CN112752798A - Resin composition, cured film, laminate, method for producing cured film, and semiconductor device - Google Patents

Abstract

The present invention provides a resin composition, a cured film using the resin composition, a laminate, a method for producing the cured film, and a semiconductor component, the resin composition comprising a polyimide precursor, a thermal base generator, and a polyimide a function selected from the group consisting of epoxy, oxetanyl, methylol, alkoxymethyl, phenolic, maleimide, cyanate, and blocked isocyanate based thermosetting compounds.

Description

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

Technical Field

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, each using the resin composition containing the polymer precursor.

Background

Polyimide resins are excellent in heat resistance and insulation properties and therefore are suitable for various applications. The use is not particularly limited, but the use as a material for an insulating film or a sealing material or a protective film is exemplified by a semiconductor device for actual mounting. (see non-patent documents 1 and 2, etc.). Also, the film is used as a base film or a cover layer of a flexible substrate.

On the other hand, polyimide resins generally have low solubility in solvents. Therefore, a method of dissolving a polymer precursor before cyclization reaction, specifically, a polyimide precursor in a solvent is often used. This makes it possible to realize excellent workability and to apply the coating to a substrate or the like in various forms and process the coating at the time of manufacturing each product as described above. Then, the polyimide precursor is heated and cyclized, thereby enabling the formation of a cured product. In addition to the high performance of polyimide resins and the like, the industrial application thereof is expected to be developed from the viewpoint of excellent suitability for such production.

Patent document 1 describes a photosensitive resin composition containing (a) a polyamide having a photopolymerizable unsaturated bond: 100 parts by mass of (B) a monomer having a photopolymerizable unsaturated double bond: 1-50 parts by mass of (C) a photopolymerization initiator: 1-20 parts by mass of (D) a thermal crosslinking agent: 5 to 30 parts by mass.

Patent document 2 describes a photosensitive resin composition containing (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.

Prior art documents

Patent document

Patent document 1: japanese patent laid-open publication No. 2003-287889

Patent document 2: japanese patent laid-open publication No. 2014-201695

Non-patent document

Non-patent document 1: science & technology co, ltd. "high functionalization and application technology of polyimide" 2008/4

Non-patent document 2: shiben Yaming/Surveillance and CMC technology library 'basis and development of polyimide materials' 2011 11-month release

Disclosure of Invention

Technical problem to be solved by the invention

In recent years, studies have been made on cyclizing a polyimide precursor at a low temperature to obtain a cured product. Further, a cured product obtained by cyclizing a polyimide precursor at a low temperature is required to have further improved properties such as elongation at break and chemical resistance.

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

Means for solving the technical problem

The present inventors have conducted extensive 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 as a result, have found that a cured film having excellent elongation at break and chemical resistance can be formed by the structure described below, thereby completing the present invention. The present invention provides the following.

< 1 > a resin composition comprising: a polyimide precursor,

A thermal alkali-producing agent, and

a thermosetting compound having a plurality of functional groups selected from the group consisting of epoxy groups, oxetane groups, methylol groups, alkoxymethyl groups, phenol groups, maleimide groups, cyanate groups and blocked isocyanate groups.

< 2 > the resin composition < 1 > wherein the thermosetting compound is a compound represented by the following formula (TC1),

X¹-(Y¹)_n……(TC1)

in the formula (TC1), X¹Represents a linking group of n valence, Y¹Represents an epoxy group, an oxetanyl group, a hydroxymethyl group, an alkoxymethyl group, a phenol group, a maleimide group, a cyanate group or a blocked isocyanate group, and n represents an integer of 2 or more.

< 3 > the resin composition according to < 2 >, wherein X of the formula (TC1)¹Comprising 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.

The resin composition according to any one of < 6 > < 1 > < 5 >, wherein a base generation temperature of the thermal base generator is lower than a curing start temperature of the thermally curable compound.

< 7 > the resin composition according to any one of < 1 > to < 6 >, wherein a content of the polymerizable monomer having a plurality of (meth) acryloyl groups is 20% by mass or less in a 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 any one of < 1 > to < 8 >, wherein the polyimide precursor has a structural unit represented by the following formula (1).

[ chemical formula 1]

In the formula (1), A¹And A²Each independently represents an oxygen atom or NH, R¹¹¹Represents a 2-valent organic group, R¹¹⁵Represents a 4-valent organic group, R¹¹³And R¹¹⁴Each independently represents a hydrogen atom or a 1-valent organic group.

< 10 > the resin composition according to < 9 >, wherein R of formula (1)¹¹³And R¹¹⁴At least one of them contains a radical polymerizable group.

< 11 > the resin composition according to < 8 > or < 10 > further comprising a photopolymerization initiator.

< 12 > the resin composition according to any one of < 1 > -11 >, wherein the resin composition is used for forming an interlayer insulating film for a rewiring layer.

< 13 > a cured film obtained by curing the resin composition as defined in any one of < 1 > -to < 12 >.

< 14 > a laminate having 2 or more layers < 13 > of the cured film with a metal layer between the 2 cured films.

< 15 > a method for producing a cured film, which comprises a film-forming step of applying the resin composition as described in any one of < 1 > to < 12 > to a substrate to form a film.

< 16 > the method for producing a cured film according to < 15 > which comprises: 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 < 16 > comprising a step of heating the film at 80 to 450 ℃.

< 18 > a semiconductor component having < 13 > said cured film or < 14 > said laminate.

Effects of the invention

According to the present invention, a resin composition capable of forming a cured film excellent in elongation at break and chemical resistance, a cured film, a laminate, a method for producing a cured film, and a semiconductor device can be provided.

Detailed Description

The present invention will be described in detail below. In the present specification, "to" are used to indicate that numerical values before and after the "to" are included as the lower limit value and the upper limit value.

The following description of the constituent elements of the present invention may be based on representative embodiments of the present invention, but the present invention is not limited to these embodiments.

In the present specification, a label of a group (atomic group) is not described, and a substituted or unsubstituted label includes both a group (atomic group) having no substituent and a group (atomic group) having a substituent. For example, "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present specification, "exposure" is not particularly limited, and in addition to exposure using light, drawing using particle beams such as electron beams and ion beams is also included in exposure. Examples of the light used for exposure generally include an active light or radiation such as far ultraviolet light, extreme ultraviolet light (EUV light), X-ray, and electron beam, which are represented by a bright line spectrum of a mercury lamp or an excimer laser.

In the present specification, "(meth) acrylate" represents both or either of "acrylate" and "methacrylate", "meth (acrylic acid)" represents both or either of "acrylic acid" and "methacrylic acid", and "(meth) acryloyl group" represents both or either of "acryloyl group" and "methacryloyl group".

In the present specification, the term "step" includes not only an independent step, but also a step that exhibits an expected function even when the step is not clearly distinguished from other steps.

The physical property parameters in the present invention are values at a temperature of 23 ℃ and a gas pressure of 101325Pa, unless otherwise specified.

In the present specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC measurement) and defined as styrene equivalent values. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined by using HLC-8220 (manufactured by TOSOH CORPORATION), and as a column, a guard column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION), for example. In this measurement, THF (tetrahydrofuran) was used as an eluent unless otherwise specified. It is assumed that a 254nm wavelength detector of UV rays (ultraviolet rays) is used for detection unless otherwise specified.

The resin composition of the present invention comprises: a polyimide precursor,

A thermal alkali-producing agent, and

a thermosetting compound having a plurality of functional groups selected from the group consisting of epoxy groups, oxetane groups, methylol groups, alkoxymethyl groups, phenol groups, maleimide groups, cyanate groups and blocked isocyanates.

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

In the resin composition of the present invention, the alkali generation temperature of the thermoalcaligenic agent is preferably lower than the curing start temperature of the thermosetting compound. By using these thermal alkali-producing agents and thermosetting compounds in combination, the effects of the present invention can be more remarkably obtained.

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

The components of the resin composition of the present invention will be described in detail below.

< polyimide precursor >

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

The polyimide precursor used in the present invention preferably contains a radical polymerizable group. The radical polymerizable group is a group capable of undergoing a crosslinking reaction by the action of a radical, and a preferable example thereof is a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth) acryloyl group, and a group represented by the following formula (III). When a polyimide precursor containing a radical polymerizable group is used, a cured film having more excellent characteristics is easily obtained. Further, the resin composition of the present invention can be used as a resin composition having excellent pattern formability in a photolithography method even when the resin composition contains a photo radical polymerization initiator.

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

[ chemical formula 2]

A¹And A²Each independently represents an oxygen atom or NH, R¹¹¹Represents a 2-valent organic group, R¹¹⁵Represents a 4-valent organic group, R¹¹³And R¹¹⁴Each independently represents a hydrogen atom or a 1-valent organic group.

A¹And A²Each independently an oxygen atom or NH, preferably an oxygen atom.

＜＜＜R¹¹¹＞＞＞

R¹¹¹Represents a 2-valent organic group. Examples of the 2-valent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, and a group containing a combination thereof, and the group preferably has 2 to 20 carbon atomsA straight chain aliphatic group, a branched chain 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 combination thereof, and more preferably an aromatic group having 6 to 20 carbon atoms.

R¹¹¹Preferably derived from diamines. The diamine used for producing the polyimide precursor includes a linear or branched aliphatic, cyclic aliphatic, or aromatic diamine. One diamine may be used alone, or two or more diamines may be used.

Specifically, the diamine preferably contains 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, and more preferably contains an aromatic group having 6 to 20 carbon atoms. Examples of the aromatic group include the following aromatic groups.

[ chemical formula 3]

In the formula, A is preferably a single bond or selected from aliphatic hydrocarbon groups having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C (═ O) -, -S-, -S (═ O)₂-, -NHCO-and combinations thereof, more preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C (-O) -, -S-, and-SO₂The group of (E) is further preferably selected from the group consisting of-CH₂-、-O-、-S-、-SO₂-、-C(CF₃)₂-and-C (CH)₃)₂-a 2-valent radical of the group consisting.

