WO2020066976A1

WO2020066976A1 - Resin composition, cured film, multilayer body, method for producing cured film and semiconductor device

Info

Publication number: WO2020066976A1
Application number: PCT/JP2019/037188
Authority: WO
Inventors: 遥菜井上; 敏明福原; 修平山口
Original assignee: 富士フイルム株式会社
Priority date: 2018-09-27
Filing date: 2019-09-24
Publication date: 2020-04-02
Also published as: JPWO2020066976A1; TW202024187A; KR20210048519A; CN112752798A; JP7237978B2

Abstract

A resin composition which contains: a polyimide precursor; a thermal base generator; and a thermosetting compound that has a plurality of functional groups which are selected from the group consisting of epoxy groups, oxetanyl groups, methylol groups, alkoxymethyl groups, phenol groups, maleimide groups, cyanate groups and blocked isocyanates. A cured film, a multilayer body, a method for producing a cured film, and a semiconductor device, each of which uses this resin composition.

Description

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

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 described above.

Polyimide resins have been applied to various uses because of their excellent heat resistance and insulation properties. The application of the semiconductor device is not particularly limited. For example, a semiconductor device for mounting may be used as a material for an insulating film or a sealing material, or as a protective film (see Non-Patent Documents 1 and 2). Further, it is also used as a base film or coverlay of a flexible substrate.
On the other hand, polyimide resins generally have low solubility in solvents. Therefore, a method of dissolving in a solvent in a state of a polymer precursor before the cyclization reaction, specifically, a polyimide precursor is often used. Thereby, excellent handling properties can be realized, and when each of the above products is manufactured, it can be applied and processed in various forms on a substrate or the like. Thereafter, the polyimide precursor can be cyclized by heating to form a cured product. In addition to the high performance of polyimide resins and the like, such industrial adaptability is increasingly expected from the viewpoint of excellent manufacturing adaptability.

Patent Document 1 discloses that (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 a polymerization initiator: 1 to 20 parts by mass and (D) a thermal crosslinking agent: 5 to 30 parts by mass 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 crosslinking agent. A photosensitive resin composition is described.

JP 2003-287889 A JP 2014-201695 A

Recently, it has been studied to cyclize a polyimide precursor at a low temperature to obtain a cured product. Further, with respect to a cured product obtained by cyclizing a polyimide precursor at a low temperature, it is desired to further improve properties such as elongation at break and chemical resistance.

Therefore, an object of the present invention is to provide a resin composition, a cured film, a laminate, a method for producing a cured film, and a semiconductor device capable of forming a cured film having excellent elongation at break and chemical resistance. .

The present inventors have conducted intensive studies on a resin composition containing at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor. And found that a cured film having excellent chemical resistance can be formed, and completed the present invention. The present invention provides the following.

<1> a polyimide precursor,
A thermal base generator,
A thermosetting compound having a plurality of functional groups selected from the group consisting of an epoxy group, an oxetanyl group, a methylol group, an alkoxymethyl group, a phenol group, a maleimide group, a cyanate group and a blocked isocyanate group,
A resin composition comprising:
<2> the resin composition according to <1>, wherein the thermosetting compound is a compound represented by the following formula (TC1);
X ^1- (Y ¹ ) _n ... (TC1)
In the formula (TC1), X ¹ represents an n-valent linking group, Y ¹ represents an epoxy group, an oxetanyl group, a methylol group, an alkoxymethyl group, a phenol group, a maleimide group, a cyanate group or a blocked isocyanate group, and n is Represents an integer of 2 or more.
<3> The resin composition according to <2>, wherein X ^{1 in the} formula (TC1) includes 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 thermobase 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 based on the total solid content of the resin composition. Stuff.
<8> The resin composition according to any one of <1> to <7>, wherein the polyimide precursor contains a radical 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 R ¹¹⁴ each 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 the formula (1) contains a radically polymerizable group.
<11> The resin composition according to <8> or <10>, further including 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 redistribution layer.
<13> A cured film obtained by curing the resin composition according to any one of <1> to <12>.
<14> A laminate having at least two cured films according to <13> and having a metal layer between the two cured films.
<15> A method for producing a cured film, comprising a film formation step of forming a film by applying the resin composition according to any one of <1> to <12> to a substrate.
<16> The method for producing a cured film according to <15>, 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 a step of heating the film at 80 to 450 ° C.
<18> A semiconductor device having the cured film according to <13> or the laminate according to <14>.

According to the present invention, 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 excellent in elongation at break and chemical resistance can be provided.

内容 Hereinafter, the content of the present invention will be described in detail. In this specification, “to” is used to mean that the numerical values described before and after it are included as the lower limit and the upper limit.

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

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

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

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

において In the resin composition of the present invention, the content of the polymerizable monomer having a plurality of (meth) acryloyl groups is preferably 20% by mass or less based on the total solid content of the resin composition. Also according to this aspect, the effects of the present invention can be more remarkably obtained. The lower limit can be more than 0% by mass.

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

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

ポリイミド The polyimide precursor used in the present invention preferably contains a radically polymerizable group. The radical polymerizable group is a group capable of undergoing a cross-linking reaction by the action of a radical, and a preferable example is a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth) acryloyl group, and a group represented by the following formula (III). When a polyimide precursor containing a radical polymerizable group is used, a cured film having more excellent properties is easily obtained. Further, when the resin composition of the present invention contains a photoradical polymerization initiator, it can be a resin composition having excellent pattern formability by a photolithography method.

The polyimide precursor preferably contains a structural unit represented by the following formula (1). With such a configuration, a resin composition having more excellent film strength can be obtained.

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

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

<<<< R ¹¹¹ >>>
R ¹¹¹ represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, a heteroaromatic group, or a group composed of a combination thereof. 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 composed of a combination thereof. Preferably, an aromatic group having 6 to 20 carbon atoms is more preferable.
Preferably, R ¹¹¹ is derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Diamines may be used alone or in combination of two or more.
Specifically, the diamine may be 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. Preferably, the diamine is a diamine containing an aromatic group having 6 to 20 carbon atoms. Examples of the aromatic group include the following.

In the formula, A is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, —O—, —C (＝ O) —, —S—, —S It is preferably a group selected from (ＮＨO) ₂ —, —NHCO— and a combination thereof, a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted by a fluorine atom, —O— , —C (＝ O) —, —S— and —SO ₂ —, more preferably —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 —.

Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 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 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenylate 4,4'- and 3,3'-diaminodiphenylmethane, 4,4'- and 3,3'-diaminodiphenylsulfone, 4,4'- and 3,3'-diaminodiphenylsulfide, 4,4 ' -And 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl (4,4'-diamino-2,2 '-Dimethylbiphenyl), 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2- (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino -3-hydroxyphenyl) sulfone, 4,4'-diaminoparaterphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (2-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis (4-aminophenyl) anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis (4-aminophenoxy) Benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenyl) benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl- 4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) Phenyl] hexafluoropropane, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 3,3 ′, 4,4′-tetraaminobiphenyl, 3,3 ′, 4,4′-tetraaminodiphenyl ether 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl 9,9'-bis (4-aminophenyl) fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane , 2- (3 ', 5'-diaminobenzoyloxy) ethyl methacrylate, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-paraphenylenediamine, acetoguanamine, 2,3,5,6- Tetramethyl-paraphenylenediamine, 2,4,6-trimethyl-metaphenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-aminophenyl) ethane, diaminobenzanilide, ester of diaminobenzoic acid, 1,5-diaminonaphtha , Diaminobenzotrifluoride, 1,3-bis (4-aminophenyl) hexafluoropropane, 1,4-bis (4-aminophenyl) octafluorobutane, 1,5-bis (4-aminophenyl) decafluoro Pentane, 1,7-bis (4-aminophenyl) tetradecafluoroheptane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (2-amino Phenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3 , 5-bis (trifluoromethyl) phenyl] hexafluoropropane, parabis (4-amino-2-trifluoromethyl Tylphenoxy) benzene, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4,4'- Bis (4-amino-2-trifluoromethylphenoxy) 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'-hexafluorotrizine and 4,4'-diaminoquaterphenyl It includes at least one diamine barrel.

