of the thermosetting compound begins means the temperature at which the peak of the exothermic reaction appears in a differential scanning calorimetry curve in which the vertical axis is heat flow (mW) and the horizontal axis is temperature (°C). do. In the case where the exothermic reaction has two or more peaks, the exothermic reaction peak at a low temperature is defined as the "temperature at which the exothermic reaction of the thermosetting compound starts (curing initiation temperature)" in the present invention.

The thermosetting compound used in the present invention is preferably a compound having a plurality of functional groups selected from an epoxy group, an oxetanyl group, a methylol group and an alkoxymethyl group. A compound having a plurality of groups is more preferable, a compound having a plurality of alkoxymethyl groups is further preferable because the effects of the present invention are likely to be obtained more remarkably, and a compound having a plurality of methoxymethyl groups is particularly preferable. preferable.

Moreover, the number of the above-mentioned functional groups contained in the thermosetting compound may be two or more, preferably three or more. The upper limit is preferably 10 or less, more preferably 6 or less.

The thermosetting compound used in the present invention is preferably a compound represented by Formula (TC1).
^X1- ( ^Y1 ) _n ...(TC1)
In formula (TC1), X ¹ represents an n-valent linking group, Y ¹ represents an epoxy group, oxetanyl group, methylol group, alkoxymethyl group, phenol group, maleimide group, cyanate group or blocked isocyanate group, and n represents Represents an integer of 2 or greater.

The n-valent linking group represented by X ¹ in formula (TC1) includes an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, -O-, -NH-, -NHCO-, -CONH-, - OCO-, -COO-, -CO-, -SO ₂ NH-, -SO ₂ - and combinations thereof. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1-30, more preferably 1-15, still more preferably 1-8, and particularly preferably 1-5. The aliphatic hydrocarbon group may be linear, branched, or cyclic, preferably linear or branched, and particularly preferably linear. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6-30, more preferably 6-15. The aromatic hydrocarbon group may be monotube or condensed ring. The heterocyclic group may be monocyclic or condensed. The heterocyclic group is preferably a monocyclic ring or a condensed ring having 2 to 4 condensed rings. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1-3. A heteroatom constituting the ring of the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The number of carbon atoms constituting the ring of the heterocyclic group is preferably 3-30, more preferably 3-18, and more preferably 3-12.

X ¹ in formula (TC1) is preferably a group containing a cyclic structure. The cyclic structure includes an aliphatic ring, an aromatic hydrocarbon ring, and a heterocyclic ring, preferably an aromatic hydrocarbon ring or a heterocyclic ring, more preferably a heterocyclic ring. The heterocycle is preferably a nitrogen-containing heterocycle. The nitrogen-containing heterocyclic ring includes a pyridine ring, a triazine ring, an imidazolidinone ring and the like, and an imidazolidinone ring is preferred.

Y ¹ in formula (TC1) represents an epoxy group, oxetanyl group, methylol group, alkoxymethyl group, phenol group, maleimide group, cyanate group or blocked isocyanate group, and an epoxy group, oxetanyl group, methylol group or alkoxymethyl group; is preferred, a methylol group or an alkoxymethyl group is more preferred, and an alkoxymethyl group is even more preferred.

An alkoxymethyl group is a group represented by —CH ₂ —ORy ¹ . Ry ¹ is an alkyl group, preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, and further preferably an alkyl group having 1 to 8 carbon atoms. An alkyl group having 1 to 3 carbon atoms is particularly preferred, and an alkyl group having 1 carbon atom (methyl group) is most preferred. That is, the alkoxymethyl group is most preferably a methoxymethyl group.

The thermosetting compound used in the present invention is also preferably a compound in which a methylol group or an alkoxymethyl group is bonded to a nitrogen atom or a carbon atom forming an aromatic ring. Preferred examples of such compounds include alkoxymethylated melamine, methylolated melamine, alkoxymethylated benzoguanamine, methylolated benzoguanamine, alkoxymethylated glycoluril, methylolated glycoluril, alkoxymethylated urea, and methylolated urea. Compounds described in paragraphs 0056 to 0065 of JP-A-2003-287889 and paragraphs 0058-0060 of JP-A-2018-084626 can also be used.

Preferred structures of compounds in which an alkoxymethyl group or a methylol group is bonded to a nitrogen atom include compounds represented by the following formulas (AM-101) to (AM-105).

In formula (AM-101), Rm ¹ to Rm ⁴ each independently represent a hydrogen atom or a group represented by formula (Rm). However, two or more of Rm ¹ to Rm ⁴ are groups represented by the formula (Rm).
In formula (AM-102), Rm ⁵ to Rm ⁸ each independently represent a hydrogen atom or a group represented by formula (Rm). However, two or more of Rm ⁵ to Rm ⁸ are groups represented by the formula (Rm).
In formula (AM-103), Rm ⁹ and Rm ¹⁰ each independently represent a group represented by formula (Rm).
In formula (AM-104), Rm ¹¹ to Rm ¹⁶ each independently represent a hydrogen atom or a group represented by formula (Rm). However, two or more of Rm ¹¹ to Rm ¹⁶ are groups represented by the formula (Rm).
In formula (AM-105), Rm ¹⁷ to Rm ²⁰ each independently represent a hydrogen atom or a group represented by formula (Rm). However, two or more of Rm ¹⁷ to Rm ²⁰ are groups represented by the formula (Rm).

(Formula (Rm))
—CH ₂ —O—Rm ¹⁰⁰
In formula (Rm), ^Rm100 represents a hydrogen atom or an alkyl group. The number of carbon atoms in the alkyl group represented by Rm ¹⁰⁰ is preferably 1 to 30, more preferably 1 to 15, even more preferably 1 to 8, particularly preferably 1 to 3, 1 is most preferred. That is, the alkoxymethyl group is most preferably a methoxymethyl group.

Examples of compounds in which an alkoxymethyl group or a methylol group is bonded to a carbon atom forming an aromatic ring include compounds represented by the following formula (AM-110).

式（ＡＭ－１１０）中、Ｘは単結合または１～４価の有機基を表し、Ｒ¹¹～Ｒ¹³は各々独立に水素原子またはアルキル基を表し、Ｒ¹⁵は水素原子、ヒドロキシル基またはアルキル基を表し、ｎ、ｐおよびｒはそれぞれ独立して１～４の整数であり、ｑは０～４の整数である。Formula (AM-110)

In formula (AM-110), X represents a single bond or a monovalent to tetravalent organic group, R ¹¹ to R ¹³ each independently represents a hydrogen atom or an alkyl group, R ¹⁵ represents a hydrogen atom, a hydroxyl group or an alkyl group, n, p and r are each independently an integer of 1-4, and q is an integer of 0-4.