Specific examples of the diamine include those selected from the group consisting of 1, 2-diaminoethane, 1, 2-diaminopropane, 1, 3-diaminopropane, 1, 4-diaminobutane and 1, 6-diaminohexane; 1, 2-or 1, 3-diaminocyclopentane, 1, 2-diaminocyclohexane, 1, 3-or 1, 4-diaminocyclohexane, 1, 2-bis (aminomethyl) cyclohexane, 1, 3-bis (aminomethyl) cyclohexane or 1, 4-bis (aminomethyl) cyclohexane, bis- (4-aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4 '-diamino-3, 3' -dimethylcyclohexylmethane and isophoronediamine; m-phenylenediamine and p-phenylenediamine, diaminotoluene, 4 '-diaminobiphenyl and 3, 3' -diaminobiphenyl, 4 '-diaminodiphenyl ether, 3-diaminodiphenyl ether, 4' -diaminodiphenylmethane and 3,3 '-diaminodiphenylmethane, 4' -diaminodiphenyl sulfone and 3,3 '-diaminodiphenyl sulfone, 4' -diaminodiphenyl sulfide and 3,3 '-diaminodiphenyl sulfide, 4' -diaminobenzophenone and 3,3 '-diaminobenzophenone, 3' -dimethyl-4, 4 '-diaminobiphenyl, 2' -dimethyl-4, 4 '-diaminobiphenyl (4, 4' -diamino-2, 2 '-dimethylbiphenyl), 3' -dimethoxy-4, 4 '-diaminobiphenyl, 2-bis (4-aminophenyl) propane, 2-bis (4-aminophenyl) hexafluoropropane, 2-bis (3-hydroxy-4-aminophenyl) propane, 2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2-bis (3-amino-4-hydroxyphenyl) propane, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 4' -diamino-terphenyl, p-phenylene, 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' -dimethyl-4, 4 '-diaminodiphenyl sulfone, 1, 3-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenyl) benzene, 3' -diethyl-4, 4 '-diaminodiphenylmethane, 3' -dimethyl-4, 4 ' -diaminodiphenylmethane, 4,4 ' -diaminooctafluorobiphenyl, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 9-bis (4-aminophenyl) -10-hydroanthracene, 3 ', 4,4 ' -tetraaminobiphenyl, 3 ', 4,4 ' -tetraaminodiphenyl ether, 1, 4-diaminoanthraquinone, 1, 5-diaminoanthraquinone, 3-dihydroxy-4, 4 ' -diaminobiphenyl, 9 ' -bis (4-aminophenyl) fluorene, 4,4 ' -dimethyl-3, 3 ' -diaminodiphenylsulfone, 3 ', 5,5 '-tetramethyl-4, 4' -diaminodiphenylmethane, ethyl 2- (3 ', 5' -diaminobenzoyloxy) methacrylate), 2, 4-diaminocumene and 2, 5-diaminocumene, 2, 5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5, 6-tetramethyl-p-phenylenediamine, 2,4, 6-trimethyl-m-phenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, 2, 7-diaminofluorene, 2, 5-diaminopyridine, 1, 2-bis (4-aminophenyl) ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1, 5-diaminonaphthalene, diaminobenzotrifluoride, 1, 3-bis (4-aminophenyl) hexafluoropropane, 1, 4-bis (4-aminophenyl) octafluorobutane, 1, 5-bis (4-aminophenyl) decafluoropentane, 1, 7-bis (4-aminophenyl) tetradecafluoroheptane, 2-bis [4- (3-aminophenoxy) phenyl ] hexafluoropropane, 2-bis [4- (2-aminophenoxy) phenyl ] hexafluoropropane, 2-bis [4- (4-aminophenoxy) -3, 5-dimethylphenyl ] hexafluoropropane, 2-bis [4- (4-aminophenoxy) -3, 5-bis (trifluoromethyl) phenyl ] hexafluoropropane, p-bis (4-amino-2-trifluoromethylphenoxy) benzene, 4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl, a salt thereof, a pharmaceutically acceptable carrier, and a pharmaceutically acceptable carrier, 4,4 '-bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4' -bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4 '-bis (3-amino-5-trifluoromethylphenoxy) diphenylsulfone, 2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl ] hexafluoropropane, 3', 5,5 '-tetramethyl-4, 4' -diaminobiphenyl, 4 '-diamino-2, 2' -bis (trifluoromethyl) biphenyl, 2 ', 5, 5', 6,6 '-hexafluorotolidine, and 4, 4' -diaminotetrabiphenyl.

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

[ chemical formula 4]

Further, a diamine having two or more alkylene glycol units in the main chain can be also preferably used. The diamine is preferably a diamine containing two or more ethylene glycol chains or propylene glycol chains in total or both of them in one molecule, and more preferably a diamine containing no aromatic ring. Specific examples thereof 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 Co., Ltd.), 1- (2- (2-aminopropoxy) ethoxy) propoxy) propan-2-amine, and 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propan-2-amine, but the present invention is not limited thereto.

The following shows the structures of 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, and JEFFAMINE (registered trademark) EDR-176.

[ chemical formula 5]

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

From the viewpoint of flexibility of the resulting cured film, R is preferred¹¹¹from-Ar⁰-L⁰-Ar⁰-represents. Wherein Ar is⁰Each independently an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 10 carbon atoms), preferably a phenylene group. L is⁰Represents a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C (═ O) -, -S-, -S (═ O)₂-, -NHCO-and a group selected from a combination of these. Preferred ranges are as defined above for A.

From the viewpoint of i-ray transmittance, R¹¹¹Preferred is a 2-valent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and ready availability, the 2-valent organic group represented by formula (61) is more preferable.

[ chemical formula 6]

R⁵⁰～R⁵⁷Each independently is a hydrogen atom, a fluorine atom or a 1-valent organic group, R⁵⁰～R⁵⁷At least one ofEach is a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group.

As R⁵⁰～R⁵⁷Examples of the 1-valent organic group in (b) include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and the like.

[ chemical formula 7]

R⁵⁸And R⁵⁹Each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group.

Examples of the diamine compound to which the structure of formula (51) or (61) is imparted include dimethyl-4, 4 '-diaminobiphenyl, 2' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl, 2' -bis (fluoro) -4,4 '-diaminobiphenyl, 4' -diaminooctafluorobiphenyl, and the like. One of these may be used, or two or more of these may be used in combination

＜＜＜R¹¹⁵＞＞＞

R in the formula (1)¹¹⁵Represents a 4-valent organic group. The 4-valent organic group is preferably a group containing an aromatic ring, and more preferably a group represented by the following formula (5) or formula (6).

[ chemical formula 8]

R¹¹²The meaning of A is the same, and the preferable range is the same.

With respect to R in the formula (1)¹¹⁵Specific examples of the 4-valent organic group include tetracarboxylic acid residues remaining after removal of the acid dianhydride group from the tetracarboxylic acid dianhydride. The tetracarboxylic dianhydride may be used alone or in combination of two or more. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).

[ chemical formula 9]

R¹¹⁵Represents a 4-valent organic group. R¹¹⁵With R of the formula (1)¹¹⁵The same is true.

Specific examples of the tetracarboxylic acid dianhydride include those selected from the group consisting of pyromellitic acid, pyromellitic acid dianhydride (PMDA), 3,3 ', 4,4 ' -biphenyltetracarboxylic acid dianhydride, 3,3 ', 4,4 ' -diphenylsulfide tetracarboxylic acid dianhydride, 3,3 ', 4,4 ' -diphenylsulfone tetracarboxylic acid dianhydride, 3,3 ', 4,4 ' -benzophenonetetracarboxylic acid dianhydride, 3,3 ', 4,4 ' -diphenylmethane tetracarboxylic acid dianhydride, 2 ', 3,3 ' -diphenylmethane tetracarboxylic acid dianhydride, 2,3,3 ', 4 ' -biphenyltetracarboxylic acid dianhydride, 2,3,3 ', 4 ' -benzophenonetetracarboxylic acid dianhydride, 4,4 ' -oxydiphthalic acid dianhydride, 2,3,6, 7-naphthalenetetracarboxylic acid dianhydride, 1,4,5, 7-naphthalenetetracarboxylic acid dianhydride, 1,4, 7-naphthalenetetracarboxylic acid dianhydride, and mixtures thereof, 2, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 1, 3-diphenylhexafluoropropane-3, 3,4, 4-tetracarboxylic dianhydride, 1,4,5, 6-naphthalenetetracarboxylic dianhydride, 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-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 1,2,3, 4-benzenetetracarboxylic dianhydride, and at least one of alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

Further, as preferable examples, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below can be given.

[ chemical formula 10]

＜＜＜R¹¹³And R¹¹⁴＞＞＞

In the formula (1), R¹¹³And R¹¹⁴Each independently represents a hydrogen atom or a 1-valent organic group. R¹¹³And R¹¹⁴At least one of them preferably contains a radical polymerizable group, and more preferably both contain a radical polymerizable group. The radical polymerizable group is a group capable of undergoing a crosslinking reaction by the action of a radical, and a preferable example thereof is a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, (meth) acryloyl group, a group represented by the following formula (III), and the like.

[ chemical formula 11]

In the formula (III), R²⁰⁰Represents a hydrogen atom or a methyl group, and more preferably a methyl group.

In the formula (III), R²⁰¹An alkylene group having 2 to 12 carbon atoms, -CH₂CH(OH)CH₂Or a (poly) oxyalkylene group having 4 to 30 carbon atoms (as the alkylene group, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms; the number of repetitions is preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms). Further, (poly) oxyalkylene represents oxyalkylene or polyoxyalkylene.

Preferred R²⁰¹Examples of (3) include ethylene, propylene, trimethylene, tetramethylene, 1, 2-butylene, 1, 3-butylene, pentamethylene, hexamethylene, octamethylene, dodecamethylene and-CH₂CH(OH)CH₂-, more preferably ethylene, propylene, trimethylene, -CH₂CH(OH)CH₂-。

Particularly preferably R²⁰⁰Is methyl, R²⁰¹Is an ethylene group.

As a preferred embodiment of the polyimide precursor in the present invention, R is¹¹³Or R¹¹⁴Examples of the 1-valent organic group in (b) include an aliphatic group, an aromatic group, an aralkyl group and the like having 1,2 or 3 acid groups, preferably 1 acid group. Specifically, there may be mentioned an aromatic group having 6 to 20 carbon atoms and having an acid group, and a 7 to e carbon group having an acid group25, or an aralkyl group. More specifically, a phenyl group having an acid group and a benzyl group having an acid group are exemplified. The acid group is more preferably a hydroxyl group. Namely, R¹¹³Or R¹¹⁴Preferred is a group having a hydroxyl group.

As a group consisting of R¹¹³Or R¹¹⁴The 1-valent organic group represented may preferably be a substituent which improves the solubility of the developer.

From the viewpoint of solubility in an aqueous developer, R¹¹³Or R¹¹⁴More preferred are a hydrogen atom, 2-hydroxybenzyl group, 3-hydroxybenzyl group and 4-hydroxybenzyl group.

From the viewpoint of solubility in organic solvents, R¹¹³Or R¹¹⁴Preferably a 1-valent organic group. The 1-valent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, and an aromatic group, and more preferably an alkyl group substituted with an aromatic group.

The number of carbon atoms of the alkyl group is preferably 1 to 30 (3 or more in the case of a cyclic group). The alkyl group may be linear, branched, or cyclic. Examples of the straight-chain 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, an octadecyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 1-ethylpentyl group, and a 2-ethylhexyl group. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of the polycyclic cyclic alkyl group include an adamantyl group, a norbornyl group, a camphyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecyl group, a camphyl group, a dicyclohexyl group, and a pinenyl group (pinenyl group). The alkyl group substituted with an aromatic group is preferably a straight-chain alkyl group substituted with an aromatic group described below.

Specific examples of the aromatic group include a substituted or unsubstituted aromatic hydrocarbon group (examples of the cyclic structure of the constituent group include a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indene ring, a perylene ring, and a fused perylene ringPentacene ring, acenaphthylene ring, phenanthrene ring, anthracene ring, fused tetra-benzene ring,

A ring, a triphenylene ring, etc.) or a substituted or unsubstituted aromatic heterocyclic group (a cyclic structure as a constituent group, a fluorene ring, a biphenyl ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an indolizine ring, an indole ring, a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxathiin ring, a phenothiazine ring, or a phenazine ring).

In the polyimide precursor, it is also preferable that the constituent unit has a fluorine atom. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less. The upper limit is not particularly limited, and is actually 50% by mass or less.

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

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

[ chemical formula 12]

A¹¹And A¹²Represents an oxygen atom or NH, R¹¹¹And R¹¹²Each independently represents a 2-valent organic group, R¹¹³And R¹¹⁴Each independently represents a hydrogen atom or a 1-valent organic group, R¹¹³And R¹¹⁴At least one of them is preferably a radical polymerizable group-containing group, more preferably a radical polymerizable groupA radical polymerizable group.

A¹¹、A¹²、R¹¹¹、R¹¹³And R¹¹⁴Independently of one another and in preferred ranges in formula (1) A¹、A²、R¹¹¹、R¹¹³And R¹¹⁴The preferred ranges of (A) are as defined above.