ジアミン Also, the following diamines (DA-1) to (DA-18) are preferable.

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

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

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

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

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

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

Diamine compounds giving 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.

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

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

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

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

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

Further, the following tetracarboxylic dianhydrides (DAA-1) to (DAA-5) are also preferable examples.

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

In the formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and a methyl group is more preferable.
In the formula (III), R ²⁰¹ is an alkylene group having 2 to 12 carbon atoms, —CH ₂ CH (OH) CH ₂ — or a (poly) oxyalkylene group having 4 to 30 carbon atoms (an alkylene group having 1 carbon atom To 12, preferably 1 to 6, more preferably 1 to 3, and the number of repetitions 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 ^R201 include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene, octamethylene, dodecamethylene. , —CH ₂ CH (OH) CH ₂ —, and more preferably an ethylene group, a propylene group, a trimethylene group, and —CH ₂ CH (OH) CH ₂ —.
Particularly preferably, R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethylene group.

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

As the aromatic group, specifically, a substituted or unsubstituted aromatic hydrocarbon group (the cyclic structure constituting the group includes a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an indene ring, an azulene ring) Ring, heptarene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene ring, triphenylene ring, etc.) or a substituted or unsubstituted aromatic heterocyclic group (group As the constituting cyclic structure, 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, quinolizi 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, phenoxatiin ring, phenothiazine ring Or a phenazine ring).

ポリイミド It is also preferable that the polyimide precursor has a fluorine atom in the structural unit. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, more preferably 20% by mass or less. There is no particular upper limit, but 50% by mass or less is practical.

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

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

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

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

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

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

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

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

It is preferable that the production of the polyimide precursor includes a step of depositing a solid. Specifically, the polyimide precursor in the reaction solution can be precipitated in water and dissolved in a solvent in which the polyimide precursor is soluble, such as tetrahydrofuran, to perform solid deposition.

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 preferably 40% by mass or more based on the total solid content of the resin composition. Is more preferably 50% by mass or more, still 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, based on the total solid content of the resin composition. , 98% by mass or less, more preferably 95% by mass or less.
The resin composition of the present invention may include only one kind of the polyimide precursor, or may include two or more kinds of the polyimide precursor. When two or more kinds are included, the total amount is preferably in the above range.

<Heat base generator>
The resin composition of the present invention contains a thermal base generator. The type of the thermal base generator is not particularly limited, but is selected from an acidic compound which generates a base when heated to 40 ° C. or more, and an ammonium salt having an anion having an pKa of 0 to 4 and an ammonium cation. It is preferable to include a thermal base generator containing at least one of these. Here, pKa1 represents the logarithm (−Log ₁₀ Ka) of the dissociation constant (Ka) of the first proton of the acid, which will be described in detail later.
By compounding such a compound, the cyclization reaction of the polyimide precursor can be performed at a low temperature. Further, since the thermal base generator does not generate a base unless heated, it can suppress cyclization of the polymer precursor during storage even when it is present together with the polymer precursor, and is excellent in storage stability.

Examples of the thermal base generator include an acidic compound (A1) that generates a base when heated to 40 ° C. or higher, an ammonium salt (A2) having an anion having a pKa of 0 to 4 and an ammonium cation, and a nonionic thermal base generator (A3). ), And 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 performed at a low temperature. In the present specification, the acidic compound refers to a compound obtained by collecting 1 g of a compound in a container, adding 50 mL of a mixed solution of ion-exchanged water and tetrahydrofuran (mass ratio: water / tetrahydrofuran = 1/4), and adding the compound for 1 hour at room temperature. The solution obtained by stirring the solution is a compound having a value of less than 7 when measured at 20 ° C. using a pH (power of hydrogen) meter.

塩基 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 further preferably 165 ° C. or lower. The base generation temperature is measured, for example, by differential scanning calorimetry, by heating the compound in a pressure-resistant capsule at 250C at 5C / min, reading the peak temperature of the lowest exothermic peak, and measuring the peak temperature as the base generation temperature. can do.

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

塩基 The base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, and more preferably a tertiary amine. Since the tertiary amine has a high basicity, the cyclization temperature of the polyimide precursor can be lowered. Further, 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 from 80 to 2,000. The lower limit is more preferably 100 or more. The upper limit is more preferably 500 or less. In addition, the value of molecular weight is a theoretical value obtained from the structural formula.

In the present embodiment, the acidic compound (A1) preferably contains at least one selected from an ammonium salt and a compound represented by the following formula (101) or (102).

において In the present embodiment, the ammonium salt (A2) is preferably an acidic compound. The ammonium salt (A2) may be a compound containing an acidic compound that generates a base when heated to 40 ° C. or higher (preferably 120 to 200 ° C.) or 40 ° C. or higher (preferably 120 to 200 ° C.) The compound may be a compound excluding an acidic compound which generates a base when heated to the step (1).

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

In the 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 the formulas (101) and (102) may be respectively bonded to form a ring.

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

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

In the present embodiment, the ammonium salt preferably has an anion having a pKa of 0 to 4 and an ammonium cation. The upper limit of the 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, and more preferably 1.0 or more. When the pKa1 of the anion is in the above range, the polymer precursor can be cyclized at a lower temperature, and further, 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 without heating can be suppressed, and the stability of the resin composition is good. When pKa1 is 0 or more, the generated base is difficult to be neutralized, and the cyclization efficiency of the polymer precursor is good.
The type of the anion is preferably one selected from a carboxylate anion, a phenol anion, a phosphate anion and a sulfate anion, and more preferably a carboxylate anion 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 a divalent or higher carboxylic acid anion having two or more carboxyl groups, and more preferably a divalent carboxylic acid anion. According to this aspect, it is possible to provide a thermal base generator that can further improve the stability, curability, and developability of the resin composition. In particular, by using an anion of a divalent carboxylic acid, the stability, curability and developability of the resin composition can be further improved.
In the present embodiment, the carboxylate anion is preferably a carboxylate anion having a pKa of 4 or less. 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 determined by Organic Structures by Physical Methods (author: Brown, HC, McDaniel, DH, Hafliger, Hafliger). Compiled by: Braude, EA, Nachod, FC; Academic Press, New York, 1955), and Data for Biochemical Research (author: Dawson, R., R.M. al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, values calculated from the structural formula using ACD / pKa (manufactured by ACD / Labs) software will be used.

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

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

In the present embodiment, the electron withdrawing group means a group having a positive Hammett's substituent constant σm. Here, σm is described by Yuno Tsuno, Synthetic Organic Chemistry Society, Vol. 631-642. Note that the electron-withdrawing group in the present embodiment is not limited to the substituents described in the above documents.
Examples of the substituent having a positive value of σm include a CF ₃ group (σm = 0.43), a CF ₃ CO group (σm = 0.63), an HC≡C group (σm = 0.21), and CH ₂ = CH group (σm = 0.06), Ac group (σm = 0.38), MeOCO group (σm = 0.37), MeCOCH = CH group (σm = 0.21), PhCO group (σm = 0 .34), H ₂ NCOCH ₂ group (σm = 0.06) and the like. Note that Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group.