Specific examples of thermosetting compounds having a methylol group or an alkoxymethyl group include compounds having the following structures. Commercially available products include 46DMOC, 46DMOEP, TM-BIP-A (manufactured by Asahi Organic Chemicals Industry Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, and DML. -34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, 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.), NIKALAC MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW- 100LM (manufactured by Sanwa Chemical Co., Ltd.) and the like.

In the present invention, a thermosetting compound having an epoxy group (hereinafter also referred to as an epoxy compound) can be used as the thermosetting compound. The epoxy compound may be a compound having two or more epoxy groups, preferably a compound having 2 to 100 epoxy groups. The upper limit of the number of epoxy groups can be, for example, 10 or less, or 5 or less. Examples of epoxy compounds include bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; Epoxy group-containing silicones such as (oxypropyl)siloxane, etc., but not limited to these. Specifically, Epiclon (registered trademark) 850-S, Epiclon (registered trademark) HP-4032, Epiclon (registered trademark) HP-7200, Epiclon (registered trademark) HP-820, Epiclon (registered trademark) HP-4700, Epiclon (registered trademark) EXA-4710, Epiclon (registered trademark) HP-4770, Epiclon (registered trademark) EXA-859CRP, Epiclon (registered trademark) EXA-1514, Epiclon (registered trademark) EXA-4880, Epiclon (registered trademark) EXA-4850-150, Epiclon EXA-4850-1000, Epiclon (registered trademark) EXA-4816, Epiclon (registered trademark) EXA-4822 (manufactured by DIC Corporation), Ricaresin (registered trademark) BEO-60E (trade name, Shin Nippon Chemical Co., Ltd.), EP-4003S, EP-4000S (manufactured by ADEKA Corporation), and the like. Compounds having the following structures can also be used.

In the present invention, a thermosetting compound having an oxetanyl group (hereinafter also referred to as an oxetane compound) can be used as the thermosetting compound. Oxetane compounds include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, and 3-ethyl-3-(2-ethylhexylmethyl)oxetane. , 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester and the like. Commercially available products include Aron oxetane series manufactured by Toagosei Co., Ltd. (eg, OXT-121, OXT-221, OXT-191, OXT-223).

In the present invention, a thermosetting compound having a blocked isocyanate group (hereinafter also referred to as a blocked isocyanate compound) can be used as the thermosetting compound. The skeleton of the blocked isocyanate compound is not particularly limited, and may be an aliphatic, alicyclic or aromatic polyisocyanate. For specific examples of the skeleton, the description in paragraph number 0144 of JP-A-2014-238438 can be referred to, the content of which is incorporated herein. Examples of the parent structure of the blocked isocyanate compound include biuret type, isocyanurate type, adduct type, bifunctional prepolymer type, and the like. Examples of blocking agents that form the block structure of blocked isocyanate compounds include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. can be done. Among these, blocking agents selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds are particularly preferred. Specific examples of the blocking agent can be referred to in paragraph 0146 of JP-A-2014-238438, the content of which is incorporated herein. Blocked isocyanate compounds are commercially available, and examples include Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (manufactured by Nippon Polyurethane Industry Co., Ltd.), and Takenate B. -830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (manufactured by Mitsui Chemicals, Inc.), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (manufactured by Asahi Kasei Corporation), Desmodur BL1100 , BL1265 MPA/X, BL3575/1, BL3272MPA, BL3370MPA, BL3475BA/SN, BL5375MPA, VPLS2078/2, BL4265SN, PL340, PL350, Sumidule BL3175 (manufactured by Sumika Bayer Urethane Co., Ltd.), etc. are preferably used. be able to.

In the present invention, a compound having a group selected from a phenol group, a maleimide group and a cyanate group can also be used as the thermosetting compound.

The content of the thermosetting compound is preferably 1 to 20% by mass based on the total solid content of the resin composition of the present invention. The lower limit is preferably 3% by mass or more, more preferably 5% by mass or more. The upper limit is preferably 18% by mass or less, more preferably 15% by mass or less.
Also, the content of the thermosetting compound is preferably 1 to 25 parts by mass with respect to 100 parts by mass of the polyimide precursor. The upper limit is preferably 23 parts by mass or less, more preferably 20 parts by mass or less. The lower limit is preferably 4 parts by mass or more, more preferably 6 parts by mass or more. When the content of the thermosetting compound is 6 parts by mass or more with respect to 100 parts by mass of the polyimide precursor, a cured film having excellent chemical resistance can be easily obtained. Further, when the content of the thermosetting compound is 20 parts by mass or less with respect to 100 parts by mass of the polyimide precursor, a cured film having excellent substrate adhesion can be easily obtained.
Also, the content of the thermosetting compound is preferably 10 to 1000 parts by mass with respect to 100 parts by mass of the thermal base generator. The upper limit is preferably 800 parts by mass or less, more preferably 600 parts by mass or less. The lower limit is preferably 20 parts by mass or more, more preferably 50 parts by mass or more.
The thermosetting compounds may be used singly or in combination of two or more. When two or more are used in combination, the total amount is preferably within the above range.

<Photoinitiator>
The resin composition of the present invention preferably contains a photopolymerization initiator. A radical photopolymerization initiator is preferred. The radical photopolymerization initiator is not particularly limited and can be appropriately selected from known radical photopolymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferred. It may also be an activator that produces an active radical by producing some action with a photoexcited sensitizer.
The radical photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within the range of about 300-800 nm (preferably 330-500 nm). The molar extinction coefficient of a compound can be measured using known methods. 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 (e.g., 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, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. mentioned. For details of these, paragraphs 0165 to 0182 of JP-A-2016-027357 and paragraphs 0138 to 0151 of WO 2015/199219 can be referred to, the contents of which are incorporated herein.

Examples of ketone compounds include compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated herein. As a commercial product, Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

Hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators described in JP-A-10-291969 and acylphosphine oxide-based initiators 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, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.
As aminoacetophenone-based initiators, 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, whose absorption maximum wavelength is matched to a wavelength light source such as 365 nm or 405 nm, can also be used.
Acylphosphine-based initiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and the like. In addition, commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) can be used.
Examples of metallocene compounds include IRGACURE-784 (manufactured by BASF).