R¹¹²With R in the formula (5)¹¹²The same applies to (1), wherein an oxygen atom is more preferred.

In the formula (1-A), the bonding position of the carbonyl group in the formula at the benzene ring is preferably 4,5, 3 ', 4'. In the formula (1-B), 1,2,4, and 5 are preferable.

In the polyimide precursor, the structural unit represented by formula (1) may be one kind, or two or more kinds. And may contain structural isomers of the structural unit represented by formula (1). The polyimide precursor may contain other types of structural units in addition to the structural unit of formula (1).

As an embodiment of the polyimide precursor in the present invention, there can be exemplified a polyimide precursor in which 50 mol% or more, further 70 mol% or more, and particularly 90 mol% or more of the total structural units are structural units represented by the formula (1). The upper limit is actually 100 mol% or less.

The polyimide precursor preferably has a weight average molecular weight (Mw) of 2000 to 500000, more preferably 5000 to 100000, and still more preferably 10000 to 50000. The number average molecular weight (Mn) is preferably 800 to 250000, more preferably 2000 to 50000, and further preferably 4000 to 25000.

The dispersion degree of the molecular weight of the polyimide precursor is preferably 1.5 to 3.5, and more preferably 2 to 3.

The polyimide precursor can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, the dicarboxylic acid or dicarboxylic acid derivative is halogenated with a halogenating agent and then reacted with a diamine.

In the method for producing a polyimide precursor, an organic solvent is preferably used when the reaction is carried out. One or more organic solvents may be used.

The organic solvent can be appropriately set according to the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone.

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

The content of the polyimide precursor in the resin composition of the present invention is preferably 20 mass% or more, more preferably 30 mass% or more, further preferably 40 mass% or more, further preferably 50 mass% or more, further preferably 60 mass% or more, and further preferably 70 mass% or more, based on the total solid content of the resin composition. 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, still more preferably 98% by mass or less, and still more preferably 95% by mass or less, based on the total solid content of the resin composition.

The resin composition of the present invention may contain only one kind of polyimide precursor, or may contain two or more kinds. When two or more are included, the total amount is preferably in the above range.

< thermal alkali production agent >

The resin composition of the present invention contains a thermal alkali generator. The kind of the thermal alkali generator is not particularly limited, and it is preferable to contain at least one thermal alkali generator selected from an acidic compound which generates an alkali when heated to 40 ℃ or higher, and an ammonium salt having an anion having a pKa1 of 0 to 4 and an ammonium cation. Wherein pKa1 represents the logarithm (-Log) of the dissociation constant (Ka) of the first proton of the acid₁₀Ka), details of which will be described later.

By compounding these compounds, the cyclization reaction of the polyimide precursor can be performed at a low temperature. Further, since the thermal alkali generator does not generate an alkali unless heated, even if it coexists with the polymer precursor, cyclization of the polymer precursor during storage can be suppressed, and the storage stability is excellent.

The thermal alkali generator preferably contains at least one selected from the group consisting of an acidic compound (A1) which generates an alkali when heated to 40 ℃ or higher, an ammonium salt (A2) having an anion having a pKa1 of 0 to 4 and an ammonium cation, and a nonionic thermal alkali generator (A3), and more preferably contains a nonionic thermal alkali generator (A3). Since these compounds generate a base when heated, the base generated from these compounds can promote the cyclization reaction of the polyimide precursor and can cyclize the polyimide precursor at a low temperature. In the present specification, the acidic compound means the following compound: compound 1g was collected in a container, 50mL of a mixed solution of ion-exchanged water and tetrahydrofuran (water/tetrahydrofuran: 1/4 by mass) was added, the mixture was stirred at room temperature for 1 hour, and the solution thus obtained was measured by pH (power of hydrogen: pH) at 20 ℃ and was found to be less than 7.

The alkali generation temperature of the thermal alkali generator used in the present invention is preferably 40 ℃ or higher, and more preferably 120 to 200 ℃. The upper limit of the alkali generation temperature is preferably 190 ℃ or less, more preferably 180 ℃ or less, and still more preferably 165 ℃ or less. The base generation temperature can be determined as follows: for example, the compound is heated to 250 ℃ at 5 ℃/min in a pressure-resistant capsule by differential scanning calorimetry, the peak temperature of the exothermic peak with the lowest temperature is read, and the peak temperature is taken as the base generation temperature.

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

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

In the present embodiment, the acidic compound (a1) preferably contains 1 or more selected from ammonium salts and compounds represented by the following formula (101) or (102).

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 which generates a base when heated to 40 ℃ or higher (preferably 120 to 200 ℃), or may be a compound other than an acidic compound which generates a base when heated to 40 ℃ or higher (preferably 120 to 200 ℃).

In the present embodiment, the ammonium salt represents a salt of an ammonium cation represented by the following formula (101) or formula (102) and an anion. The anion may be bonded to any part of the ammonium cation via a covalent bond, and may be present outside the molecule of the ammonium cation, but is preferably present outside the molecule of the ammonium cation. The presence of an anion outside the molecule of the ammonium cation indicates that the ammonium cation and the anion are not bonded to each other via a covalent bond. Hereinafter, the anion outside the molecule of the cation portion is also referred to as a counter anion.

Formula (101) formula (102)

[ chemical formula 13]

In the formulae (101) and (102), R¹～R⁶Each independently represents a hydrogen atom or a hydrocarbon group, R⁷Represents a hydrocarbon group. R in the formulae (101) and (102)¹And R²、R³And R⁴、R⁵And R⁶、R⁵And R⁷May be bonded to form a ring.

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

[ chemical formula 14]

In the formulae (Y1-1) to (Y1-5), R¹⁰¹Represents an n-valent organic radical, R¹And R⁷Has the same meaning as that of the formula (101) or the formula (102).

In the formulae (Y1-1) to (Y1-5), Ar¹⁰¹And Ar¹⁰²Each independently represents 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 pKa1 of 0 to 4 and an ammonium cation. The upper limit of the pKa1 of the anion is more preferably 3.5 or less, and still 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 the stability of the resin composition can be improved. When pKa1 is 4 or less, the thermal alkali generator has good stability, and generation of alkali without heating can be suppressed, so that the resin composition has good stability. When pKa1 is 0 or more, the generated base is not easily neutralized, and the cyclization efficiency of the polymer precursor is good.

The kind of the anion is preferably 1 selected from the group consisting of a carboxylate anion, a phenol anion, a phosphate anion and a sulfate anion, and from the viewpoint of satisfying both the stability of the salt and the thermal decomposability, a carboxylate anion is more preferred. That is, the ammonium salt is more preferably a salt of an ammonium cation with a carboxylate anion.

The carboxylate anion is preferably an anion of a 2-valent or higher carboxylic acid having 2 or more carboxyl groups, and more preferably an anion of a 2-valent carboxylic acid. According to this aspect, the thermal alkali generator can be provided which can further improve the stability, curability, and developability of the resin composition. In particular, the use of the anion of the 2-valent carboxylic acid can further improve the stability, curability, and developability of the resin composition.

In the present embodiment, the carboxylate anion is preferably an anion of a carboxylic acid having pKa1 of 4 or less. The pKa1 is more preferably 3.5 or less, and still more preferably 3.2 or less. According to this embodiment, the stability of the resin composition can be further improved.

Among them, pKa1 represents the logarithm of the inverse of the dissociation constant of the first proton of an acid, and can be found in Determination of Organic Structures by Physical Methods (authors: Brown, H.C., McDaniel, D.H., Hafliger, O.A., Nachod, F.C.; editions: Braude, E.A., Nachod, F.C.; Academic Press, New York,1955) or Data for Biochemical Research (authors: Dawson, R.M.C.et al; Oxford, Clarendon Press, 1959). As for the compounds not described in these documents, values calculated from the structural formulae using software using ACD/pKa (manufactured by ACD/Labs) were used.

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

[ chemical formula 15]

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 substituent constant σ m. Among them, σ m is described in detail in general, Journal of Synthetic Organic Chemistry, Japan, Vol.23, No. 8 (1965), p.631-642. The electron-withdrawing group in the present embodiment is not limited to the substituents described in the above documents.

Examples of the substituent having a positive σ m include CF₃Base (. sigma.m.0.43), CF₃CO group (σ m ═ 0.63), HC ≡ C group (σ m ≡ 0.21), CH group₂CH (σ m) group 0.06, Ac (σ m) group 0.38, MeOCO (σ m) group 0.37, MeCOCH (σ m) CH group 0.21, PhCO (σ m) group 0.34, H₂NCOCH₂And a group (σ m ═ 0.06). In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group.

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

[ chemical formula 16]

In the formulae (EWG-1) to (EWG-6), R^x1～R^x3Each independently represents 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.

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

Formula (XA)

[ chemical formula 17]

In the formula (XA), L¹⁰Represents a single bond or an alkylene group, an alkenylene group, an aromatic group, -NR^XAnd in combinations thereof a linking group having a valence of 2, R^XRepresents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group.

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

< specific thermal alkali-producing agent >

Examples of the nonionic thermal alkali generator (a3) include compounds represented by the formula (B1) or the formula (B2).

[ chemical formula 18]

In the formulae (B1), (B2), Rb¹、Rb²And Rb³Each independently represents an organic group having no tertiary amine structure, a halogen atom or a hydrogen atom. Wherein, Rb is¹And Rb²And not both hydrogen atoms. And, Rb¹、Rb²And Rb³Has no carboxyl group. In the present specification, the tertiary amine structure refers to a structure in which 3 bonds of a nitrogen atom having a valence of 3 are all covalently bonded to a hydrocarbon-based carbon atom. Therefore, the case where the carbon atom to which the bond is bonded forms a carbon atom of a carbonyl group does not fall within the above range, that is, the case where the carbon atom forms an amide group together with a nitrogen atom does not fall within the above range.

Among the formulae (B1) and (B2), Rb is preferred¹、Rb²And Rb³At least 1 of which comprises a cyclic structure, more preferably at least 2 comprise a cyclic structure. The cyclic structure may be monocyclic or fused ringAny one, preferably a single ring or 2 condensed rings. The monocyclic system is preferably a 5-membered ring or a 6-membered ring, and preferably a 6-membered ring. The monocyclic cyclohexane ring and the benzene ring are preferred, and the cyclohexane ring is more preferred.

More specifically, Rb¹And Rb²Preferably a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms) or an aralkyl group (preferably having 7 to 25 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 12 carbon atoms). These groups may have a substituent in a range in which the effect of the present invention is exerted. Rb¹And Rb²May be bonded to each other to form a ring. The ring to be formed is preferably a 4-to 7-membered nitrogen-containing heterocycle. In particular, Rb¹And Rb²Preferably a linear, branched or cyclic alkyl group which may have a substituent (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), and a cycloalkyl group which may have a substituent (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), more preferably, and further preferably a cyclohexyl group which may have a substituent.

As Rb³Examples thereof include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, further preferably 2 to 6 carbon atoms), an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 12 carbon atoms), an aralkenyl group (preferably 8 to 24, more preferably 8 to 20, further preferably 8 to 16 carbon atoms), an alkoxy group (preferably 1 to 24, more preferably 2 to 18, further preferably 3 to 12 carbon atoms), an aryloxy group (preferably 6 to 22, more preferably 6 to 18, further preferably 6 to 12 carbon atoms), or an aralkyloxy group (preferably 7 to 23, more preferably 7 to 19, further preferably 7 to 12 carbon atoms). Among them, preferred are cycloalkyl groups (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), aralkenyl groups, and aralkyloxy groups. Rb³The compound may further have a substituent within a range in which the effects of the present invention are exhibited.