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

In the 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 represents an aromatic group. Represents

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

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

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

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

In the 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 simultaneously hydrogen atoms. Further, Rb ¹ , Rb ² and Rb ³ do not have a carboxyl group. In this specification, a tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, this does not apply when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when forming an amide group together with a nitrogen atom.

In formulas (B1) and (B2), at least one of Rb ¹ , Rb ² and Rb ³ preferably has a cyclic structure, and more preferably at least two of them have a cyclic structure. The cyclic structure may be either a single ring or a condensed ring, and is 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, and more preferably a 6-membered ring. The single ring is preferably a cyclohexane ring and a benzene ring, and more preferably a cyclohexane ring.

More specifically, Rb ¹ and Rb ^{2 each} represent a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), and an alkenyl group (preferably having 2 to 24 carbon atoms). , 2 to 18 are more preferable, 3 to 12 are more preferable, an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), or an arylalkyl group (having 7 carbon atoms) To 25, more preferably 7 to 19, and even more preferably 7 to 12). 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 formed ring is preferably a 4- to 7-membered nitrogen-containing heterocyclic ring. Rb ¹ and Rb ² are particularly an optionally substituted linear, branched or cyclic alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms). More preferably, it is a cycloalkyl group which may have a substituent (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms). A cyclohexyl group which may be further preferred.

As Rb ³ , an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms) and an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, To 10), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms), and an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). Preferably, 7 to 12 are more preferable, an arylalkenyl group (preferably having 8 to 24 carbon atoms, more preferably 8 to 20, more preferably 8 to 16), and an alkoxyl group (preferably having 1 to 24 carbon atoms, 2 to 2) 18 is more preferable, and 3 to 12 is more preferable. The aryloxy group (6 to 22 carbon atoms is preferable, 6 to 18 is more preferable, and 6 to 12 is more preferable. There), or arylalkyloxy group (having 7 to 23 carbon atoms, more preferably 7 to 19, more preferably 7 to 12) are exemplified. Of these, a cycloalkyl group (preferably having 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 within a range in which the effects of the present invention can be obtained.

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

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 having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), and an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and 3 to 12 carbon atoms. ), An aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12), and an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, 7 to 12 are more preferable), and may have a substituent within a range in which the effects of the present invention are exhibited. Above all, Rb ¹³ is preferably an arylalkyl group.

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

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

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

Rb ¹¹ and Rb ¹² have the same meanings as Rb ¹¹ and Rb ¹² in the formula (B1-1).
Rb ¹⁵ and Rb ^{16 each} represent a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6), and an alkenyl group (preferably having 2 to 12 carbon atoms, preferably having 2 to 6 carbon atoms). More preferably, 2 to 3 are more preferable, an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10), and an arylalkyl group (preferably having 7 to 23 carbon atoms, and 7 To 19 are more preferable, and 7 to 11 are more preferable), and a hydrogen atom or a methyl group is preferable.
Rb ¹⁷ is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 3 to 8), and an aryl group. (Preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and still more preferably 6 to 12), and an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and still more preferably 7 to 12). And among them, an aryl group is preferable.

The molecular weight of the nonionic thermal base generator (A3) is preferably 800 or less, more preferably 600 or less, and 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 still 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 more thermal base generators can be used. When two or more kinds are used, the total amount is preferably in the above range.

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

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

硬化 The curing start 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 start temperature of the thermosetting compound is defined as the difference between the temperature of 1 mg of a sample (thermosetting compound) and the temperature of 25 ° C. at a rate of 5 ° C./min. And the temperature at which the exothermic reaction of the thermosetting compound starts. The temperature at which the exothermic reaction of the thermosetting compound starts means the temperature at which the peak of the exothermic reaction appears in the differential scanning calorimetry curve in which the vertical axis represents heat flow (mW) and the horizontal axis represents temperature (° C.). I do. When there are two or more exothermic reaction 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 start 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, and a functional group selected from a methylol group and an alkoxymethyl group. It is more preferable that the compound has a plurality of compounds, and it is further preferable that the compound has a plurality of alkoxymethyl groups because the effect of the present invention is more easily obtained, and it is particularly preferable that the compound has a plurality of methoxymethyl groups. preferable.

数 The number of the above-mentioned functional groups contained in the thermosetting compound may be two or more, and is 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 the formula (TC1).
X ^1- (Y ¹ ) _n ... (TC1)
In the formula (TC1), X ¹ represents an n-valent linking group, Y ¹ represents an epoxy group, an oxetanyl group, a methylol group, an alkoxymethyl group, a phenol group, a maleimide group, a cyanate group or a blocked isocyanate group, and n is Represents an integer of 2 or more.

Examples of the n-valent linking group represented by X ^{1 in the} formula (TC1) include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, —O—, —NH—, —NHCO—, —CONH—, and —. OCO—, —COO—, —CO—, —SO ₂ NH—, —SO ₂ — and combinations thereof. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 15, still more preferably 1 to 8, and particularly preferably 1 to 5. The aliphatic hydrocarbon group may be linear, branched or cyclic, preferably linear or branched, and particularly preferably linear. The aromatic hydrocarbon group preferably has 6 to 30 carbon atoms, more preferably 6 to 15 carbon atoms. The aromatic hydrocarbon group may be a single tube or a condensed ring. The heterocyclic group may be a single ring or a condensed ring. The heterocyclic group is preferably a single ring or a condensed ring having 2 to 4 condensed numbers. The number of hetero atoms constituting the ring of the heterocyclic group is preferably from 1 to 3. The hetero atom 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 from 3 to 30, more preferably from 3 to 18, and even more preferably from 3 to 12.

X ^{1 in the} formula (TC1) is preferably a group containing a cyclic structure. Examples of the cyclic structure include an aliphatic ring, an aromatic hydrocarbon ring, and a heterocyclic ring, and are preferably an aromatic hydrocarbon ring or a heterocyclic ring, and more preferably a heterocyclic ring. The heterocycle is preferably a nitrogen-containing heterocycle. Examples of the nitrogen-containing heterocyclic ring include a pyridine ring, a triazine ring, an imidazolidinone ring and the like, and an imidazolidinone ring is preferable.

Y ^{1 in the} formula (TC1) represents an epoxy group, an oxetanyl group, a methylol group, an alkoxymethyl group, a phenol group, a maleimide group, a cyanate group or a blocked isocyanate group, and is an epoxy group, an oxetanyl group, a methylol group or an alkoxymethyl group. Preferably, it is a methylol group or an alkoxymethyl group, more preferably an alkoxymethyl group.

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. It is particularly preferably an alkyl group having 1 to 3 carbon atoms, and most preferably an alkyl group having 1 carbon atom (methyl group). That is, the alkoxymethyl group is most preferably a methoxymethyl group.

熱 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. As such compounds, alkoxymethylated melamine, methylolated melamine, alkoxymethylated benzoguanamine, methylolated benzoguanamine, alkoxymethylated glycoluril, methylolated glycoluril, alkoxymethylated urea, and methylolated urea are preferred. Further, compounds described in paragraphs 0056 to 0065 of JP-A-2003-287889 and paragraphs 0058 to 0060 of JP-A-2018-084626 can also be used.