市販品ではＩＲＧＡＣＵＲＥ ＯＸＥ ０１、ＩＲＧＡＣＵＲＥ ＯＸＥ ０２、ＩＲＧＡＣＵＲＥ ＯＸＥ ０３、ＩＲＧＡＣＵＲＥ ＯＸＥ ０４（以上、ＢＡＳＦ社製）、アデカオプトマーＮ－１９１９（（株）ＡＤＥＫＡ製、特開２０１２－０１４０５２号公報に記載の光ラジカル重合開始剤２）も好適に用いられる。また、ＴＲ－ＰＢＧ－３０４（常州強力電子新材料有限公司製）、アデカアークルズＮＣＩ－８３１およびアデカアークルズＮＣＩ－９３０（（株）ＡＤＥＫＡ製）も用いることができる。また、ＤＦＩ－０９１（ダイトーケミックス株式会社製）を用いることができる。
さらに、また、フッ素原子を有するオキシム化合物を用いることも可能である。そのようなオキシム化合物の具体例としては、特開２０１０－２６２０２８号公報に記載されている化合物、特表２０１４－５００８５２号公報の段落０３４５に記載されている化合物２４、３６～４０、特開２０１３－１６４４７１号公報の段落０１０１に記載されている化合物（Ｃ－３）などが挙げられる。
最も好ましいオキシム化合物としては、特開２００７－２６９７７９号公報に示される特定置換基を有するオキシム化合物や、特開２００９－１９１０６１号公報に示されるチオアリール基を有するオキシム化合物などが挙げられる。As the radical photopolymerization initiator, an oxime compound is more preferable. By using an oxime compound, the exposure latitude can be improved more effectively. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.
Specific examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, and compounds described in JP-A-2006-342166.
Preferred oxime compounds include, for example, compounds having the following structures, 3-benzooxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxy iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one , and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. In the resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as a radical photopolymerization initiator. An oxime-based photopolymerization initiator has a >C=N--O--C(=O)-- linking group in the molecule.

Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA Co., Ltd., the light described in JP-A-2012-014052 A radical polymerization initiator 2) is also preferably used. In addition, TR-PBG-304 (manufactured by Changzhou Yuan Electronics New Materials Co., Ltd.), Adeka Arkles NCI-831 and Adeka Arkles NCI-930 (manufactured by ADEKA Co., Ltd.) can also be used. Also, DFI-091 (manufactured by Daito Chemix Co., Ltd.) can be used.
Furthermore, it is also possible to use oxime compounds having fluorine atoms. Specific examples of such oxime compounds include compounds described in JP-A-2010-262028, compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013. Examples thereof include compound (C-3) described in paragraph 0101 of JP-A-164471.
The most preferable oxime compounds include oxime compounds having specific substituents described in JP-A-2007-269779 and oxime compounds having a thioaryl group described in JP-A-2009-191061.

式（Ｉ）中、Ｒ^I00は、炭素数１～２０のアルキル基、１個以上の酸素原子によって中断された炭素数２～２０のアルキル基、炭素数１～１２のアルコキシル基、フェニル基、炭素数１～２０のアルキル基、炭素数１～１２のアルコキシル基、ハロゲン原子、シクロペンチル基、シクロヘキシル基、炭素数２～１２のアルケニル基、１個以上の酸素原子によって中断された炭素数２～１８のアルキル基および炭素数１～４のアルキル基の少なくとも１つで置換されたフェニル基、またはビフェニルであり、Ｒ^I01は、式（ＩＩ）で表される基であるか、Ｒ^I00と同じ基であり、Ｒ^I02～Ｒ^I04は各々独立に炭素数１～１２のアルキル、炭素数１～１２のアルコキシまたはハロゲンである。

式中、Ｒ^I05～Ｒ^I07は、上記式（Ｉ）のＲ^I02～Ｒ^I04と同じである。From the viewpoint of exposure sensitivity, photoradical polymerization initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl selected from the group consisting of imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds; are preferred.
More preferred radical photopolymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds. More preferably, at least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds, more preferably metallocene compounds or oxime compounds, and oxime compounds. is even more preferred.
Further, the photoradical polymerization initiator includes benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone such as N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), 2-benzyl -aromatic ketones such as 2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, alkylanthraquinones, etc. quinones condensed with the aromatic ring of , benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, and benzyl derivatives such as benzyl dimethyl ketal can also be used. A compound represented by the following formula (I) can also be used.

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

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

Further, as the radical photopolymerization initiator, compounds described in paragraphs 0048 to 0055 of WO 2015/125469 can also be used.

When a photopolymerization initiator is included, 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 still more preferably 1.0 to 10% by mass. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more photopolymerization initiators are contained, the total is preferably within the above range.

<Thermal radical polymerization initiator>
The resin composition of the present invention may contain a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or promotes a polymerization reaction of a compound having a radically polymerizable group. By adding a thermal radical polymerization initiator, in addition to cyclization of the polyimide precursor, if the polyimide precursor has a radically polymerizable group, the polymerization reaction of the polyimide precursor can also proceed, so a higher degree of heat resistance can be achieved. can be achieved.
Specific examples of thermal radical polymerization initiators include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.

When a thermal radical polymerization initiator is included, 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. Yes, more preferably 5 to 15% by mass. One type of thermal radical polymerization initiator may be contained, or two or more types may be contained. When two or more thermal radical polymerization initiators are contained, the total is preferably within the above range.

<Polymerizable Monomer>
The resin composition of the present invention may contain a polymerizable monomer having multiple (meth)acryloyl groups. The number of (meth)acryloyl groups possessed by the polymerizable monomer may be two or more, preferably three or more. The upper limit is preferably 15 or less, more preferably 10 or less, even more preferably 8 or less.

The molecular weight of the polymerizable monomer is preferably 2000 or less, more preferably 1500 or less, even more preferably 900 or less. The lower limit of the molecular weight of the polymerizable monomer is preferably 100 or more, more preferably 150 or more.

Moreover, the polymerizable monomer includes compounds having a boiling point of 100° C. or higher under normal pressure. Examples include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol Penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol (meth)acrylate, trimethylolpropane tri(acryloyloxypropyl)ether, tri(acryloyloxyethyl)isocyanurate, glycerin and trimethylolethane. Compounds obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth)acrylated are described in JP-B-48-041708, JP-B-50-006034, and JP-A-51-037193. Urethane (meth)acrylates such as those described in JP-A-48-064183, JP-B-49-043191, JP-B-52-030490, polyester acrylates, epoxy resins and (meth)acryl Polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products with acids, and mixtures thereof can be mentioned. Compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Further, polyfunctional (meth)acrylate obtained by reacting polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth)acrylate and an ethylenically unsaturated bond can also be used. Further, as a polymerizable monomer other than the above, JP 2010-160418, JP 2010-129825, described in Patent No. 4364216, etc., having a fluorene ring, having an ethylenically unsaturated bond Also included are compounds having two or more groups and cardo resins. Furthermore, other examples include specific unsaturated compounds described in JP-B-46-043946, JP-B-01-040337, JP-B-01-040336, and JP-A-02-025493. vinyl phosphonic acid-based compounds, and the like. Compounds containing perfluoroalkyl groups described in JP-A-61-022048 can also be used. Furthermore, the journal of Japan Adhesive Association vol. 20, No. 7, 300-308 (1984) as photopolymerizable monomers and oligomers can also be used.