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

[ chemical formula 19]

In the formula, Rb¹¹And Rb¹²And Rb³¹And Rb³²Respectively with Rb of formula (B1)¹And Rb²The same is true.

Rb¹³The alkyl group (preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), an alkenyl group (preferably has 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), an aryl group (preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an aralkyl group (preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 12 carbon atoms), and has a substituent within a range in which the effects of the present invention are exhibited. Wherein, Rb is¹³Preferably an aralkyl group.

Rb³³And Rb³⁴Each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, further preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, further preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms), an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 11 carbon atoms), and preferably a hydrogen atom.

Rb³⁵The alkyl group is preferably an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, further preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an aralkyl group (preferably having 7 to 23 carbon atoms, further preferably 7 to 19 carbon atoms, further preferably 7 to 12 carbon atoms), and preferably an aryl group.

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

[ chemical formula 20]

Rb¹¹And Rb¹²With Rb in the formula (B1-1)¹¹And Rb¹²The same is true.

Rb¹⁵And Rb¹⁶The alkyl group is preferably a hydrogen atom, an alkyl group (preferably a carbon number of 1 to 12, more preferably 1 to 6, further preferably 1 to 3), an alkenyl group (preferably a carbon number of 2 to 12, more preferably 2 to 6, further preferably 2 to 3), an aryl group (preferably a carbon number of 6 to 22, more preferably 6 to 18, further preferably 6 to 10), an aralkyl group (preferably a carbon number of 7 to 23, more preferably 7 to 19, further preferably 7 to 11), and preferably a hydrogen atom or a methyl group.

Rb¹⁷The aromatic hydrocarbon compound is preferably an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 3 to 8 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an aralkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 12 carbon atoms), and particularly preferably an aryl group.

The molecular weight of the nonionic thermal alkali generator (a3) is preferably 800 or less, more preferably 600 or less, and still more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and further preferably 300 or more.

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

[ chemical formula 21]

[ chemical formula 22]

[ chemical formula 23]

[ chemical formula 24]

The content of the thermal alkali 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 still more preferably 20% by mass or less. One or more than two kinds of the thermal alkali-producing agents can be used. When two or more are used, the total amount is preferably within the above range.

< thermosetting compound >

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

The molecular weight (weight average molecular weight in the case of a polymer) of the thermosetting compound is preferably 100 to 10000. The lower limit is preferably 150 or more, and more preferably 200 or more. The upper limit is preferably 1000 or less, and more preferably 500 or less.

The curing start temperature of the thermosetting compound is preferably 100 to 350 ℃. The lower limit is preferably 110 ℃ or higher, and more preferably 120 ℃ or higher. The upper limit is preferably 200 ℃ or lower, more preferably 180 ℃ or lower. In the present invention, the curing start temperature of the thermosetting compound is a temperature at which the exothermic reaction of the thermosetting compound starts, which is measured by heating 1mg of the sample (thermosetting compound) from a state of 25 ℃ at a heating rate of 5 ℃/min and performing differential scanning calorimetry. The temperature at which the exothermic reaction of the thermosetting compound starts is a temperature at which a peak of the exothermic reaction appears in a differential scanning calorimetry curve in which the vertical axis represents a heat flow (mW) and the horizontal axis represents a temperature (deg.c). When the heat-generating reaction peak has 2 or more, the heat-generating reaction peak at a relatively low temperature is defined as "temperature at which the heat-generating 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 the group consisting of epoxy groups, oxetane groups, hydroxymethyl groups and alkoxymethyl groups, more preferably a compound having a plurality of functional groups selected from the group consisting of hydroxymethyl groups and alkoxymethyl groups, and is more preferably a compound having a plurality of alkoxymethyl groups, and particularly preferably a compound having a plurality of methoxymethyl groups, from the viewpoint of easily obtaining the effects of the present invention more remarkably.

The number of the functional groups contained in the thermosetting compound may be 2 or more, and preferably 3 or more. The upper limit is preferably 10 or less, and more preferably 6 or less.

The thermosetting compound used in the present invention is preferably a compound represented by the formula (TC 1).

X¹-(Y¹)_n……(TC1)

In the formula (TC1), X¹Represents a linking group of n valence, Y¹Represents an epoxy group, an oxetanyl group, a hydroxymethyl group, an alkoxymethyl group, a phenol group, a maleimide group, a cyanate group or a blocked isocyanate group, and n represents an integer of 2 or more.

X as formula (TC1)¹Examples of the n-valent linking group include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, heterocyclic groups, -O-, -NH-, -NHCO-, -CONH-, -OCO-, -COO-, -CO-, -SO₂NH-、-SO₂-and combinations of these. 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 any of linear, branched and cyclic,preferably straight or branched, and especially preferably straight. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 15. The aromatic hydrocarbon group may be a single ring or a condensed ring. The heterocyclic group may be a single ring or a condensed ring. The heterocyclic group is preferably a monocyclic ring or a condensed ring having a condensed number of 2 to 4. The number of hetero atoms constituting the ring of the heterocyclic group is preferably 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 3 to 30, more preferably 3 to 18, and still more preferably 3 to 12.

X of formula (TC1)¹Groups containing cyclic structures are preferred. Examples of the cyclic structure include an aliphatic ring, an aromatic hydrocarbon ring, and a heterocyclic ring, and 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 heterocycle include a pyridine ring, a triazine ring, and an imidazolidinone ring is preferable.

Y of formula (TC1)¹Represents an epoxy group, an oxetanyl group, a hydroxymethyl group, an alkoxymethyl group, a phenol group, a maleimide group, a cyanate group or a blocked isocyanate group, preferably an epoxy group, an oxetanyl group, a hydroxymethyl group or an alkoxymethyl group, more preferably a hydroxymethyl group or an alkoxymethyl group, and still more preferably an alkoxymethyl group.

The alkoxymethyl group is represented by-CH₂-ORy¹The group shown. Ry¹The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, still more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 3 carbon atoms, and most preferably an alkyl group (methyl group) having 1 carbon atom. That is, the alkoxymethyl group is most preferably a methoxymethyl group.

The thermosetting compound used in the present invention is also preferably a compound in which a hydroxymethyl group or an alkoxymethyl group is bonded to a carbon atom forming a nitrogen atom or an aromatic ring. Preferred examples of these compounds include alkoxymethylated melamine, hydroxymethylated melamine, alkoxymethylated benzoguanamine, hydroxymethylbenzoguanamine, alkoxymethylated glycoluril, hydroxymethylated glycoluril, alkoxymethylated urea, and hydroxymethylated urea. Further, the compounds described in the paragraphs 0056 to 0065 of Japanese patent application laid-open No. 2003-287889 and the paragraphs 0058 to 0060 of Japanese patent application laid-open No. 2018-084626 can also be used.

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

[ chemical formula 25]

In the formula (AM-101), Rm¹～Rm⁴Each independently represents a hydrogen atom or a group represented by the formula (Rm). Wherein Rm¹～Rm⁴2 or more of (a) are groups represented by formula (Rm).

In the formula (AM-102), Rm⁵～Rm⁸Each independently represents a hydrogen atom or a group represented by the formula (Rm). Wherein Rm⁵～Rm⁸2 or more of (a) are groups represented by formula (Rm).

In the formula (AM-103), Rm⁹And Rm¹⁰Each independently represents a group represented by the formula (Rm).

In the formula (AM-104), Rm¹¹～Rm¹⁶Each independently represents a hydrogen atom or a group represented by the formula (Rm). Wherein Rm¹¹～Rm¹⁶2 or more of (a) are groups represented by formula (Rm).

In the formula (AM-105), Rm¹⁷～Rm²⁰Each independently represents a hydrogen atom or a group represented by the formula (Rm). Wherein Rm¹⁷～Rm²⁰2 or more of (a) are groups represented by formula (Rm).

(formula (Rm))

-CH₂-O-Rm¹⁰⁰

In the formula (Rm), Rm¹⁰⁰Represents a hydrogen atom or an alkyl group. Rm¹⁰⁰The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 15, still more preferably 1 to 8, particularly preferably 1 to 3, and most preferably 1. That is, the alkoxymethyl group is most preferably a methoxy groupA methyl group.

Examples of the compound of an alkoxymethyl group or a hydroxymethyl group and a carbon atom forming an aromatic ring include compounds represented by the following formula (AM-110).

Formula (AM-110)

[ chemical formula 26]

In the formula (AM-110), X represents a single bond or an organic group having a valence of 1 to 4, R¹¹～R¹³Each independently represents a hydrogen atom or an alkyl group, R¹⁵Represents a hydrogen atom, a hydroxyl group or an alkyl group, n, p and r are each independently an integer of 1 to 4, and q is an integer of 0 to 4.

Specific examples of the thermosetting compound having a hydroxymethyl group or an alkoxymethyl group include compounds having the following structures. Commercially available products include 46DMOC, 46DMOEP, TM-BIP-A (manufactured by ASAHI YUKIZAI CORPORATION), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylBisOC-P, DML-PFP, DML-PSBP, DML-Tris PC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPA, HML-TPHAP, HMML-TPA, HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., manufactured by Ltd., manufactured by NikalMX-290, KANILAC-280-PHbC, PHbPHbC-270, LTMX-36220, LTLM 2, LTLM-36CO 2, manufactured by TokyL-P.

[ chemical formula 27]

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 2 or more epoxy groups, and 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 the epoxy compound include bisphenol a type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; epoxy group-containing silicones such as polymethyl (glycidoxypropyl) siloxane, but the epoxy group-containing silicones are not limited to these. Specifically, EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4850-150, EPICLON EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822 (registered trademark) Corporation, RIKARESIN (registered trademark) BEO-60E (registered trademark, New Japan, Inc. 4003S, EP, etc. Further, compounds having the following structures can also be used.

[ chemical formula 28]

In the present invention, a thermosetting compound having an oxetanyl group (hereinafter, also referred to as an oxetane compound) can be used as the thermosetting compound. Examples of the oxetane compound include 3-ethyl-3-hydroxymethyloxetane, 1, 4-bis { [ (3-ethyl-3-oxetane) methoxy ] methyl } benzene, 3-ethyl-3- (2-ethylhexylmethyl) oxetane, and 1, 4-benzenedicarboxylic acid-bis [ (3-ethyl-3-oxetane) methyl ] ester. Examples of commercially available products include ARONE OXETANE series (e.g., OXT-121, OXT-221, OXT-191, and OXT-223) manufactured by TOAGOSEI CO.

In the present invention, a thermosetting compound having a blocked isocyanate group (hereinafter, also referred to as a blocked isocyanate compound) can also 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. As a specific example of the skeleton, reference can be made to the description of japanese patent application laid-open No. 0144 of jp 2014-238438 a, the contents of which are incorporated in the present specification. Examples of the matrix structure of the blocked isocyanate compound include a biuret type, an isocyanate type, an adduct type, and a bifunctional prepolymer type. Examples of the blocking agent for forming a block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, thiol compounds, imidazole compounds, and imide compounds. Among them, a blocking agent selected from an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, and a pyrazole compound is particularly preferable. As a specific example of the blocking agent, reference can be made to the description in Japanese patent application laid-open No. 2014-238438, paragraph number 0146, the content of which is incorporated in the present specification. The blocked isocyanate compound is commercially available, and for example, CORONATE AP STABLE M, CORONATE2503, 2515, 2507, 2513, 2555, MILLIONATE MS-50 (manufactured by Nippon Polyurethane Industry Co., Ltd.), TAKENATE B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (manufactured by Mitsui Chemicals, Inc.), RANATE 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K8260 45, MF-K8560, E402-B80B, SBN-70D, SBB-70P, K (manufactured by Asahi Kasei corporation), Desmodbl corporation 355, MFP 533575, MF-K33B, E402/B80/3675, SBN-70D, SBB-366000 (manufactured by Asahi Kasei corporation), DSM 353575, MFP 5375/3675, MFP A3375/3675, MFBL 3/3475, MFP 3/3675, MFP 3/BL 3, MFP 9/3, MFP-B60/3, MFP 3, MFB 80, MFP 3, MF, BL4265SN, PL340, PL350, and Sumidur BL3175 (manufactured by Covestro AG).