Preferred structures of the compound having an alkoxymethyl group or a methylol group 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 the formula (Rm), Rm ¹⁰⁰ represents a hydrogen atom or an alkyl group. The number of carbon atoms of the alkyl group represented by Rm ¹⁰⁰ is preferably 1 to 30, more preferably 1 to 15, still more preferably 1 to 8, and particularly preferably 1 to 3, Most preferably, it is 1. 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, for example, a compound represented by the following formula (AM-110).

Formula (AM-110)

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

Specific examples of the thermosetting compound having a methylol group or an alkoxymethyl group include a compound having the following structure. Commercial products include 46DMOC, 46DMOP, TM-BIP-A (manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML. -34X, DML-EP, DML-POP, 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, NIKALA Such as MW-100LM ((Ltd.) manufactured by Sanwa Chemical) 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, and is 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 resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resin such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether; polymethyl (glycidyl) Examples thereof include, but are not limited to, epoxy group-containing silicones such as (roxypropyl) siloxane. Specifically, Epicron (registered trademark) 850-S, Epicron (registered trademark) HP-4032, Epicron (registered trademark) HP-7200, Epicron (registered trademark) HP-820, Epicron (registered trademark) HP-4700, Epicron® EXA-4710, Epicron® HP-4770, Epicron® EXA-859CRP, Epicron® EXA-1514, Epicron® EXA-4880, Epicron® EXA-4850-150, EPICLON EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822 (manufactured by DIC Corporation), Rica Resin (registered trademark) BEO-60E (trade name, Shin-Nippon Rika Co., Ltd., EP-4003S, Such as P-4000S ((Ltd.) ADEKA), and the like. Further, a compound having the following structure can also be used.

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

では In the present invention, a thermosetting compound having a blocked isocyanate group (hereinafter, also referred to as a blocked isocyanate compound) may 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. Regarding specific examples of the skeleton, the description in paragraph No. 0144 of JP-A-2014-238438 can be referred to, and the contents thereof are incorporated herein. Examples of the parent structure of the blocked isocyanate compound include a biuret type, an isocyanurate type, an adduct type, and a bifunctional prepolymer type. Examples of the blocking agent forming the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, imide compounds, and the like. Can be. Among these, a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferred. As specific examples of the blocking agent, the description in paragraph No. 0146 of JP-A-2014-238438 can be referred to, and the contents thereof are incorporated in the present specification. The blocked isocyanate compound is available as a commercial product, for example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (all manufactured by Nippon Polyurethane Industry Co., Ltd.), Takenate B -830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (all 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 (all manufactured by Asahi Kasei Corporation), Desmodur BL1100 , BL1265 @ MPA / X, BL357 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Sumidur BL3175 (above, manufactured by Sumika Bayer Urethane Co.) can be preferably used, and the like.

では 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 at most 18% by mass, more preferably at most 15% by mass.
Further, 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 at most 23 parts by mass, more preferably at most 20 parts by mass. 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 is easily obtained. When the content of the thermosetting compound is 20 parts by mass or less based on 100 parts by mass of the polyimide precursor, a cured film having excellent substrate adhesion is easily obtained.
Further, 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 at least 20 parts by mass, more preferably at least 50 parts by mass.
One thermosetting compound may be used alone, or two or more thermosetting compounds may be used in combination. When two or more kinds are used in combination, the total amount is preferably within the above range.

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

公知 A known compound can be arbitrarily used as the photoradical polymerization initiator. For example, halogenated hydrocarbon derivatives (eg, 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. No. For the details thereof, the descriptions in paragraphs 0165 to 0182 of JP-A-2016-027357 and paragraphs 0138 to 0151 of WO 2015/199219 can be referred to, and the contents are incorporated herein.

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

As the photoradical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be suitably used. More specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 and an acylphosphine oxide-based initiator described in Patent No. 4225988 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127 (trade name: all manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179 in which the absorption maximum wavelength is matched to a light source having a wavelength of 365 nm or 405 nm can also be used.
Examples of the acylphosphine initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names, both manufactured by BASF) can be used.
Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF).

An oxime compound is more preferably used as the photoradical polymerization initiator. By using the oxime compound, the exposure latitude can be more effectively improved. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.
As specific examples of the oxime compound, compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, and compounds described in JP-A-2006-342166 can be used.
Preferred oxime compounds include, for example, compounds having the following structures, 3-benzooxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyimiminobtan-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 the photoradical polymerization initiator. The oxime-based photopolymerization initiator has a> C = NOC (= O)-linking group in the molecule.

Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (both manufactured by BASF) and Adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, JP 2012-014052A). A radical polymerization initiator 2) is also preferably used. Also, TR-PBG-304 (manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), Adeka Aquel's NCI-831 and Adeka Aquel's NCI-930 (manufactured by ADEKA Corporation) can be used. Further, DFI-091 (manufactured by Daito Mix) can be used.
Furthermore, it is also possible to use an oxime compound having a fluorine atom. Specific examples of such oxime compounds include compounds described in JP-A-2010-262028, compounds 24 and 36 to 40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013-2013. Compound (C-3) described in paragraph 0101 of JP-A-164471.
The most preferred oxime compounds include oxime compounds having a specific substituent described in JP-A-2007-269779, oxime compounds having a thioaryl group described in JP-A-2009-191061, and the like.

From the viewpoint of exposure sensitivity, the photoradical polymerization initiator may be a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triaryl 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 photoradical polymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds. At least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound is more preferable, and a metallocene compound or an oxime compound is more preferably used. Is even more preferred.
The photo-radical polymerization initiators include N, N'-tetraalkyl-4,4'-diaminobenzophenone such as benzophenone, 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, alkylanthraquinone, etc. And benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkyl benzoin, and benzyl derivatives such as benzyl dimethyl ketal. Further, a compound represented by the following formula (I) can also be used.

In the 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 at least one oxygen atom, 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 at least one oxygen atom 18 alkyl group and at least one substituted phenyl group of the alkyl group having 1 to 4 carbon atoms or a biphenyl,, R ^I01 is a group represented by formula (II), the same as R ^I00 And R ^I02 to R ^I04 are each independently alkyl having 1 to 12 carbons, alkoxy or halogen having 1 to 12 carbons.

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

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

When a photopolymerization initiator is contained, its content is preferably from 0.1 to 30% by mass, more preferably from 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. More preferably, it is from 0.5 to 15% by mass, more preferably from 1.0 to 10% by mass. The photopolymerization initiator may contain only one kind or two or more kinds. 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 a radical by the energy of heat and initiates or promotes a polymerization reaction of a compound having a radical polymerizable group. By adding a thermal radical polymerization initiator, the cyclization of the polyimide precursor and, when the polyimide precursor has a radical polymerizable group, the polymerization reaction of the polyimide precursor can be advanced, so that higher heat resistance can be achieved. Can be achieved.
Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.

When a thermal radical polymerization initiator is contained, its content is preferably from 0.1 to 30% by mass, more preferably from 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. And more preferably 5 to 15% by mass. The thermal radical polymerization initiator may contain only one kind or two or more kinds. 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 a plurality of (meth) acryloyl groups. The number of (meth) acryloyl groups contained in the polymerizable monomer may be two or more, and is preferably three or more. The upper limit is preferably 15 or less, more preferably 10 or less, and still more preferably 8 or less.