In addition to the above, compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964, compounds described in paragraphs 0087 to 0131 of WO 2015/199219 can also be preferably used, the contents of which are herein incorporated into the book.

Further, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylated, which are described together with specific examples as formulas (1) and (2) in JP-A-10-062986, It can be used as a polymerizable monomer.

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

As the polymerizable monomer, dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; Nippon Kayaku Co., Ltd. ), A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.), and these (meth)acryloyl groups are bound via ethylene glycol residues or propylene glycol residues. A compound having a structure having

Examples of commercially available polymerizable monomers include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, SR-209, a bifunctional methacrylate having four ethyleneoxy chains, manufactured by Sartomer. 231, 239, Nippon Kayaku Co., Ltd. DPCA-60, a hexafunctional acrylate having 6 pentyleneoxy chains, TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS-10 , UAB-140 (manufactured by Nippon Paper Industries), 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 (Japan Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blenmer PME400 (manufactured by NOF Corporation), etc. mentioned.

Examples of polymerizable monomers include urethane acrylates such as those described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, JP-B-02-016765, 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 described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238 are used. can also be used.

The polymerizable monomer may be a compound having an acid group such as a carboxyl group or a phosphoric acid group. The polymerizable monomer having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and the unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid group. is more preferable. Particularly preferably, in a polymerizable monomer obtained by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give an acid group, the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. is a compound. Commercially available products include, for example, M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
The acid value of the polymerizable monomer having an acid group is preferably 0.1-40 mgKOH/g, particularly preferably 5-30 mgKOH/g. If the acid value of the polymerizable monomer is within the above range, the production and handling properties are excellent, and the developability is also excellent. Moreover, the polymerizability is good.

The content of the polymerizable monomer is preferably 20% by mass or less, more preferably 18% by mass or less, and 15% by mass or less with respect to the total solid content of the resin composition of the present invention. is more preferred. The lower limit may be greater than 0% by mass, 1% by mass or more, or 3% by mass or more.
It is also preferred that the resin composition of the present invention does not substantially contain a polymerizable monomer. According to this aspect, the elongation at break and chemical resistance of the resulting cured film can be further improved. In the present specification, the term "substantially free of polymerizable monomer" means that the content of the polymerizable monomer is 0.01% by mass or less with respect to the total solid content of the resin composition. , 0.005% by mass or less, and more preferably not contained. Although the detailed reason why such an effect is obtained is unknown, it is presumed that the polymerization reaction of the polymerizable monomer tends to proceed earlier than the cyclization reaction of the polyimide precursor. For this reason, if a polymerizable monomer is present during the cyclization reaction of the polyimide precursor, the polymerization reaction of the polymerizable monomer advances, presumably making it difficult for the cyclization of the polyimide precursor to proceed. Since the resin composition does not substantially contain a polymerizable monomer, the cyclization of the polyimide precursor is facilitated, and it is speculated that the elongation at break and chemical resistance of the resulting cured film could be further improved. be.

<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. Organic solvents include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.
Esters such as 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 (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.) )), 3-alkyloxypropionate alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- methyl ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionate alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate) etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyloxy-2-methylpropion methyl acid and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, pyruvate Suitable examples include propyl acid, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like.
Ethers such as 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 Preferred examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like.
Preferred examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone.
Suitable examples of aromatic hydrocarbons include toluene, xylene, anisole, limonene, and the like.
Suitable sulfoxides include, for example, dimethyl sulfoxide.
Suitable 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 coating surface, it is also preferable to mix two or more solvents.
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 A mixed solvent is preferred. A combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

From the viewpoint of coating properties, the content of the solvent is preferably an amount such that the total solid concentration of the resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass. More preferably, the amount is from 10 to 70% by mass, and even more preferably from 40 to 70% by mass. The solvent content may be adjusted according to the desired thickness and application method.
Only one kind of solvent may be contained, or two or more kinds may be contained. When two or more solvents are contained, the total is preferably within the above range.

<Migration inhibitor>
The resin composition of the present invention preferably further contains a migration inhibitor. By containing a migration inhibitor, it becomes possible to effectively suppress migration of metal ions derived from the metal layer (metal wiring) into the resin composition layer.
Migration inhibitors are not particularly limited, but heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, 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-based compounds, and hydrazide derivative-based compounds. In particular, triazole compounds such as 1,2,4-triazole and benzotriazole, and tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole are preferably used.

An ion trapping agent that traps anions such as halogen ions can also be used.

Other migration inhibitors include rust inhibitors described in paragraph 0094 of JP-A-2013-015701, compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, and JP-A-2011-059656. The compounds described in paragraph 0052, the compounds described in paragraphs 0114, 0116 and 0118 of JP-A-2012-194520, the compounds described in paragraph 0166 of WO 2015/199219, and the like can be used.

Specific examples of migration inhibitors 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% by mass, based on the total solid content of the resin composition, and 0.05 to 2.0%. 0% by mass, more 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, the total is preferably within the above range.

<Polymerization inhibitor>
The resin composition of the present invention preferably contains a polymerization inhibitor. Polymerization inhibitors include, for example, 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. In addition, 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. Also, 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% by mass with respect to the total solid content of the resin composition of the present invention. 0.02 to 3% by mass, and even more preferably 0.05 to 2.5% by mass. 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.

<Metal adhesion improver>
The resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used for electrodes, wiring, and the like. A silane coupling agent etc. are mentioned as a metal adhesion improving agent.

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

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

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and still more preferably 0 parts by mass with respect to 100 parts by mass of the polymer precursor. .5 to 5 parts by mass. When it is at least the above lower limit value, the adhesiveness between the cured film and the metal layer after the curing step is improved, and when it is at most the above upper limit value, the heat resistance and mechanical properties of the cured film after the curing step are improved. One type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, the total is preferably within the above range.