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

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, and more preferably 5% by mass or more. The upper limit is preferably 18% by mass or less, and more preferably 15% by mass or less.

The content of the thermosetting compound is preferably 1 to 25 parts by mass per 100 parts by mass of the polyimide precursor. The upper limit is preferably 23 parts by mass or less, and more preferably 20 parts by mass or less. The lower limit is preferably 4 parts by mass or more, and more preferably 6 parts by mass or more. When the content of the thermosetting compound is 6 parts by mass or more per 100 parts by mass of the polyimide precursor, a cured film having excellent chemical resistance can be 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 adhesiveness can be easily obtained.

The content of the thermosetting compound is preferably 10 to 1000 parts by mass per 100 parts by mass of the thermal alkali generator. The upper limit is preferably 800 parts by mass or less, and more preferably 600 parts by mass or less. The lower limit is preferably 20 parts by mass or more, and more preferably 50 parts by mass or more.

The thermosetting compound may be used alone or in combination of two or more. When two or more kinds are used simultaneously, the total amount thereof is preferably in the above range.

< photopolymerization initiator >

The resin composition of the present invention preferably contains a photopolymerization initiator. 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 a photosensitive activity to light rays from an ultraviolet region to a visible region is preferable. Also, the active agent may have some action with a photo-excited sensitizer to generate an active radical.

The photo radical polymerization initiator preferably contains at least one compound having an absorption coefficient of at least about 50 mol in the range of about 300 to 800nm (preferably 330 to 500 nm). The molar absorption coefficient of a compound can be measured by a known method. For example, it is preferable to perform measurement using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer, manufactured by Varian corporation) at a concentration of 0.01g/L using an ethyl acetate solvent.

As the photo radical polymerization initiator, a known compound can be arbitrarily used. Examples thereof include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbisimidazole and oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium hydroxides, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron-arene complexes. For details of these, reference can be made to the descriptions of paragraphs 0165 to 0182 of japanese patent application laid-open No. 2016-027357 and paragraphs 0138 to 0151 of international publication No. 2015/199219, which are incorporated in the present specification.

Examples of the ketone compound include those described in paragraph 0087 of Japanese patent application laid-open No. 2015-087611, which are incorporated herein by reference. Among commercially available products, KAYACURE DETX (Nippon Kayaku co., ltd.) is also preferably used.

As the photo radical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, an aminoacetophenone-based initiator described in Japanese patent laid-open No. 10-291969 and an acylphosphine oxide-based initiator described in Japanese patent No. 4225898 can be used.

As the hydroxyacetophenone-based initiator, IRGACURE 184(IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: manufactured by BASF Co., Ltd.) were used.

As the aminoacetophenone initiator, commercially available IRGACURE 907, IRGACURE 369 and IRGACURE 379 (trade name: manufactured by BASF) were used.

As the aminoacetophenone-based initiator, a compound described in Japanese patent laid-open publication No. 2009-191179, which has a maximum absorption wavelength matching a light source having a wavelength of 365nm or 405nm, can also be used.

Examples of the acylphosphine initiator include 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, IRGACURE-819 or IRGACURE-TPO (trade name: manufactured by BASF) can be used as a commercially available product.

Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF corporation).

The photo radical polymerization initiator is more preferably an oxime compound. By using the oxime compound, the exposure latitude can be further effectively improved. Among oxime compounds, oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also function as a photocuring accelerator.

Specific examples of the oxime compound include compounds described in Japanese patent application laid-open Nos. 2001-233842, 2000-080068, and 2006-342166.

Preferred examples of the oxime compounds include compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. In the resin composition of the present invention, an oxime compound (oxime-based photopolymerization initiator) is particularly preferably used as the photo radical polymerization initiator. The oxime-based photopolymerization initiator has a linking group of > C — N — O — C (═ O) -in the molecule.

[ chemical formula 29]

Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (manufactured by BASF Co., Ltd.), and ADEKA OPTOMER N-1919 (photo radical polymerization initiator 2 described in ADEKA CORPORATION, Japanese patent application laid-open No. 2012 and 014052) can also be preferably used. Also, TR-PBG-304 (manufactured by Changzhou powerful electronic New Material Co., Ltd.), ADEKAARKLS NCI-831 and ADEKAARKLS NCI-930 (manufactured by ADEKA CORPORATION) can be used. DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can be used.

Further, an oxime compound having a fluorine atom can also be used. Specific examples of these oxime compounds include the compounds described in Japanese patent application laid-open No. 2010-262028, the compounds 24, 36 to 40 described in section 0345 of Japanese patent application laid-open No. 2014-500852, and the compound (C-3) described in section 0101 of Japanese patent application laid-open No. 2013-164471.

Most preferred oxime compounds include an oxime compound having a specific substituent as shown in Japanese patent laid-open Nos. 2007-269779 and a thioaryl group as shown in Japanese patent laid-open Nos. 2009-191061.

From the viewpoint of exposure sensitivity, the photo radical polymerization initiator is a compound selected from the group consisting of trihalomethyl triazine compounds, benzyl dimethyl ketal compounds, α -hydroxyketone compounds, α -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium hydroxide compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadienyl-benzene-iron complexes and bases thereof, halomethyl oxadiazole compounds, 3-aryl substituted coumarin compounds.

More preferred photo radical polymerization initiators are trihalomethyl triazine compounds, α -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium hydroxide compounds, benzophenone compounds, acetophenone compounds, further preferably at least one compound selected from the group consisting of trihalomethyl triazine compounds, α -aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds, still further preferably metallocene compounds or oxime compounds are used, and still further preferably oxime compounds are used.

Further, as the photo radical polymerization initiator, N ' -tetraalkyl-4, 4 ' -diaminobenzophenone such as benzophenone and N, N ' -tetramethyl-4, 4 ' -diaminobenzophenone (Michler's ketone)), aromatic ketones such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-acetone-1, quinones obtained by fusing an aromatic ring such as alkylanthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkyl benzoin, and benzyl derivatives such as benzyl dimethyl ketal can be used. Further, a compound represented by the following formula (I) can also be used.

[ chemical formula 30]

In the formula (I), R^I00Is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by 1 or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkyl group having 2 to 18 carbon atoms interrupted by 1 or more oxygen atoms in an alkenyl group having 2 to 12 carbon atoms, and a phenyl group or a biphenyl group substituted with at least one of an alkyl group having 1 to 4 carbon atoms, R^I01Is a group represented by the formula (II), or with R^I00Same radicals, R^I02～R^I04Each independently is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen.

[ chemical formula 31]

In the formula, R^I05～R^I07With R of the above formula (I)^I02～R^I04The same is true.

Further, as the photo radical polymerization initiator, compounds described in paragraphs 0048 to 0055 of international publication No. 2015/125469 can be used.

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

< thermal radical polymerization initiator >

The resin composition of the present invention may contain a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates radicals by the energy of heat and initiates or accelerates the polymerization reaction of a compound having a radical polymerizable group. By adding the thermal radical polymerization initiator, cyclization of the polyimide precursor can be performed, and since the polymerization reaction of the polymer precursor is also performed when the polyimide precursor has a radical polymerizable group, a higher heat resistance can be achieved. Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of Japanese patent application laid-open No. 2008-063554.

When the thermal radical polymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 5 to 15% by mass, based on the total solid content of the resin composition of the present invention. The thermal radical polymerization initiator may contain only one kind, or may contain two or more kinds. When two or more thermal radical polymerization initiators are contained, the total amount thereof 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 2 or more, and preferably 3 or more. The upper limit is preferably 15 or less, more preferably 10 or less, and further preferably 8 or less.

The molecular weight of the polymerizable monomer is preferably 2000 or less, more preferably 1500 or less, and further 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.

Further, examples of the polymerizable monomer include compounds having a boiling point of 100 ℃ or higher under normal pressure. Examples thereof include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol 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, compounds obtained by (meth) acrylation of a polyfunctional alcohol with ethylene oxide or propylene oxide added thereto, JP-B-48-041708, JP-B-50-006034, urethanes of (meth) acrylic acid disclosed in JP-B-51-037193, urethanes of (meth) acrylic acid, and the like, The polyester acrylates described in JP-A-48-064183, JP-A-49-043191 and JP-A-52-030490, and the polyfunctional acrylates or methacrylates such as epoxy acrylates as a reaction product of an epoxy resin and (meth) acrylic acid, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of Japanese patent laid-open No. 2008-292970 are also suitable. Further, there can be mentioned a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth) acrylate. In addition, examples of the polymerizable monomer other than the above-mentioned monomers include compounds having 2 or more ethylenically unsaturated bond-containing groups and having a fluorene ring as described in japanese patent application laid-open nos. 2010-160418, 2010-129825, and 4364216, and cardo (cardo) resins. Further, as another example, specific unsaturated compounds described in Japanese patent publication No. 46-043946, Japanese patent publication No. 01-040337, and Japanese patent publication No. 01-040336, vinylphosphonic acid-based compounds described in Japanese patent publication No. 02-025493, and the like can be cited. Furthermore, a compound containing a perfluoroalkyl group as described in Japanese patent application laid-open No. 61-022048 can also be used. Further, those described as photocurable monomers and oligomers in the Journal of the addition Society of Japan, vol.20, No.7, pages 300 to 308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese patent application laid-open No. 2015-034964 and the compounds described in paragraphs 0087 to 0131 of International publication No. 2015/199219 can be preferably used, and these contents are incorporated in the present specification.

Further, compounds described as the formula (1) and the formula (2) in jp-a-10-062986 and specific examples thereof, which are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylating, can also be used as the polymerizable monomer.

Further, the compounds described in paragraphs 0104 to 0131 of Japanese patent application laid-open No. 2015-187211 can also be used as the polymerizable monomer, and these contents are incorporated in the present specification.

Examples of the polymerizable monomer include dipentaerythritol triacrylate (commercially available product is KAYARAD-330; Nippon Kayaku Co., manufactured by Ltd.), dipentaerythritol tetraacrylate (commercially available product is KAYARAD-320; Nippon Kayaku Co., manufactured by Ltd., A-TMMT: Shin-Nakamura Chemical Co., manufactured by Ltd.), dipentaerythritol penta (meth) acrylate (commercially available product is KAYARAD-310; Nippon Kayaku Co., manufactured by Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available product is KAYARAD DPHA; Nippon Kayaku Co., manufactured by Ltd., A-DPH; Shin-Nakamura Chemical Co., manufactured by Ltd.), and compounds having a structure in which these (meth) acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues.