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

In addition, examples of the polymerizable monomer include compounds having a boiling point of 100 ° C. or more 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 A compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, Japanese Patent Publication No. 48-0417 No. 8, JP-B-50-006034, and urethane (meth) acrylates as described in JP-A-51-037193, JP-A-48-064183, and JP-A-49-043191. And polyfunctional acrylates and methacrylates such as polyester acrylates described in JP-B-52-030490, epoxy acrylates which are reaction products of epoxy resins with (meth) acrylic acid, and mixtures thereof. Can be. Further, compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Further, a polyfunctional (meth) acrylate obtained by reacting a compound having an ethylenically unsaturated bond with a cyclic ether group such as glycidyl (meth) acrylate with a polyfunctional carboxylic acid can also be mentioned. In addition, as a polymerizable monomer other than those described above, it has a fluorene ring and an ethylenically unsaturated bond described in JP-A-2010-160418, JP-A-2010-129825, and JP-A-4364216. Compounds having two or more groups and cardo resins are also included. Other examples include specific unsaturated compounds described in JP-B-46-043946, JP-B-01-040337 and JP-B-01-040336, and JP-A-02-025493. And the like. Further, compounds containing a perfluoroalkyl group described in JP-A-61-022048 can also be used. Furthermore, the Journal of the Adhesion Society of Japan @vol. 20, no. 7, pages 300 to 308 (1984), as photopolymerizable monomers and oligomers can also be used.

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

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

Furthermore, the compounds described in paragraphs 0104 to 0131 of JP-A-2015-18872 can also be used as the polymerizable monomer, and the contents thereof are incorporated herein.

Examples of the polymerizable monomer include dipentaerythritol triacrylate (a commercially available product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), and dipentaerythritol tetraacrylate (a commercially available product, KAYARAD D-320; Nippon Kayaku Co., Ltd.) ), A-TMMT: Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available: KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (Commercially available products are KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.) Compounds having the following structures:

Commercially available polymerizable monomers include, for example, SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer, SR-209, manufactured by Sartomer, which is a bifunctional methacrylate having four ethyleneoxy chains, 231, 239; DPCA-60, a hexafunctional acrylate having six pentyleneoxy chains, TPA-330, a trifunctional acrylate having three isobutyleneoxy chains, and urethane oligomer UAS-10, manufactured by Nippon Kayaku Co., Ltd. , 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, A -600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BREMMER PME400 (manufactured by NOF Co., Ltd.), and the like.

Examples of the polymerizable monomer include urethane acrylates described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, and JP-B-02-016765. Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-017654, JP-B-62-039417, and JP-B-62-039418 are also suitable. Further, compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277563, JP-A-63-260909, and JP-A-01-105238 may be used as radical polymerizable compounds. It can also be used.

The polymerizable monomer may be a compound having an acid group such as a carboxyl group and 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 anhydride to form an acid group. Is more preferable. Particularly preferably, in a polymerizable monomer obtained by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound to have an acid group, the aliphatic polyhydroxy compound is preferably pentaerythritol or dipentaerythritol. Is a compound. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
The preferred acid value of the polymerizable monomer having an acid group is 0.1 to 40 mgKOH / g, particularly preferably 5 to 30 mgKOH / g. When the acid value of the polymerizable monomer is in the above range, it is excellent in production and handleability, and further excellent in developability. Further, 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 preferably 15% by mass or less based on the total solid content of the resin composition of the present invention. Is more preferred. The lower limit may be more than 0% by mass, 1% by mass or more, or 3% by mass or more.
It is also preferable that the resin composition of the present invention does not substantially contain a polymerizable monomer. According to this aspect, the elongation at break and the chemical resistance of the obtained cured film can be further improved. In this specification, the case where the polymerizable monomer is not substantially contained means that the content of the polymerizable monomer is 0.01% by mass or less based on the total solid content of the resin composition. , 0.005% by mass or less, and more preferably not contained. Although the detailed reason for obtaining such an effect 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, when the polymerizable monomer is present during the cyclization reaction of the polyimide precursor, it is presumed that the polymerization reaction of the polymerizable monomer proceeds first and the cyclization of the polyimide precursor does not easily progress. It is presumed that the cyclization of the polyimide precursor easily progressed because the resin composition did not substantially contain a polymerizable monomer, and the resulting cured film could have further improved elongation at break and chemical resistance. You.

<Solvent>
The resin composition of the present invention preferably contains a solvent. As the solvent, a known solvent can be arbitrarily used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.
As esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone , Δ-valerolactone, alkyl alkyloxyacetates (eg, methyl alkyloxyacetate, ethylalkyloxyacetate, butylalkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, methyl ethoxyacetate, etc.) )), Alkyl 3-alkyloxypropionates (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, 3-methoxypropionate) Ethyl ester, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate)), alkyl 2-alkyloxypropionates (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2 Propyl alkyloxypropionate and the like (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyl Methyl oxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate , Pyruvate Chill, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like as preferred.
As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Suitable examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.
Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like.
Suitable aromatic hydrocarbons include, for example, 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 coated surface, a form in which two or more solvents are mixed is also preferable.
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 or more solvents selected from butyrolactone, dimethylsulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, or two or more solvents Is preferred. Particularly preferred is a combination of dimethyl sulfoxide and γ-butyrolactone.

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

<Migration inhibitor>
It is preferable that the resin composition of the present invention further contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress migration of metal ions derived from the metal layer (metal wiring) into the resin composition layer.
The migration inhibitor is not particularly limited, but may be a heterocycle (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, Compounds having pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thioureas and sulfanyl groups, hindered phenol compounds , Salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole and benzotriazole, and tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

イオン Alternatively, an ion trapping agent for trapping anions such as halogen ions can be used.

Other examples of the migration inhibitor include rust preventives 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. Compounds described in paragraph 0052, compounds described in paragraphs 0114, 0116 and 0118 of JP-A-2012-194520, compounds described in paragraph 0166 of WO 2015/199219, and the like can be used.

Specific examples of the migration inhibitor include the following compounds.

When the resin composition has a migration inhibitor, the content of the migration inhibitor is preferably from 0.01 to 5.0% by mass, and more preferably from 0.05 to 2% by mass, based on the total solid content of the resin composition. The content is more preferably 0.0% by mass, and further preferably 0.1 to 1.0% by mass. The migration inhibitor may be only one kind or two or more kinds. When two or more types of 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. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, and 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, －Nitroso 2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, bis (4 -Hydroxy-3,5-tert-butyl) phenylmethane and the like are preferably used. Further, the polymerization inhibitors described in paragraph 0060 of JP-A-2015-127817 and the compounds described in paragraphs 0031 to 0046 of WO2015 / 125469 can also be used. Further, the following compounds can be used (Me is a methyl group).

When the resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably from 0.01 to 5% by mass based on the total solid content of the resin composition of the present invention. It is more preferably 0.02 to 3% by mass, and further preferably 0.05 to 2.5% by mass. The polymerization inhibitor may be only one kind or two or more kinds. When there are two or more polymerization inhibitors, 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 the adhesion to a metal material used for an electrode or a wiring. Examples of the metal adhesion improver include a silane coupling agent.

Examples of the silane coupling agent include the compounds described in paragraph 0167 of WO 2015/199219, the compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, and the paragraphs of WO 2011/080992. Compounds described in 0063 to 0071, compounds described in paragraphs 0060 to 0061 of JP-A-2014-191252, compounds described in paragraphs 0045 to 0052 of JP-A-2014-041264, and compounds described in WO 2014/099754. The compounds described in paragraph 0055 are mentioned. 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. It is also preferable to use the following compound as the silane coupling agent. In the following formula, Et represents an ethyl group.