<Other additives>
The resin composition of the present invention may optionally contain various additives, such as thermal acid generators, sensitizing dyes, chain transfer agents, surfactants, higher fatty acid derivatives, 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 anti-aggregation agent, and the like. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the composition.

<<Thermal acid generator>>
The resin composition of the present invention may contain a thermal acid generator. When the specific thermal base generator has a protective group, the thermal acid generator is used for elimination of the protective group.

The content of the thermal acid generator is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the polymer precursor. By containing 0.01 parts by mass or more of the thermal acid generator, the cross-linking reaction and cyclization of the polymer precursor are promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved. Moreover, 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 electrical insulation of the cured film.
One type of thermal acid generator may be used, or two or more types 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. A sensitizing dye absorbs specific actinic radiation and enters an electronically excited state. The sensitizing dye in an electronically excited state comes into contact with a thermosetting accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, etc., and causes electron transfer, energy transfer, heat generation, and the like. As a result, the thermosetting accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo chemical changes and are decomposed to generate radicals, acids, or bases. For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP-A-2016-027357 can be referred to, the contents of which 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% by mass, based on the total solid content of the resin composition of the present invention. It is more preferably 1 to 15% by mass, even more preferably 0.5 to 10% by mass. The sensitizing dyes may be used singly 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 Kobunshi Dictionary, 3rd edition (edited by Kobunshi Gakkai, 2005), pp. 683-684. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. They can either donate hydrogen to less active radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals. In particular, thiol compounds can be preferably used.
In addition, the chain transfer agent can also use compounds described in paragraphs 0152 to 0153 of WO 2015/199219.

When the resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, preferably 1 to 20 parts by mass, per 100 parts by mass of the total solid content of the resin composition of the present invention. 10 parts by weight is more preferred, and 1 to 5 parts by weight is even more preferred. 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, the total is preferably within the above range.

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

In addition, surfactants can also be used compounds described in paragraphs 0159 to 0165 of WO 2015/199219.

When the resin composition of the present invention has a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass with respect to the total solid content of the resin composition of the present invention. , more preferably 0.005 to 1.0% by mass. One type of surfactant may be used, or two or more types may be used. When two or more surfactants are used, the total is preferably within the above range.

<<Higher Fatty Acid Derivatives>>
In order to prevent polymerization inhibition caused by oxygen, the resin composition of the present invention contains higher fatty acid derivatives such as behenic acid and behenic acid amide, which are unevenly distributed on the surface of the composition during the drying process after application. You may let
Moreover, the higher fatty acid derivative can also use the compound of the paragraph 0155 of international publication 2015/199219.
When the resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass based on 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 thereof may be used. When two or more higher fatty acid derivatives are used, the total is preferably within the above range.

<Restrictions on other contained substances>
From the viewpoint of coating surface properties, 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 insulation, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Metals include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When multiple metals are included, the total of these metals is preferably within the above range.
In addition, as a method for reducing metal impurities unintentionally contained in the resin composition of the present invention, a raw material having a low metal content is selected as a raw material constituting the resin composition of the present invention. Examples include a method in which the raw material constituting the product is subjected to filter filtration, and a method in which the inside of the apparatus is lined with polytetrafluoroethylene or the like to perform distillation under conditions in which contamination is suppressed as much as possible.

Considering the use of the resin composition of the present invention as a semiconductor material, the content of halogen atoms is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and less than 200 ppm by mass from the viewpoint of wiring corrosion. is more preferred. Among them, those present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Halogen atoms include chlorine and bromine atoms. The total amount of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is preferably within the above range.

A conventionally known container can be used as the container for the resin composition of the present invention. In addition, in order to suppress the contamination of raw materials and compositions with impurities, the storage container is a multi-layer bottle whose inner wall is made of 6 types and 6 layers of resin, and 6 types of resin are used in a 7-layer structure. It is also preferred to use a bottle that has been sealed. Examples of such a container include the container described in JP-A-2015-123351.

[Preparation of resin composition]
The resin composition of the present invention can be prepared by mixing the components described above. The mixing method is not particularly limited, and conventionally known methods can be used.
Moreover, 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 filter pore size is preferably 1 µm or less, more preferably 0.5 µm or less, and even more preferably 0.1 µm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. A filter that has been pre-washed with an organic solvent may be used. In the filter filtration step, multiple types of filters may be connected in series or in parallel for use. When multiple types of filters are used, filters with different pore sizes or materials may be used in combination. Also, various materials may be filtered multiple times. When filtering multiple times, circulation filtration may be used. Moreover, you may filter by pressurizing. When pressurizing and filtering, the pressure to pressurize is preferably 0.05 MPa or more and 0.3 MPa or less.
In addition to filtration using a filter, impurities may be removed using an adsorbent. You may combine filter filtration and the impurity removal process using an adsorbent. 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, Laminate, Semiconductor Device, and Manufacturing Method Thereof]
Next, cured films, laminates, semiconductor devices, and manufacturing methods thereof will be described.
The cured film of the present invention is obtained by curing the resin composition of the present invention. The film thickness of the cured film of the present invention can be, for example, 0.5 μm or more, and can be 1 μm or more. Moreover, as an upper limit, it can be set to 100 μm or less, and can also be set to 30 μm or less.

Two or more layers, or three to seven layers of the cured film of the present invention 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.

Fields to which the cured film of the present invention can be applied include insulating films for semiconductor devices, interlayer insulating films for rewiring layers, stress buffer films, and the like. In addition, pattern formation by etching of a sealing film, a substrate material (a base film or a coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting as described above can be used. For these applications, for example, Science & Technology Co., Ltd. "High Functionality and Application Technology of Polyimide" April 2008, Masaaki Kakimoto / supervised, CMC Technical Library "Basics and Development of Polyimide Materials" Published November 2011 , Japan Polyimide/Aromatic Polymer Study Group/Edited "Latest Polyimide Fundamentals and Applications", NTS, August 2010, etc. can be referred to.

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

The method for producing a cured film of the present invention includes using the resin composition of the present invention. Specifically, it preferably includes 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; (c) developing the exposed resin composition layer; (d) A 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. . In this heating step, the thermal base generator and the thermosetting compound act to obtain sufficient curability.

A 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. In the method for producing a laminate of the present embodiment, after forming a cured film according to the above method for producing a cured film, the step (a), or the steps (a) to (c), or (a ) to (d) are performed. In particular, it is preferable to perform each of the above steps in order multiple times, for example, 2 to 5 times (that is, 3 to 6 times in total). By laminating the cured films in this manner, a laminate can be obtained. In the present invention, it is particularly preferred 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 at least (a), preferably (a) to (c) or (a) to (d) ) can be performed a plurality of times to obtain a cured film laminate.