Commercially available products of polymerizable monomers include, for example, SR-494 which is a 4-functional acrylate having 4 vinylene chains manufactured by Sartomer Company, Inc., SR-209, 231, 239 which is a 2-functional acrylate having 4 vinyloxy chains manufactured by Sartomer Company, SR-209, manufactured by Inc., Nippon Kayaku Co., manufactured by Ltd., DPCA-60 which is a 6-functional acrylate having 6 pentylene oxy chains manufactured by Ltd., TPA-330 which is a 3-functional acrylate having 3 isobutoxy chains, urethane oligomer UAS-10, urethane oligomer UAB-140 (PPONN PAPER INDUSTRIES CO., manufactured by LTD.), ESNK TER M-40G, NK ESTER 4G, NK ESTER M-9300, NK ESTER A-9300, UA-7200(Shin-Nakamura, manufactured by Lyaku Co., manufactured by Ltd.), Nippon Co., 40 HA 40, Nippon Kayaku Co., manufactured by Ltd., Niyaku Co., Ltd., Japan, and so-60, ltd, manufactured), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600(Kyoeisha chemical co., ltd), BLEMMER PME400(NOF corporation, manufactured), and the like.

As the polymerizable monomer, urethane acrylates such as those disclosed in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293 and JP-B-02-016765, and urethane compounds having an ethylene oxide skeleton such as those disclosed in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417 and JP-B-62-039418 are also preferable. Further, as the radical polymerizable compound, compounds having an amino structure or a sulfide structure in the molecule as described in Japanese patent application laid-open Nos. 63-277653, 63-260909 and 01-105238 can be used.

The polymerizable monomer may be a compound having an acid group such as a carboxyl group or a phosphoric acid group. The polymerizable monomer having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a polymerizable monomer having an acid group obtained by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. In particular, among the polymerizable monomers having an acid group obtained by reacting an unreacted hydroxyl group of an aliphatic polyhydric compound with a non-aromatic carboxylic acid anhydride, the aliphatic polyhydric compound is preferably a compound of pentaerythritol and/or dipentaerythritol. Examples of commercially available products include M-510 and M-520 as a polybasic acid-modified acrylic oligomer manufactured by TOAGOSEI CO., Ltd.

The acid value of the polymerizable monomer having an acid group is preferably 0.1 to 40mgKOH/g, and particularly preferably 5 to 30 mgKOH/g. When the acid value of the polymerizable monomer is within the above range, the production and handling properties are excellent, and the developability is excellent. 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 further preferably 15% by mass or less, based on the total solid content of the resin composition of the present invention. The lower limit may be more than 0% by mass, 1% by mass or more, or 3% by mass or more.

The resin composition of the present invention preferably contains substantially no polymerizable monomer. According to this embodiment, the elongation at break and chemical resistance of the obtained cured film can be further improved. In the present specification, the term "substantially free of polymerizable monomer" means that the content of polymerizable monomer is 0.01% by mass or less, preferably 0.005% by mass or less, and more preferably free of polymerizable monomer, based on the total solid content of the resin composition. The detailed reason for obtaining these effects is not clear, but it is presumed that the polymerization reaction of the polymerizable monomer proceeds more easily than the cyclization reaction of the polyimide precursor. Therefore, it is presumed that when the polymerizable monomer is present at the time of cyclization reaction of the polyimide precursor, the polymerization reaction of the polymerizable monomer proceeds first, and cyclization of the polyimide precursor becomes difficult. It is presumed that the resin composition does not substantially contain a polymerizable monomer, so that cyclization of the polyimide precursor is facilitated, and as a result, elongation at break and chemical resistance of the obtained cured film can be further improved.

< solvent >

The resin composition of the present invention preferably contains a solvent. The solvent may be any known solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.

As the esters, preferred esters include, 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 alkoxyacetates (for example, methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (for example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, etc.), Ethyl 3-ethoxypropionate, etc.)), alkyl esters of 2-alkoxypropionic acid (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl 2-oxobutyrate, etc, Ethyl 2-oxobutyrate, and the like.

Examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.

Preferred ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone.

As the aromatic hydrocarbons, for example, preferable aromatic hydrocarbons include toluene, xylene, anisole, limonene and the like.

The sulfoxide is preferably a sulfoxide, and dimethyl sulfoxide is exemplified.

Preferable examples of the amide include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-dimethylacetamide, and N, N-dimethylformamide.

The solvent is preferably a mixture of two or more types from the viewpoint of improvement of the coating surface shape and the like.

In the present invention, it is preferable that the solvent is one or a mixture of two or more selected from the group consisting of methyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ -butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate. Particularly preferably, dimethyl sulfoxide and γ -butyrolactone are used simultaneously.

The content of the solvent is preferably 5 to 80% by mass, more preferably 5 to 75% by mass, even more preferably 10 to 70% by mass, and even more preferably 40 to 70% by mass, of the total solid content concentration of the resin composition of the present invention, from the viewpoint of coatability. The content of the solvent may be adjusted depending on the desired thickness and 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 amount thereof is preferably in the above range.

< migration inhibitor >

The resin composition of the present invention preferably further comprises a migration inhibitor.

By including the migration inhibitor, it is possible to effectively inhibit the transfer of metal ions originating from the metal layer (metal wiring) into the resin composition layer.

The migration inhibitor is not particularly limited, and examples thereof include compounds having a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, and triazine ring), compounds having a thiourea group and a mercapto group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole-based compounds such as 1,2, 4-triazole and benzotriazole, and tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

Further, an ion scavenger that scavenges anions such as halogen ions can also be used.

As other migration inhibitors, there can be used rust inhibitors described in paragraph 0094 of Japanese patent application laid-open No. 2013-015701, compounds described in paragraphs 0073-0076 of Japanese patent application laid-open No. 2009-283711, compounds described in paragraph 0052 of Japanese patent application laid-open No. 2011-059656, compounds described in paragraphs 0114, 0116 and 0118 of Japanese patent application laid-open No. 2012-194520, compounds described in paragraph 0166 of International publication No. 2015/199219, and the like.

Specific examples of the migration inhibitor include the following compounds.

[ chemical formula 32]

When the resin composition contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and still more preferably 0.1 to 1.0% by mass, based on the total solid content of the resin composition. The migration inhibitor may be one kind alone, or two or more kinds thereof. When the number of migration inhibitors is two or more, the total amount thereof is preferably within the above range.

< polymerization inhibitor >

The resin composition of the present invention preferably contains a polymerization inhibitor. As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, p-t-butylcatechol, 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4 '-thiobis (3-methyl-6-t-butylphenol), 2' -methylenebis (4-methyl-6-t-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum base, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1, 2-cyclohexanediaminetetraacetic acid, glycoletherdiamine tetraacetic acid, 2, 6-di-t-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, di-t-butylphenol, p-t-butyl-p-cresol, pyrogallol, p-t-butylcatechol, p-butylcatechol, 1, 4-benzo, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamine) phenol, N-nitroso-N- (1-naphthyl) hydroxylamine ammonium salt, bis (4-hydroxy-3, 5-tert-butyl) phenylmethane and the like. Further, the polymerization inhibitor described in paragraph 0060 of Japanese patent laid-open publication No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International publication No. 2015/125469 can also be used. Further, the following compound (Me is methyl) can also be used.

[ chemical formula 33]

When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, and still more preferably 0.05 to 2.5% by mass, based on the total solid content of the resin composition of the present invention. The polymerization inhibitor may be one kind alone, or two or more kinds thereof. When the polymerization inhibitor is two or more, the total amount thereof is preferably in the above range.

< modifier for improving adhesion of metal >

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

Examples of the silane coupling agent include a compound described in paragraph 0167 of International publication No. 2015/199219, a compound described in paragraphs 0062 to 0073 of Japanese patent application laid-open No. 2014-191002, a compound described in paragraphs 0063 to 0071 of International publication No. 2011/080992, a compound described in paragraphs 0060 to 0061 of Japanese patent application laid-open No. 2014-191252, a compound described in paragraphs 0045 to 0052 of Japanese patent application laid-open No. 2014-041264, and a compound described in paragraph 0055 of International publication No. 2014/097594. Further, it is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of Japanese patent application laid-open No. 2011-128358. Further, the following compounds are also preferably used as the silane coupling agent. In the following formula, Et represents an ethyl group.

[ chemical formula 34]

Further, as the metal adhesion improver, compounds described in paragraphs 0046 to 0049 of Japanese patent application laid-open No. 2014-186186 and sulfides described in paragraphs 0032 to 0043 of Japanese patent application laid-open No. 2013-072935 can be used.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and still more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the polymer precursor. When the lower limit value is set to the above-mentioned lower limit value or more, the adhesion between the cured film and the metal layer after the curing step is good, and when the upper limit value is set to the below-mentioned upper limit value, the heat resistance and the mechanical properties of the cured film after the curing step are good. The metal adhesion improver may be one kind alone, or two or more kinds thereof. When two or more kinds are used, the total of them is preferably in the above range.

< other additives >

The resin composition of the present invention can contain, as necessary, various additives, for example, a thermal acid generator, a sensitizing dye, a chain transfer agent, a surfactant, a higher fatty acid derivative, inorganic particles, a curing agent, a curing catalyst, a filler, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, and the like, as long as the effects of the present invention are not impaired. When these additives are blended, the total blending amount thereof is preferably 3% by mass or less of the solid content of the composition.

Thermal acid production agent

The resin composition of the present invention may contain a thermal acid generator. When the specific thermal base generator has a protecting group, the thermal acid generator is used for the removal of the protecting group.

The content of the thermal acid generator is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more, per 100 parts by mass of the polymer precursor. The thermal acid generator is contained in an amount of 0.01 part by mass or more, whereby the crosslinking reaction and the cyclization of the polymer precursor are promoted, and thus the mechanical properties and the medicine resistance of the cured film can be further improved. In addition, the content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less, from the viewpoint of electrical insulation of the cured film.

The thermal acid generator may be used alone or in combination of two or more. When two or more kinds are used, the total amount is preferably in the above range.

Sensitizing pigment

The resin composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs a specific active radiation to become an electron excited state. The sensitizing dye in an electron excited state is brought into contact with a thermosetting accelerator, a thermal radical polymerization initiator, a photo radical polymerization initiator, or the like, and functions such as electron transfer, energy transfer, heat generation, and the like are generated. Thereby, the thermal curing accelerator, the thermal radical polymerization initiator, and the photo radical polymerization initiator are chemically changed and decomposed to generate radicals, acids, or bases. The details of the sensitizing dye can be found in paragraphs 0161 to 0163 of Japanese patent application laid-open No. 2016-027357, which is incorporated herein by reference.

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, more preferably 0.1 to 15% by mass, and still more preferably 0.5 to 10% by mass, based on the total solid content of the resin composition of the present invention. The sensitizing pigment 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. Chain transfer agents are defined, for example, in page 683-684 of The third edition of The Polymer dictionary (The Society of Polymer Science, Japan, 2005). As the chain transfer agent, for example, a compound group having SH, PH, SiH, and GeH in a molecule is used. These radicals can be generated by supplying hydrogen to a low-activity radical to generate a radical, or by deprotonation after oxidation. In particular, a thiol compound can be preferably used.

Further, as the chain transfer agent, compounds described in paragraphs 0152 to 0153 of International publication No. 2015/199219 can be used.

When the resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, and still more preferably 1 to 5 parts by mass, based on 100 parts by mass of the total solid content of the resin composition of the present invention. The chain transfer agent may be one kind only, or two or more kinds. When the chain transfer agent is two or more, the total range is preferably the above range.

Surface active agent

Various surfactants may be added to the resin composition of the present invention in order to further improve coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. Also, the following surfactants are also preferable.

[ chemical formula 35]

Further, as the surfactant, the compounds described in paragraphs 0159 to 0165 of International publication No. 2015/199219 can 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, more preferably 0.005 to 1.0% by mass, relative to the total solid content of the resin composition of the present invention. The surfactant may be one kind only, or two or more kinds. When the number of the surfactants is two or more, the total range is preferably the above range.