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

The content of the metal adhesion improver is preferably from 0.1 to 30 parts by mass, more preferably from 0.5 to 15 parts by mass, and still more preferably from 0 to 15 parts by mass, per 100 parts by mass of the polymer precursor. It is in the range of 5 to 5 parts by mass. When the amount is not less than the lower limit, the adhesion between the cured film and the metal layer after the curing step is good, and when the amount is not more than the above upper limit, the heat resistance and mechanical properties of the cured film after the curing step are good. The metal adhesion improver may be only one kind or two or more kinds. 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 contain various additives, for example, a thermal acid generator, a sensitizing dye, a chain transfer agent, a surfactant, and a higher fatty acid derivative, as long as the effects of the present invention are not impaired. , Inorganic particles, a curing agent, a curing catalyst, a filler, an antioxidant, an ultraviolet absorber, an anti-agglomeration 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 at least 0.01 part by mass, more preferably at least 0.1 part by mass, based on 100 parts by mass of the polymer precursor. Since the crosslinking reaction and the cyclization of the polymer precursor are promoted by containing 0.01 parts by mass or more of the thermal acid generator, the mechanical properties and chemical resistance of the cured film can be further improved. Further, the content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less, from the viewpoint of the electrical insulation of the cured film.
Only one thermal acid generator may be used, or two or more thermal acid generators may be used. When two or more kinds are used, the total amount is preferably within the above range.

<< Sensitizing dye >>
The resin composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs a specific actinic radiation and enters an electronically excited state. The sensitizing dye in the electronically excited state comes into contact with a thermosetting accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and causes effects such as electron transfer, energy transfer, and heat generation. As a result, the thermal curing accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo chemical changes and are decomposed to generate radicals, acids, or bases. For the details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated herein.

When the resin composition of the present invention contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01 to 20% by mass relative to the total solid content of the resin composition of the present invention. The content is more preferably 1 to 15% by mass, and further preferably 0.5 to 10% by mass. The sensitizing dyes may be used alone or in combination of two or more.

<< Chain transfer agent >>
The resin composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in Polymer Dictionary, Third Edition (edited by The Society of Polymer Science, 2005), pages 683-684. As the chain transfer agent, for example, a compound group having SH, PH, SiH, and GeH in the molecule is used. These can generate a radical by donating hydrogen to a low activity radical, or can generate a radical by being oxidized and then deprotonated. In particular, a thiol compound can be preferably used.
Further, as the chain transfer agent, compounds described in paragraphs 0152 to 0153 of WO 2015/199219 can also be used.

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

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

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

When the resin composition of the present invention has a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass based on the total solid content of the resin composition of the present invention. , More preferably 0.005 to 1.0% by mass. The surfactant may be only one kind or two or more kinds. When two or more surfactants are used, the total is preferably within the above range.

<< Higher fatty acid derivative >>
In order to prevent polymerization inhibition caused by oxygen, the resin composition of the present invention is added with a higher fatty acid derivative such as behenic acid or behenic acid amide, and is unevenly distributed on the surface of the composition in a drying process after application. May be.
Further, as the higher fatty acid derivative, a compound described in paragraph 0155 of WO 2015/199219 can be used.
When the resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass based on the total solid content of the resin composition of the present invention. The higher fatty acid derivative may be only one kind or two or more kinds. When there are two or more higher fatty acid derivatives, the total is preferably within the above range.

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

From the viewpoint of insulating properties, the metal content of the resin composition of the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are included, the total of these metals is preferably within the above range.
In addition, as a method for reducing metal impurities unintentionally contained in the resin composition of the present invention, a material having a low metal content is selected as a raw material constituting the resin composition of the present invention. Examples of the method include filtering the raw material constituting the product with a filter, lining the inside of the apparatus with polytetrafluoroethylene or the like, and performing distillation under the condition that contamination is suppressed as much as possible.

The resin composition of the present invention has a halogen atom content of 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 corrosiveness, when considering the use as a semiconductor material. Is more preferred. Above all, those present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, even more preferably less than 0.5 ppm by mass. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that each of the chlorine atom and the bromine atom, or the total of the chlorine ion and the bromine ion is within the above range.

従来 As the container for storing the resin composition of the present invention, a conventionally known container can be used. In addition, as a storage container, for the purpose of suppressing impurities from being mixed into raw materials and compositions, the inner wall of the container is formed into a multi-layer bottle composed of six types and six layers of resin, or six types of resin is formed into a seven-layer structure. It is also preferred to use a bottle that has been used. Examples of such a container include a container described in JP-A-2015-123351.

[Preparation of resin composition]
The resin composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited, and can be performed by a conventionally known method.
In addition, it is preferable to perform filtration using a filter for the purpose of removing foreign substances 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. The filter may be one that has been washed in advance with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different pore sizes or materials may be used in combination. Further, various materials may be filtered plural times. When filtration is performed a plurality of times, circulation filtration may be used. Also, filtration may be performed under pressure. In the case of performing filtration by applying pressure, the pressure to be applied is preferably 0.05 MPa or more and 0.3 MPa or less.
In addition to the filtration using a filter, a treatment for removing impurities using an adsorbent may be performed. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.

[Cured film, laminate, semiconductor device, and manufacturing method thereof]
Next, a cured film, a laminate, a semiconductor device, and a method for manufacturing the same will be described.
The cured film of the present invention is obtained by curing the resin composition of the present invention. The thickness of the cured film of the present invention can be, for example, 0.5 μm or more, and can be 1 μm or more. Further, the upper limit can be set to 100 μm or less, and can be set to 30 μm or less.

(4) The cured film of the present invention may be formed into a laminate by laminating two or more, more preferably three to seven layers. 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.

分野 Fields to which the cured film of the present invention can be applied include an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like. Other examples include patterning a sealing film, a substrate material (a base film or a coverlay of a flexible printed board, an interlayer insulating film), or an insulating film for mounting as described above by etching. These applications are described in, for example, Science & Technology Co., Ltd. “Highly Functional Polyimides and Applied Technologies” April 2008, Masaaki Kakimoto / Supervisor, CMC Technical Library “Basics and Development of Polyimide Materials” November 2011 , Japan Polyimide / Aromatic Polymer Study Group / ed., "Latest Polyimides: Fundamentals and Applications", NTT, August 2010.

The cured film according to the present invention can also be used for producing plate surfaces such as offset plate surfaces or screen plate surfaces, for use in etching molded parts, and for producing protective lacquers and dielectric layers in electronics, particularly microelectronics.

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

方法 The method for producing a laminate according to a preferred embodiment of the present invention includes the method for producing a cured film of the present invention. According to the method for manufacturing a laminate of the present embodiment, after forming a cured film according to the above-described method for producing a cured film, the step (a), the steps (a) to (c), or the step (a) is performed again. ) To (d) are performed. In particular, it is preferable to perform each of the above steps in order, a plurality of 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 preferable to provide a metal layer on the portion where the cured film is provided, between the cured films, or both. In the production of the laminate, it is not necessary to repeat all the steps (a) to (d). As described above, at least (a), preferably (a) to (c) or (a) to (d) By performing the step (2) a plurality of times, a laminate of a cured film can be obtained.