<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 (layered).
The type of substrate can be appropriately determined depending on the application, but semiconductor manufacturing substrates such as silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films , reflective film, metal substrates such as Ni, Cu, Cr, and Fe, paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, plasma display panel (PDP) electrode plates, etc. are not particularly limited. In the present invention, a semiconductor fabrication substrate is particularly preferred, and a silicon substrate is more preferred.
Moreover, when forming a resin composition layer on the surface of a resin layer or the surface of a metal layer, a resin layer or a metal layer becomes a board|substrate.
Coating is preferable as a means for applying the resin composition to the substrate.
Specifically, applicable means include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and ink jet method. From the viewpoint of uniformity of the thickness of the resin composition layer, the spin coating method, slit coating method, spray coating method, and inkjet method are more preferable. A resin layer having a desired thickness can be obtained by appropriately adjusting the 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 a circular substrate such as a wafer, a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular substrate, a slit coating method, a spray coating method, an inkjet method, etc. Law and the like are preferred. In the case of spin coating, 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 drying to remove the solvent after forming the resin composition layer and after the film forming step (layer forming step). The drying temperature is preferably 50 to 150°C, more preferably 70 to 130°C, even more preferably 90 to 110°C. The drying time is exemplified from 30 seconds to 20 minutes, preferably from 1 minute to 10 minutes, more preferably from 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 amount of exposure is not particularly defined as long as the resin composition can be cured, but for example, it is preferable to irradiate 100 to 10,000 mJ/cm ² , and more preferably 200 to 8,000 mJ/cm ² in terms of exposure energy at a wavelength of 365 nm. more preferred.
The exposure wavelength can be appropriately determined in the range of 190-1000 nm, preferably 240-550 nm.
In relation to the light source, 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 (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer laser (wavelength: 157 nm), (5) extreme ultraviolet; EUV (wavelength: 13.6 nm), (6) electron beam, and the like. For the resin composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferred, and exposure with i-line is particularly preferred. Thereby, 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 portions (non-exposed portions) are removed. The developing method is not particularly limited as long as a desired pattern can be formed.
Development is performed using a developer. The developer can be used without any particular limitation as long as the unexposed portion (non-exposed portion) is removed. The developer preferably contains an organic solvent, and more preferably contains 90% or more of the organic solvent. In the present invention, the developer preferably contains an organic solvent with a ClogP value of −1 to 5, more preferably an organic solvent with a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting the structural formula in ChemBioDraw.
Organic solvents 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. . ethyl ethoxyacetate, etc.)), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, 3-methoxypropionic acid ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionate alkyl esters (e.g. methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl propyl oxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvate Ethyl acid, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and , ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and aromatic hydrocarbons such as toluene, xylene, anisole, limonene. etc., dimethyl sulfoxide is preferably exemplified as sulfoxides.
In the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred.
The developer preferably contains 50% by mass or more of the organic solvent, more preferably 70% by mass or more of the organic solvent, and even more preferably 90% by mass or more of the organic solvent. Further, the developer may contain 100% by mass of the organic solvent.

The development time is preferably 10 seconds to 5 minutes. The temperature of the developer during development is not particularly specified, but the development is usually carried out at 20 to 40°C.
After processing with the developer, rinsing may be performed. Rinsing is preferably done with a solvent different from the developer. For example, the solvent contained in the resin composition can be used for rinsing. Rinsing time is preferably 5 seconds to 1 minute.

<Heating process>
The production method of the present invention preferably includes a heating step after a film forming step (layer forming step), a drying step, or a developing step. In the heating step, the cyclization reaction of the polymer precursor and the curing reaction of the thermosetting compound 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, further preferably 140° C. or higher, and 150° C. or higher. is more preferred, 160° C. or higher is even more preferred, and 170° C. or higher is even more preferred. The upper limit is preferably 500° C. or lower, more preferably 450° C. or lower, even more preferably 350° C. or lower, even more preferably 250° C. or lower, and 220° C. or lower. Even more preferable.
Heating is preferably carried out from the temperature at the start of heating to the maximum heating temperature at a temperature rising rate of 1 to 12°C/min, more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min. By setting the temperature increase rate to 1° C./min or more, excessive volatilization of amine can be prevented while ensuring productivity, and by setting the temperature increase rate to 12° C./min or less, the cured film can be cured. 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, even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at which the process of heating up 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 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 from the temperature.
The heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, even more preferably 30 to 240 minutes.
Particularly when forming a multi-layer laminate, the heating temperature is preferably 180° C. to 320° C., more preferably 180° C. to 260° C., from the viewpoint of adhesion between the layers of the cured film. Although the reason for this is not clear, it is believed that the ethynyl groups of the polymer precursor between the layers are cross-linked with each other at this temperature.

Heating may be done 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, heated from 180° C. to 200° C. at 2° C./min, and held at 200° C. for 120 minutes. , may be performed. The heating temperature in the pretreatment step is preferably 100 to 200°C, more preferably 110 to 190°C, even more preferably 120 to 185°C. In this pretreatment step, it is also preferable to carry out the treatment while irradiating ultraviolet rays as described in US Pat. No. 9,159,547. Such a pretreatment process can improve the properties of the film. The pretreatment step is preferably performed for 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, pretreatment step 1 may be performed at 100 to 150°C, and then pretreatment step 2 may be performed at 150 to 200°C.
Further, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5°C/min.

The heating step is preferably carried out in an atmosphere of low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium, or argon, in order to prevent decomposition of the polymer precursor. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.

<Metal layer 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 development.
The metal layer is not particularly limited, and existing metal species can be used. Copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified. More preferred.
A 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, electroplating, electroless plating, etching, printing, and a combination thereof can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electroplating can be mentioned.
The thickness of the metal layer is preferably 0.1 to 50 μm, more preferably 1 to 10 μm, at the thickest portion.