Higher fatty acid derivatives

In order to prevent inhibition of polymerization by oxygen, a higher fatty acid derivative such as behenic acid or behenamide may be added to the resin composition of the present invention so as to be locally present on the surface of the composition during drying after application.

Further, as the higher fatty acid derivative, a compound described in paragraph 0155 of international publication No. 2015/199219 can be used.

When the resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass based on the total solid content of the resin composition of the present invention. The higher fatty acid derivative may be one kind alone, or two or more kinds thereof. When the number of the higher fatty acid derivatives is two or more, the total range is preferably the above range.

< restrictions on other contained substances >

From the viewpoint of coating surface shape, the moisture content of the resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and still more preferably less than 0.6% by mass.

From the viewpoint of insulation properties, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and still more preferably less than 0.5 mass ppm. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, and nickel. When a plurality of metals are contained, it is preferable that the sum of these metals is in the above range.

Further, as a method for reducing metal impurities unexpectedly contained in the resin composition of the present invention, there can be mentioned a method in which a raw material having a small metal content is selected as a raw material constituting the resin composition of the present invention, the raw material constituting the resin composition of the present invention is subjected to filter filtration, and the inside of the apparatus is lined with polytetrafluoroethylene or the like to distill under conditions in which contamination is suppressed as much as possible.

In view of the use as a semiconductor material and the corrosion of wiring, the content of the halogen atom in the resin composition of the present invention is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and still more preferably less than 200 mass ppm. Among these, the substance present in the state of the halogen ion is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and further preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. The total of chlorine atoms and bromine atoms or chlorine ions and bromine ions is preferably in the above-mentioned range.

As the container for the resin composition of the present invention, a conventionally known container can be used. Further, for the purpose of suppressing the contamination of impurities into the raw material or the composition, it is also preferable to use a multilayer bottle in which the inner wall of the container is composed of 6 kinds of 6-layer resins, or a bottle in which 6 kinds of resins are formed into a 7-layer structure. Examples of such a container include those disclosed in Japanese patent laid-open publication No. 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.

For the purpose of removing foreign matter such as dust and fine particles in the composition, filtration using a filter is preferably performed. The pore diameter of the filter is preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be previously washed with an organic solvent. In the filtration step of the filter, a plurality of filters may be used in parallel or in series. When a plurality of filters are used, filters having different pore sizes or different materials may be used in combination. Also, various materials may be filtered multiple times. When the filtration is performed a plurality of times, the filtration may be a circulating filtration. Further, the filtration may be performed after the pressurization. When the filtration is performed after the pressurization, the pressurization is preferably performed at a pressure of 0.05MPa or more and 0.3MPa or less.

In addition to filtration using a filter, an impurity removal treatment using an adsorbent may be performed. It is also possible to combine filter filtration and impurity removal treatment using an adsorbent material. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

[ cured film, laminate, semiconductor device, and methods for producing these ]

Next, the cured film, the laminate, the semiconductor device, and the methods for manufacturing these 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 set to, for example, 0.5 μm or more and 1 μm or more. The upper limit value may be 100 μm or less, and may be 30 μm or less.

The cured film of the present invention may be laminated with 2 or more layers, and further laminated with 3 to 7 layers to form a laminate. The laminate having 2 or more layers of the cured films of the present invention preferably has a metal layer between the cured films. These metal layers can be preferably used as metal wirings such as a rewiring layer.

Examples of the field 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 pressure buffer film, and the like. In addition, a sealing film, a substrate material (a base film, a cap layer, or an interlayer insulating film of a flexible printed circuit board), an insulating film for practical mounting use such as described above, or the like may be patterned by etching. For these uses, for example, reference can be made to Science & Technology co, ltd, "high functionalization and application Technology of polyimide" 4 months 2008, kaki benayu mingming/prison, CMC technical library "foundation and development of polyimide material" 11 months 2011 issue, japan polyimide aromatic system polymer research institute/compilation "latest polyimide foundation and application" NTS, 8 months 2010, and the like.

The cured film of the present invention can also be used for the production of printing plates such as offset printing plates and screen printing plates, the use of molded parts, and the production of protective paints and dielectric layers for electronics, particularly microelectronics.

The method for producing a cured film of the present invention includes the case of using the resin composition of the present invention. Specifically, the steps including the following (a) to (d) are preferable.

(a) Film forming step for forming a film by applying a resin composition to a substrate

(b) After the film forming step, an exposure step of an exposure film

(c) A developing step of developing the exposed resin composition layer

(d) A heating step of heating the developed resin composition at 80 to 450 DEG C

As in this embodiment, the exposed resin layer can be further cured by heating after development. In this heating step, the thermal alkali-generating agent and the thermosetting compound act to obtain sufficient curability.

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

< film formation step (layer formation step) >

The production method according to a preferred embodiment of the present invention includes a film formation step (layer formation step) of applying the resin composition to a substrate to form a film (layer).

The type of the substrate may be appropriately set according to the application, but is not particularly limited, and examples thereof include a semiconductor substrate such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon, a semiconductor substrate such as quartz, glass, an optical film, a ceramic material, a vapor deposited film, a magnetic film, a reflective film, a metal substrate such as Ni, Cu, Cr, and Fe, paper, an sog (spin On glass), a TFT (thin film transistor) array substrate, and an electrode plate of a Plasma Display Panel (PDP). In the present invention, a semiconductor 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.

The method of applying the resin composition to a substrate is preferably coating.

Specifically, examples of suitable methods include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, a slit coating method, and an ink jet method. From the viewpoint of the thickness uniformity of the resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an ink jet method are more preferable. By adjusting the solid content concentration and the coating conditions appropriately according to the method, a resin layer having a desired thickness can be obtained. The coating method can be appropriately selected according to the shape of the substrate, and a spin coating method, a spray coating method, an ink jet method, and the like are preferable as long as the substrate is a circular substrate such as a chip, and a slit coating method, a spray coating method, an ink jet method, and the like are preferable as long as the substrate is a rectangular substrate. In the case of spin coating, the coating can be applied at a rotation speed of, for example, 500 to 2000rpm for about 10 seconds to 1 minute.

< drying Process >

The production method of the present invention may further include a step of drying the resin composition layer to remove the solvent after the film formation step (layer formation step). The preferable drying temperature is 50 to 150 ℃, more preferably 70 to 130 ℃, and further preferably 90 to 110 ℃. The drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.

< Exposure Process >

The production method of the present invention may include an exposure step of exposing the resin composition layer. The exposure amount is not particularly limited as long as the resin composition can be cured, and for example, it is preferably 100 to 10000mJ/cm in terms of exposure energy at a wavelength of 365nm²More preferably, the irradiation is 200 to 8000mJ/cm²。

The exposure wavelength can be set appropriately within the range of 190 to 1000nm, and is preferably 240 to 550 nm.

The exposure wavelength is described in relation to a light source, and examples thereof include (1) semiconductor laser light (wavelength 830nm, 532nm, 488nm, 405nm, etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), width (3 wavelengths of g, h, i-ray), (4) excimer laser light, KrF excimer laser light (wavelength 248nm), ArF excimer laser light (wavelength 193nm), F2 excimer laser light (wavelength 157nm), and (5) extreme ultraviolet light; EUV (wavelength 13.6nm), (6) electron beam, and the like. The resin composition of the present invention is particularly preferably exposed to a high-pressure mercury lamp, and particularly preferably exposed to i-rays. This makes it possible to obtain particularly high exposure sensitivity.

< development processing step >

The production method of the present invention may include a development treatment step of performing a development treatment on the exposed resin composition layer. By performing development, an unexposed portion (unexposed portion) is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and for example, a developing method such as spin immersion, spraying, dipping, or ultrasonic waves can be used.

The development is performed using a developer. The developing solution can be used without particular limitation as long as the unexposed portion (unexposed portion) can be removed. Preferably, the developer solution contains an organic solvent, and more preferably, the developer solution contains 90% or more of an organic solvent. In the present invention, the developer preferably contains an organic solvent having a ClogP value of-1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be determined as a calculated value by inputting the structural formula by chembidraw (chemibiological diagram).

As the organic solvent, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ -butyrolactone, ε -caprolactone, δ -valerolactone, alkyl alkoxyacetates (for example, methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (for example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxypropionate, etc.), Ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionate (example: methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate and the like (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate and the like, and ethers such as diethylene glycol dimethyl ether, 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 acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as aromatic hydrocarbons, for example, toluene, xylene, anise ether, limonene, etc., and as sulfoxides, dimethyl sulfoxide, etc., may be suitably cited.

In the present invention, cyclopentanone and γ -butyrolactone are particularly preferable, and cyclopentanone is more preferable.

Preferably, the developer is an organic solvent in an amount of 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more. The developer may be an organic solvent in an amount of 100 mass%.

The developing time is preferably 10 seconds to 5 minutes. The temperature of the developing solution during development is not particularly limited, and the development can be usually carried out at 20 to 40 ℃.

After the treatment with the developer, rinsing may be further performed. The rinsing is preferably performed with a different solvent than the developer. For example, the resin composition can be washed with a solvent contained in the resin composition. The rinsing time is preferably 5 seconds to 1 minute.

< heating Process >

The production method of the present invention preferably includes a step of heating after the film formation step (layer formation step), the drying step, or the development 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 ℃ or higher, more preferably 80 ℃ or higher, further preferably 140 ℃ or higher, further preferably 150 ℃ or higher, further preferably 160 ℃ or higher, and further preferably 170 ℃ or higher. The upper limit is preferably 500 ℃ or lower, more preferably 450 ℃ or lower, further preferably 350 ℃ or lower, further preferably 250 ℃ or lower, and further preferably 220 ℃ or lower.

The heating is preferably performed at a temperature rise rate of 1 to 12 ℃/min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ℃/min, and still more preferably 3 to 10 ℃/min. The temperature increase rate is set to 1 ℃/min or more, whereby excessive volatilization of the amine can be prevented while ensuring productivity, and the temperature increase rate is set to 12 ℃/min or less, whereby residual stress of the cured film can be relaxed.

The temperature at the start of heating is preferably 20 to 150 ℃, more preferably 20 to 130 ℃, and still more preferably 25 to 120 ℃. The temperature at the start of heating indicates the temperature at the start of the heating step to the maximum heating temperature. For example, when the resin composition is applied to a substrate and then dried, the temperature of the dried film (layer) is preferably gradually increased from a temperature 30 to 200 ℃ lower than the boiling point of the solvent contained in the resin composition.

The heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and further preferably 30 to 240 minutes.

In particular, in the case of forming a multilayer laminate, from the viewpoint of adhesion between layers of the cured film, the heating is preferably performed at a heating temperature of 180 to 320 ℃, and more preferably at 180 to 260 ℃. The reason is not clear, but is considered to be because the ethynyl groups of the polymer precursors between the layers are crosslinked with each other by setting the temperature to this temperature.

The heating may be performed in stages. For example, the pretreatment step may be carried out by raising the temperature from 25 ℃ to 180 ℃ at 3 ℃/min and holding the temperature at 180 ℃ for 60 minutes, raising the temperature from 180 ℃ to 200 ℃ at 2 ℃/min and holding the temperature at 200 ℃ for 120 minutes. The heating temperature in the pretreatment step is preferably 100 to 200 ℃, more preferably 110 to 190 ℃, and still more preferably 120 to 185 ℃. In this pretreatment step, it is also preferable to perform treatment while irradiating ultraviolet rays as described in U.S. Pat. No. 9159547. These pretreatment steps can improve the film properties. The pretreatment step may be performed in a short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be carried out in two or more stages, for example, the pretreatment step 1 may be carried out at a temperature of 100 to 150 ℃ and the pretreatment step 2 may be carried out at a temperature of 150 to 200 ℃.