<Film forming step (layer forming step)>
The 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 the substrate can be appropriately determined according to the application, but a semiconductor production substrate such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, an optical film, a ceramic material, a vapor-deposited film, and a magnetic film , A reflective film, a metal substrate of Ni, Cu, Cr, Fe, etc., paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, and an electrode plate of a plasma display panel (PDP). In the present invention, a semiconductor fabrication substrate is particularly preferable, and a silicon substrate is more preferable.
When the resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer serves as a substrate.
As a means for applying the resin composition to the substrate, coating is preferable.
Specifically, as means to be applied, dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, slit coating, And an inkjet method. From the viewpoint of the uniformity of the thickness of the resin composition layer, more preferred are a spin coating method, a slit coating method, a spray coating method and an ink jet method. A resin layer having a desired thickness can be obtained by adjusting an appropriate solid content concentration and application conditions according to the method. The coating method can also 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, or an inkjet method is preferable. For a rectangular substrate, a slit coating method, a spray coating method, or an inkjet method is used. Method is preferred. In the case of the spin coating method, for example, a rotation speed of 500 to 2000 rpm can be applied for about 10 seconds to 1 minute.

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

<Exposure process>
The production method of the present invention may include an exposure step of exposing the resin composition layer. The amount of exposure is not particularly limited as long as the resin composition can be cured. For example, irradiation is preferably 100 to 10,000 mJ / cm ² , and more preferably 200 to 8000 mJ / cm ^{2 in} terms of exposure energy at a wavelength of 365 nm. More preferred.
The exposure wavelength can be appropriately determined within the range of 190 to 1000 nm, and preferably 240 to 550 nm.
The exposure wavelength is, in terms of the light source, (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-line (wavelength 436 nm), h Line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer Laser (wavelength: 157 nm); (5) extreme ultraviolet; EUV (wavelength: 13.6 nm); (6) electron beam. With respect to 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, a particularly high exposure sensitivity can be obtained.

<Development process>
The production method of the present invention may include a development processing step of performing development processing on the exposed resin composition layer. By performing the development, an unexposed portion (non-exposed portion) is removed. The developing method is not particularly limited as long as a desired pattern can be formed. For example, a developing method such as paddle, spray, immersion, or ultrasonic wave can be adopted.
Development is performed using a developer. The developer can be used without particular limitation as long as the unexposed portions (non-exposed portions) are removed. The developer preferably contains an organic solvent, and more preferably the developer contains 90% or more of the organic solvent. In the present invention, the developer preferably contains an organic solvent having a ClogP value of -1 to 5, more preferably an organic solvent having a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting a structural formula in ChemBioDraw.
Examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and γ-butyrolactone. , Ε-caprolactone, δ-valerolactone, alkyl alkyl oxyacetates (eg, methyl alkyl oxyacetate, ethyl oxyacetate, alkyl butyl oxyacetate (eg, methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, Ethyl ethoxyacetate, etc.), alkyl 3-alkyloxypropionates (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, 3-methoxypropionate) Ethyl pionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate)), alkyl 2-alkyloxypropionates (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2 Propyl alkyloxypropionate and the like (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyl Methyl oxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate , Pyruvate Tyl, 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, and the like, and Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and the like, and aromatic hydrocarbons such as toluene, xylene, anisole, limonene, and the like. As the sulfoxides, dimethyl sulfoxide is preferably exemplified.
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 an organic solvent, more preferably 70% by mass or more of an organic solvent, and even more preferably 90% by mass or more of an organic solvent. Further, 100% by mass of the developer may be an organic solvent.

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

<Heating process>
The manufacturing method of the present invention preferably includes a heating step after the film forming step (layer forming step), the drying step, or the developing step. In the heating step, a cyclization reaction of the polymer precursor and a 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 more preferably 150 ° C. or higher. Is more preferably 160 ° C. or higher, and even more preferably 170 ° C. or higher. The upper limit is preferably 500 ° C. or lower, more preferably 450 ° C. or lower, even more preferably 350 ° C. or lower, further preferably 250 ° C. or lower, and more preferably 220 ° C. or lower. Even more preferred.
Heating is preferably performed at a rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, even more preferably 3 to 10 ° C./min. By setting the heating rate to 1 ° C./min or more, the amine can be prevented from being excessively volatilized while securing the productivity. By setting the heating rate to 12 ° C./min or less, the cured film can be cured. The residual stress can be reduced.
The temperature at the start of heating is preferably from 20 ° C to 150 ° C, more preferably from 20 ° C to 130 ° C, even more preferably from 25 ° C to 120 ° C. The temperature at the start of heating refers to the temperature at which the step of heating to the maximum heating temperature is started. For example, when the resin composition is applied on a substrate and then dried, it is the temperature of the film (layer) after the drying, 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 from 10 to 360 minutes, more preferably from 20 to 300 minutes, even more preferably from 30 to 240 minutes.
In particular, when a multilayer laminate is formed, the heating temperature is preferably from 180 ° C. to 320 ° C., and more preferably from 180 ° C. to 260 ° C., from the viewpoint of adhesion between the cured films. Although the reason is not clear, it is considered that the ethynyl groups of the polymer precursor between the layers are undergoing a crosslinking reaction at this temperature.

The heating may be performed stepwise. As an example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min, maintained at 180 ° C. for 60 minutes, raised from 180 ° C. to 200 ° C. at 2 ° C./min, and maintained at 200 ° C. for 120 minutes. , Etc., may be performed. The heating temperature in the pretreatment step is preferably from 100 to 200 ° C, more preferably from 110 to 190 ° C, and even more preferably from 120 to 185 ° C. In this pretreatment step, it is also preferable to perform the treatment while irradiating ultraviolet rays as described in US Pat. No. 9,159,547. By such a pretreatment step, the characteristics of the film can be improved. The pretreatment step may be performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may include two or more steps. For example, pretreatment step 1 may be performed at a temperature in the range of 100 to 150 ° C., and then pretreatment step 2 may be performed at a temperature in the range of 150 to 200 ° C.
Furthermore, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.

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

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

<Lamination process>
It is preferable that the manufacturing method of the present invention further includes a lamination step.
The laminating step means (a) a film forming step (layer forming step), (b) an exposing step, (c) a developing step, and (d) a heating step on the surface of the cured film (resin layer) or the metal layer. Are performed in this order. However, an embodiment in which only the film forming step (a) is repeated may be employed. Further, the heating step (d) may be performed at the end of or in the middle of the lamination. That is, the steps (a) to (c) may be repeated a predetermined number of times, and then the heating of (d) may be performed to cure the laminated resin composition layers at once. In addition, (e) a metal layer forming step may be included after the (c) developing step. In this case, even if heating (d) is performed each time, after laminating a predetermined number of times, (d) Heating may be performed. Needless to say, the laminating step may further include the above-mentioned drying step, heating step and the like as appropriate.
When the laminating step is further performed after the laminating step, a surface activation treatment step may be further performed after the heating step, after the exposing step, or after the metal layer forming step. As the surface activation treatment, a plasma treatment is exemplified.
The above lamination step is preferably performed 2 to 5 times, more preferably 3 to 5 times.
For example, a configuration of three to seven resin layers is preferable, such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, and more preferably three to five layers.
In the present invention, it is particularly preferable that after the metal layer is provided, a cured film (resin layer) of the resin composition is further formed so as to cover the metal layer. Specifically, a mode in which (a) a film forming step, (b) an exposing step, (c) a developing step, (e) a metal layer forming step, and (d) a heating step are repeated in this order, or (a) a film forming step Step, (b) exposure step, (c) development step, and (e) repetition in the order of the metal layer forming step, and (d) heating step is provided at the end or in the middle in a lump. By alternately performing the laminating step of laminating the resin composition layer (resin) and the metal layer forming step, the resin composition layer (resin layer) and the metal layer can be laminated alternately.