<Lamination process>
Preferably, the production method of the present invention further includes a lamination step.
The lamination step means that the surface of the cured film (resin layer) or metal layer is again subjected to (a) film formation step (layer formation step), (b) exposure step, (c) development treatment step, (d) heating step are performed in this order. However, only the film forming step (a) may be repeated. Also, (d) the heating step may be performed collectively at the end or in the middle of lamination. That is, the steps (a) to (c) may be repeated a predetermined number of times, and thereafter the laminated resin composition layers may be cured at once by heating (d). In addition, after the (c) development step, (e) a metal layer forming step may be included, and even if the heating of (d) is performed each time at this time, after stacking a predetermined number of times, (d) is collectively performed. Heating may be performed. Needless to say, the lamination step may further include the drying step, the heating step, and the like as appropriate.
When the lamination step is further performed after the lamination 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 lamination step is preferably performed 2 to 5 times, more preferably 3 to 5 times.
For example, the resin layer is preferably composed of 3 to 7 layers, such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, and more preferably 3 to 5 layers.
In the present invention, it is particularly preferable to form a cured film (resin layer) of the resin composition so as to cover the metal layer after providing the metal layer. Specifically, (a) film formation step, (b) exposure step, (c) development step, (e) metal layer formation step, and (d) heating step are repeated in this order, or (a) film formation (b) the exposure step, (c) the development step, and (e) the metal layer formation step, and the step (d) is collectively provided at the end or in the middle. By alternately performing the lamination step of laminating the resin composition layer (resin) and the metal layer forming step, the resin composition layer (resin layer) and the metal layer can be alternately laminated.

The present invention also discloses semiconductor devices comprising the cured films or laminates of the present invention. Specific examples of a semiconductor device using the resin composition of the present invention for forming an interlayer insulating film for a rewiring layer can refer to the descriptions in paragraphs 0213 to 0218 of JP-A-2016-027357 and the description in FIG. The contents of which are incorporated herein.

EXAMPLES The present invention will be described more specifically with reference to examples below. The materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. "Parts" and "%" are based on mass unless otherwise specified.

<Synthesis Example 1>
[Synthesis of polyimide precursor (A-1: polyimide precursor having no radically polymerizable group) from pyromellitic dianhydride, 4,4'-diaminodiphenyl ether and benzyl alcohol]
14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140° C. for 12 hours) and 14.22 g (131.58 mmol) of benzyl alcohol were suspended in 50 mL of N-methylpyrrolidone. , dried over molecular sieves. The suspension was heated at 100° C. for 3 hours. The reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) of pyridine and 90 mL of N-methylpyrrolidone were added. The reaction mixture was then cooled to -10.degree. C. and 16.12 g (135.5 mmol) of _SOCl.sub.2 was added over 10 minutes while maintaining the temperature at -10.+-.4.degree. The viscosity increased during the addition of _SOCl2 . After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. A solution of 11.08 g (58.7 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was then added dropwise to the reaction mixture at -5 to 0°C over 20 minutes. After reacting the reaction mixture at 0° C. for 1 hour, 70 g of ethanol was added and stirred overnight at room temperature. The polyimide precursor was then precipitated in 5 liters of water and the water-polyimide precursor mixture was stirred at a speed of 5000 rpm for 15 minutes. The polyimide precursor was filtered off, stirred again in 4 liters of water for 30 minutes and filtered again. The resulting polyimide precursor was then dried under reduced pressure at 45° C. for 3 days. The weight average molecular weight of this polyimide precursor was 18,000.

A-1

<Synthesis Example 2>
[Synthesis of polyimide precursor (A-2: polyimide precursor having radically polymerizable group) from pyromellitic dianhydride, 4,4′-diaminodiphenyl ether and 2-hydroxyethyl methacrylate]
14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20 .4 g of pyridine (258 mmol) and 100 g of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at a temperature of 60° C. for 18 hours to prepare the diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Then, after chlorinating the resulting diester with SOCl ₂ , it was converted into a polyimide precursor with 4,4′-diaminodiphenyl ether in the same manner as in Synthesis Example 1, and the polyimide precursor was obtained in the same manner as in Synthesis Example 1. Obtained. The weight average molecular weight of this polyimide precursor was 19,000.

A-2

<Synthesis Example 3>
[Synthesis of polyimide precursor (A-3: polyimide precursor having radically polymerizable group) from 4,4′-oxydiphthalic anhydride, 4,4′-diaminodiphenyl ether and 2-hydroxyethyl methacrylate]
20.0 g (64.5 mmol) of 4,4′-oxydiphthalic anhydride (dried at 140° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate and 0.05 g of hydroquinone , 20.4 g of pyridine (258 mmol) and 100 g of diglyme were mixed and stirred at a temperature of 60° C. for 18 hours to prepare a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate. . Then, after chlorinating the resulting diester with SOCl ₂ , it was converted into a polyimide precursor with 4,4′-diaminodiphenyl ether in the same manner as in Synthesis Example 1, and the polyimide precursor was obtained in the same manner as in Synthesis Example 1. Obtained. The weight average molecular weight of this polyimide precursor was 18,000.

A-3

<Synthesis Example 4>
[Polyimide precursor from 4,4′-oxydiphthalic anhydride, 4,4′-diamino-2,2′-dimethylbiphenyl (orthotolidine) and 2-hydroxyethyl methacrylate (A-4: having a radically polymerizable group Synthesis of polyimide precursor)]
20.0 g (64.5 mmol) of 4,4′-oxydiphthalic anhydride (dried at 140° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate and 0.05 g of hydroquinone , 20.4 g of pyridine (258 mmol) and 100 g of diglyme were mixed and stirred at a temperature of 60° C. for 18 hours to prepare a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate. . Then, after chlorinating the resulting diester with SOCl ₂ , it was converted to a polyimide precursor with 4,4'-diamino-2,2'-dimethylbiphenyl in the same manner as in Synthesis Example 1, and A polyimide precursor was obtained by the method of The weight average molecular weight of this polyimide precursor was 19,000.

A-4

<Examples and Comparative Examples>
Each resin composition was obtained by mixing the components shown in the table below. The resulting resin composition was filtered under pressure through a filter with a pore width of 0.8 μm.

（Ｃ）熱硬化性化合物
Ｃ－１～Ｃ－３：下記構造の化合物

（Ｄ）光重合開始剤
Ｄ－１、Ｄ－２：下記構造の化合物

（Ｅ）熱塩基発生剤
Ｅ－１～Ｅ－３：下記構造の化合物

（Ｆ）重合禁止剤
Ｆ－１、Ｆ－２：下記構造の化合物

（Ｇ）添加剤
Ｇ－１、Ｇ－２：下記構造の化合物

（Ｈ）シランカップリング剤
Ｈ－１、Ｈ－２：下記構造の化合物

（Ｉ）溶剤
Ｉ－１：γ－ブチロラクトン
Ｉ－２：ジメチルスルホキシドThe raw materials listed in the above table are as follows.
(A) Polyimide precursors A-1 to A-4: polyimide precursors A-1 to A-4 synthesized above
(B) Polymerizable monomer:
B-1, B-2: compounds having the following structures

(C) thermosetting compounds C-1 to C-3: compounds having the following structures

(D) Photopolymerization initiators D-1 and D-2: compounds having the following structures

(E) Thermal base generators E-1 to E-3: compounds having the following structures

(F) Polymerization inhibitors F-1 and F-2: compounds having the following structures

(G) Additives G-1, G-2: compounds having the following structures

(H) Silane coupling agents H-1, H-2: compounds having the following structures

(I) solvent I-1: γ-butyrolactone I-2: dimethyl sulfoxide

<Production of cured film>
Each resin composition was applied onto a silicon wafer by spin coating to form a resin composition layer. The silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100° C. for 4 minutes to form a uniform resin composition layer having a thickness of 20 μm on the silicon wafer. The resin composition layer on the silicon wafer is exposed with an exposure energy of 400 mJ/cm ² using a broadband exposure machine (Ushio Inc.: UX-1000SN-EH01), and the exposed photosensitive resin composition layer ( The resin layer) was heated at a rate of 5° C./min in a nitrogen atmosphere, reaching 180° C., and then heated for 2 hours. The cured resin layer was immersed in a 3% hydrofluoric acid solution to separate the resin layer from the silicon wafer to obtain a cured film.

<Breaking elongation>
The elongation at break of the resulting cured film was measured. The elongation at break of the cured film was measured using a tensile tester (Tensilon) at a crosshead speed of 300 mm/min, a width of 10 mm, and a sample length of 50 mm. was measured in accordance with JIS-K6251 (Japanese Industrial Standards) under the environment of . Breaking elongation is Eb = (L _b - L ₀ )/L ₀ (E _b : breaking elongation, L ₀ : length of test piece before test, L _b : length of test piece when cut ). For evaluation, the breaking elongation was measured 10 times and the average value was used. The results were classified and evaluated as follows.
A: Breaking elongation is 60% or more B: Breaking elongation is 50% or more and less than 60% C: Breaking elongation is less than 50%

<Chemical resistance>
The resulting cured film was immersed in the following chemicals under the following conditions, and the dissolution rate was calculated.
Chemical: 90:10 (mass ratio) mixture of dimethyl sulfoxide (DMSO) and 25% by mass tetramethylammonium hydroxide (TMAH) solution Evaluation conditions: The resin layer was immersed in the solution at 75°C for 15 minutes, and the The film thicknesses were compared and the dissolution rate (nm/min) was calculated.
A: Less than 250 nm/min B: 250 nm/min or more and less than 500 nm/min C: 500 nm/min or more

<Lithography evaluation>
Each resin composition was spin-coated onto a silicon wafer. The silicon wafer to which the resin composition was applied was dried on a hot plate at 100° C. for 4 minutes to form a uniform resin composition layer with a thickness of 20 μm on the silicon wafer. The resin composition layer on the silicon wafer was exposed using a stepper (Nikon NSR 2005 i9C). Exposure was performed with i-line at a wavelength of 365 nm at exposure energies of 200, 300, 400, 500, 600, 700, and 800 mJ/cm ² using a line-and-space photomask from 5 μm to 25 μm in increments of 1 μm. , exposure was performed to obtain a resin layer. This resin layer was developed with cyclopentanone for 60 seconds. The smaller the line width of the obtained resin layer (line pattern), the more fine the pattern can be formed, and the result is favorable. In addition, the more the minimum line width that can be formed is more difficult to change with respect to the fluctuation of the exposure amount, the greater the arbitrariness of the exposure amount in forming a fine pattern, which is a favorable result.
A: The line width is less than 10 μm B: The line width is 10 μm or more and less than 20 μm C: The line width is 20 μm or more, or a pattern having a line width with sharp edges was not obtained.

As shown in the table above, in the examples, cured films having good elongation at break and excellent chemical resistance could be formed.

Claims (14)

a polyimide precursor containing a radically polymerizable group;
a photoradical polymerization initiator;
a thermal base generator;
a thermosetting compound having a plurality of functional groups selected from the group consisting of epoxy groups, oxetanyl groups, methylol groups, alkoxymethyl groups, phenol groups, maleimide groups, cyanate groups and blocked isocyanate groups;
a polymerizable monomer having 2 to 8 (meth)acryloyl groups and having a molecular weight of 900 or less;
A resin composition comprising
The content of the photoradical polymerization initiator is 1.0 to 10% by mass with respect to the total solid content of the resin composition,
The content of the thermosetting compound is 1 to 25 parts by mass with respect to 100 parts by mass of the polyimide precursor, and 10 to 1000 parts by mass with respect to 100 parts by mass of the thermal base generator,
The content of the polymerizable monomer is 3 to 15% by mass with respect to the total solid content of the resin composition,
Resin composition. The resin composition according to claim 1, wherein the thermosetting compound is a compound represented by the following formula (TC1);
X ¹ −(Y ¹ ) _n (TC1)
In formula (TC1), X ¹ represents an n-valent linking group, Y ¹ represents an epoxy group, oxetanyl group, methylol group, alkoxymethyl group, phenol group, maleimide group, cyanate group or blocked isocyanate group, and n represents Represents an integer of 2 or more. The resin composition according to claim 2, wherein ^X1 of the formula (TC1) contains a cyclic structure. The resin composition according to any one of claims 1 to 3, wherein the thermosetting compound is a compound having multiple alkoxymethyl groups. The resin composition according to any one of claims 1 to 3, wherein the thermosetting compound is a compound having multiple methoxymethyl groups. The resin composition according to any one of claims 1 to 5, wherein the base generation temperature of the thermal base generator is lower than the curing initiation temperature of the thermosetting compound. The polyimide precursor has a structural unit represented by the following formula (1), the resin composition according to any one of claims 1 to 6;

In formula (1), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, R ¹¹³ and Each R ¹¹⁴ independently represents a hydrogen atom or a monovalent organic group; provided that at least one of R ¹¹³ and R ¹¹⁴ contains a radically polymerizable group. The resin composition according to any one of claims 1 to 7, which is used for forming an interlayer insulating film for rewiring layers. A cured film obtained by curing the resin composition according to any one of claims 1 to 7. A laminate having two or more layers of the cured film according to claim 9 and having a metal layer between the two layers of the cured film. A method for producing a cured film, comprising a film forming step of applying the resin composition according to any one of claims 1 to 7 to a substrate to form a film. 12. The method for producing a cured film according to claim 11, comprising an exposure step of exposing the film and a developing step of developing the film. The method for producing a cured film according to claim 12, comprising heating the film at 80 to 450°C. A semiconductor device comprising the cured film according to claim 9 or the laminate according to claim 10.