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

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

<Synthesis example 1>
[Synthesis of polyimide precursor (A-1: polyimide precursor having no radical 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 ° C. and 16.12 g (135.5 mmol) SOCl ₂ was added over 10 minutes keeping the temperature at −10 ± 4 ° C. The viscosity increased during the addition of SOCl ₂ . After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution of 11.08 g (58.7 mmol) of 4,4′-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at −5 to 0 ° C. over 20 minutes. Next, the reaction mixture was reacted at 0 ° C. for 1 hour, and then 70 g of ethanol was added, followed by stirring at room temperature overnight. The polyimide precursor was then precipitated in 5 liters of water, and the water-polyimide precursor mixture was stirred at 5000 rpm for 15 minutes. The polyimide precursor was removed by filtration, stirred again for 30 minutes in 4 liters of water, and filtered again. Next, the obtained polyimide precursor was 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 a polyimide precursor (A-2: a polyimide precursor having a radical 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 and 20 0.4 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 produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Next, the obtained diester is chlorinated with SOCl ₂ , and then converted into a polyimide precursor with 4,4′-diaminodiphenyl ether in the same manner as in Synthesis Example 1, and the polyimide precursor is converted 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 And 20.4 g of pyridine (258 mmol) and 100 g of diglyme were stirred at a temperature of 60 ° C. for 18 hours to produce a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate. . Next, the obtained diester is chlorinated with SOCl ₂ , and then converted into a polyimide precursor with 4,4′-diaminodiphenyl ether in the same manner as in Synthesis Example 1, and the polyimide precursor is converted 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 (orthotrizine) and 2-hydroxyethyl methacrylate (A-4: having a radical 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 And 20.4 g of pyridine (258 mmol) and 100 g of diglyme were stirred at a temperature of 60 ° C. for 18 hours to produce a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate. . Next, the obtained diester was chlorinated with SOCl ₂ , and then converted to a polyimide precursor with 4,4′-diamino-2,2′-dimethylbiphenyl in the same manner as in Synthesis Example 1. Thus, a polyimide precursor was obtained. The weight average molecular weight of this polyimide precursor was 19,000.

A-4

<Examples and Comparative Examples>
The components shown in the following table were mixed to obtain each resin composition. The obtained resin composition was subjected to pressure filtration through a filter having a pore width of 0.8 μm.

The raw materials described 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 structure

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

(D) Photopolymerization initiator D-1, D-2: a compound having the following structure

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

(F) Polymerization inhibitors F-1, F-2: compounds having the following structure

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

(H) Silane coupling agent H-1, H-2: Compound having the following structure

(I) Solvent I-1: γ-butyrolactone I-2: Dimethyl sulfoxide

<Production of cured film>
Each resin composition was applied on a silicon wafer by a spin coating method 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 was exposed to light at an exposure energy of 400 mJ / cm ² using a broadband exposure machine (UX-1000SN-EH01 manufactured by Ushio Inc.), and the exposed photosensitive resin composition layer ( The resin layer) was heated at a rate of 5 ° C./min in a nitrogen atmosphere, and after reaching 180 ° C., was heated for 2 hours. The cured resin layer was immersed in a 3% hydrofluoric acid solution, and the resin layer was separated from the silicon wafer to obtain a cured film.

<Elongation at break>
The breaking elongation of the obtained 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. The measurement was carried out in accordance with JIS-K6251 (Japanese Industrial Standard) under the following environment. Elongation at _{_{break, Eb = (L b -L 0}} ) / L 0 (E b: elongation at break, L _0: length of the test piece before the test, L _b: the length of the specimen when the specimen was cut ). For evaluation, the elongation at break was measured 10 times each, and the average value was used. The results were classified and evaluated as follows.
A: Elongation at break is 60% or more B: Elongation at break is 50% or more and less than 60% C: Elongation at break is less than 50%

<Chemical resistance>
The obtained cured film was immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated.
Chemicals: 90:10 (mass ratio) mixture of dimethyl sulfoxide (DMSO) and 25% by mass of tetramethylammonium hydroxide (TMAH) solution Evaluation conditions: Before and after immersing the resin layer in the solution at 75 ° C. for 15 minutes The film thickness was 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 on 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 having 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 is performed with i-line, at a wavelength of 365 nm, using a line and space photomask in increments of 1 μm from 5 μm to 25 μm at exposure energy of 200, 300, 400, 500, 600, 700, 800 mJ / cm ^2. 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 finer the pattern can be formed, which is a preferable result. In addition, as the minimum line width that can be formed hardly changes with respect to the fluctuation of the exposure amount, the arbitrariness of the exposure amount in the formation of the fine pattern increases, and a preferable result is obtained.
A: The line width is less than 10 μm. B: The line width is 10 μm or more and less than 20 μm.

As shown in the above table, in Examples, a cured film having good elongation at break and excellent chemical resistance was able to be formed.

Claims

A polyimide precursor,
A thermal base generator,
A thermosetting compound having a plurality of functional groups selected from the group consisting of an epoxy group, an oxetanyl group, a methylol group, an alkoxymethyl group, a phenol group, a maleimide group, a cyanate group and a blocked isocyanate group,
A resin composition comprising:
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 the formula (TC1), X 1 represents an n-valent linking group, Y 1 represents an epoxy group, an oxetanyl group, a methylol group, an alkoxymethyl group, a phenol group, a maleimide group, a cyanate group or a blocked isocyanate group, and n is Represents an integer of 2 or more.
X 1 comprises a cyclic structure, a resin composition according to claim 2 of the formula (TC1).
The resin composition according to any one of claims 1 to 3, wherein the thermosetting compound is a compound having a plurality of alkoxymethyl groups.
樹脂 The resin composition according to any one of claims 1 to 3, wherein the thermosetting compound is a compound having a plurality of 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 start temperature of the thermosetting compound.
The resin composition according to any one of claims 1 to 6, wherein the content of the polymerizable monomer having a plurality of (meth) acryloyl groups is 20% by mass or less based on the total solid content of the resin composition.
(8) The resin composition according to any one of (1) to (7), wherein the polyimide precursor contains a radical polymerizable group.
9. The resin composition according to claim 1, 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 R 114 each independently represents a hydrogen atom or a monovalent organic group.
At least one comprises a radical polymerizable group, a resin composition according to claim 9 of R 113 and R 114 in the formula (1).
(11) The resin composition according to (8) or (10), further comprising a photopolymerization initiator.
The resin composition according to any one of claims 1 to 11, which is used for forming an interlayer insulating film for a redistribution layer.
A cured film obtained by curing the resin composition according to any one of claims 1 to 12.
A laminate having two or more cured films according to claim 13, and a metal layer between the two cured films.
A method for producing a cured film, comprising a film forming step of forming a film by applying the resin composition according to any one of claims 1 to 12 to a substrate.
The method for producing a cured film according to claim 15, further comprising an exposure step of exposing the film and a developing step of developing the film.
17. The method for producing a cured film according to claim 16, comprising a step of heating the film at 80 to 450 ° C.
A semiconductor device having the cured film according to claim 13 or the laminate according to claim 14.