The heating and cooling may be performed after the heating, and the cooling rate in this case is preferably 1 to 5 ℃/min.

In the heating step, it is preferable to perform the heating step under an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, in order to prevent decomposition of the polymer precursor. The oxygen concentration is preferably 50ppm (by volume) or less, more preferably 20ppm (by volume) or less.

< Process for Forming Metal layer >

The production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the resin composition layer after the development treatment.

The metal layer is not particularly limited, and conventional metal species can be used, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten, more preferably copper and aluminum, and still more preferably copper.

The method for forming the metal layer is not particularly limited, and conventional methods can be applied. For example, the methods described in Japanese patent laid-open Nos. 2007-157879, 2001-521288, 2004-214501 and 2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, a method of combining these, and the like can be considered. More specifically, there are a patterning method in which sputtering, photolithography, and etching are combined, and a patterning method in which photolithography and electrolytic plating are combined.

The thickness of the metal layer is preferably 0.1 to 50 μm, more preferably 1 to 10 μm, in the thickest wall portion.

< laminating Process >

The production method of the present invention preferably further comprises a lamination step.

The laminating step is a series of steps including (a) a film forming step (layer forming step), (b) an exposure step, (c) a development treatment step, and (d) a heating step, which are sequentially performed again on the surface of the cured film (resin layer) or the metal layer. However, the film forming step (a) may be repeated. The heating step (d) may be performed at the end or in the middle of the lamination.

That is, the following method may be adopted: repeating the steps (a) to (c) a predetermined number of times, and then heating the laminate (d), thereby collectively curing the laminated resin composition layers. In addition, the developing step (c) may be followed by the metal layer forming step (e), and in this case, the heating of (d) may be performed every time or may be performed collectively after the lamination is performed a predetermined number of times. It is needless to say that the lamination step may appropriately include the drying step, the heating step, and the like.

When the lamination step is further performed after the lamination step, the surface activation treatment step may be further performed after the heating step, after the exposure step, or after the metal layer formation step. As the surface activation treatment, plasma treatment is exemplified.

The laminating step is preferably performed 2 to 5 times, and more preferably 3 to 5 times.

For example, a structure in which the resin layer is 3 layers or more and 7 layers or less, such as resin layer/metal layer/resin layer/metal layer, is preferable, and 3 layers or more and 5 layers or less is more preferable.

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 formed so as to cover the metal layer. Specifically, there may be mentioned a method of sequentially repeating the film formation step (a), the exposure step (b), the development step (c), the metal layer formation step (e), and the heating step (d), or a method of sequentially repeating the film formation step (a), the exposure step (b), the development step (c), and the metal layer formation step (e), and collectively providing the heating step (d) at the end or in the middle. The resin composition layer (resin layer) and the metal layer can be alternately laminated by alternately performing the laminating step of laminating the resin composition layer (resin) and the metal layer forming step.

A semiconductor device having the cured film or laminate of the present invention is also disclosed in the present invention. As a specific example of a semiconductor device in which the resin composition of the present invention is used for forming an interlayer insulating film for a rewiring layer, reference can be made to the descriptions in paragraphs 0213 to 0218 of Japanese patent laid-open No. 2016-.

Examples

The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, contents of treatment, and treatment procedures shown in the following examples can be appropriately changed without departing from the scope of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are on a mass basis.

< Synthesis example 1 >

[ polyimide precursor derived from pyromellitic dianhydride, 4' -diaminodiphenyl ether, and benzyl alcohol (A-1: Synthesis of polyimide precursor having no radical polymerizable group ].

14.06g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ℃ C. for 12 hours) and 14.22g (131.58 mmol) of benzyl alcohol were suspended in 50mL of N-methylpyrrolidone, and dried using a molecular sieve. The suspension was heated at 100 ℃ for 3 hours. The reaction mixture was cooled to room temperature and 21.43g (270.9 mmol) of pyridine and 90mL of N-methylpyrrolidone were added. Followed byThe reaction mixture was cooled to-10 ℃ and 16.12g (135.5 mmol) of SOCl were added over 10 minutes while maintaining the temperature at-10. + -. 4 ℃₂. Addition of SOCl₂During this time, the viscosity increases. After dilution with 50mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, a solution prepared by dissolving 11.08g (58.7 mmol) of 4, 4' -diaminodiphenyl ether in 100mL of N-methylpyrrolidone was added dropwise to the reaction mixture at-5 to 0 ℃ over 20 minutes. Subsequently, after the reaction mixture was reacted at 0 ℃ for 1 hour, 70g of ethanol was added and stirred at room temperature overnight. Next, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimide precursor mixture was stirred at 5000rpm for 15 minutes. The polyimide precursor was removed by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Subsequently, the obtained polyimide precursor was dried at 45 ℃ for 3 days under reduced pressure. The weight average molecular weight of the polyimide precursor was 18,000.

A-1

[ chemical formula 36]

< Synthesis example 2 >

[ Synthesis of polyimide precursor derived from pyromellitic dianhydride, 4' -diaminodiphenyl ether, and 2-hydroxyethyl methacrylate (A-2: polyimide precursor having radical polymerizable group) ].

A diester of pyromellitic acid and 2-hydroxyethyl methacrylate was produced by mixing 14.06g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ℃ C. for 12 hours), 16.8g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 20.4g of pyridine (258 mmol) and 100g of diglyme (diethylene glycol dimethyl ether) and stirring the mixture at 60 ℃ C. for 18 hours. Then, by SOCl₂After the obtained diester was chlorinated, 4' -diaminodiphenyl ether was converted into a polyimide precursor in the same manner as in Synthesis example 1, and the resulting polyimide precursor was converted into a polyimide precursor in the same manner as in Synthesis example 1The method of (3) gives a polyimide precursor. The weight average molecular weight of the polyimide precursor was 19,000.

A-2

[ chemical formula 37]

< Synthesis example 3 >

[ Synthesis of polyimide precursor derived from 4,4 '-oxydiphthalic anhydride, 4' -diaminodiphenyl ether, and 2-hydroxyethyl methacrylate (A-3: polyimide precursor having radical polymerizable group) ].

A diester of 4,4 '-oxydiphthalic anhydride and 2-hydroxyethyl methacrylate was prepared by mixing 20.0g (64.5 mmol) of 4, 4' -oxydiphthalic anhydride (dried at 140 ℃ C. for 12 hours), 16.8g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 20.4g of pyridine (258 mmol) and 100g of diglyme, and stirring at 60 ℃ for 18 hours. Then, by SOCl₂After the obtained diester was chlorinated, 4' -diaminodiphenyl ether was converted into a polyimide precursor in the same manner as in synthesis example 1, and a polyimide precursor was obtained in the same manner as in synthesis example 1. The weight average molecular weight of the polyimide precursor was 18,000.

A-3

[ chemical formula 38]

< Synthesis example 4 >

[ Synthesis of polyimide precursor derived from 4,4 ' -oxydiphthalic anhydride, 4 ' -diamino-2, 2 ' -dimethylbiphenyl (tolidine) and 2-hydroxyethyl methacrylate (A-4: polyimide precursor having radical polymerizable group) ].

20.0g (64.5 mmol) of 4, 4' -oxydiphthalic anhydride (dried at 140 ℃ for 12 hours) and 16.8g (129 mmol) were addedMole) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 20.4g of pyridine (258 mmol) and 100g of diglyme were mixed and stirred at 60 ℃ for 18 hours to produce a diester of 4, 4' -oxydiphthalic anhydride and 2-hydroxyethyl methacrylate. Then, by SOCl₂After the obtained diester was chlorinated, the obtained diester was converted into a polyimide precursor by 4,4 '-diaminobiphenyl-2, 2' -dimethylbiphenyl in the same manner as in synthesis example 1, and a polyimide precursor was obtained in the same manner as in synthesis example 1. The weight average molecular weight of the polyimide precursor was 19,000.

A-4

[ chemical formula 39]

< examples and comparative examples >

Each resin composition was obtained by mixing the components shown in the following table. The obtained resin composition was subjected to pressure filtration through a filter having a pore width of 0.8 μm.

[ Table 3]

The raw materials listed in the above table are as follows.

(A) Polyimide precursor

A-1 to A-4: polyimide precursors A-1 to A-4 synthesized as described above

(B) Polymerizable monomer (b):

b-1, B-2: a compound of the structure

[ chemical formula 40]

(C) Thermosetting compound

C-1 to C-3: a compound of the structure

[ chemical formula 41]

(D) Photopolymerization initiator

D-1, D-2: a compound of the structure

[ chemical formula 42]

(E) Thermal alkali-producing agent

E-1 to E-3: a compound of the structure

[ chemical formula 43]

(F) Polymerization inhibitor

F-1, F-2: a compound of the structure

[ chemical formula 44]

(G) Additive agent

G-1, G-2: a compound of the structure

[ chemical formula 45]

(H) Silane coupling agent

H-1, H-2: a compound of the structure

[ chemical formula 46]

(I) Solvent(s)

I-1: gamma-butyrolactone

I-2: dimethyl sulfoxide

< production of cured film >

Each resin composition was applied to 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 ℃ for 4 minutes, whereby a uniform resin composition layer having a thickness of 20 μm was formed on the silicon wafer. Using a broadband exposure machine (manufactured by USHIO INC., UX-1000SN-EH01) at 400mJ/cm²The exposure energy of (2) is to expose the resin composition layer on the silicon wafer, and the exposed resin composition layer (resin layer) is heated at a temperature rising rate of 5 ℃/minute in a nitrogen atmosphere to 180 ℃ and then heated for 2 hours. The cured resin layer was immersed in a 3% hydrofluoric acid solution, and the resin layer was peeled off from the silicon wafer to obtain a cured film.

< elongation at break >

The elongation at break of the obtained cured film was measured. The elongation at break of the cured film was measured by a tensile Tester (TENSILON) under conditions of a crosshead speed of 300 mm/min, a width of 10mm, and a sample length of 50mm in the longitudinal direction and the width direction of the film at 25 ℃ and 65% Relative Humidity (RH) according to JIS-K6251 (Japanese Industrial Standard). Elongation at break through E_b＝(L_b-L₀)/L₀(E_b: elongation at Break, L₀: length, L of test piece before test_b: the length of the test piece when the test piece has been cut). In the evaluation, the elongation at break was measured 10 times each, and the average value was used. The results were differentiated as followsAnd evaluated.

A: elongation at break of 60% or more

B: the elongation at break is more than 50 percent and less than 60 percent

C: the elongation at break is less than 50 percent

< chemical resistance >

The obtained cured film was immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated.

Medicine preparation: 90:10 (mass ratio) mixture of dimethyl sulfoxide (DMSO) and 25 mass% tetramethylammonium hydroxide (TMAH) solution

Evaluation conditions were as follows: the resin layer was immersed in the solution at 75 ℃ for 15 minutes, and the film thickness before and after the immersion was compared to calculate the dissolution rate (nm/min).

A: less than 250 nm/min

B: 250 nm/min or more and less than 500 nm/min

C: 500 nm/min or more

< evaluation of lithography >

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 ℃ for 4 minutes, whereby a resin composition layer having a uniform film thickness of 20 μm was formed on the silicon wafer. The resin composition layer on the silicon wafer was exposed using a stepper (Nikon NSR 2005i 9C). The exposure was carried out using i-rays at a wavelength of 365nm and at 200, 300, 400, 500, 600, 700, 800mJ/cm²The resin layer was obtained by exposure from 5 to 25 μm using a line-space mask with 1 μm scale. The resin layer was developed with cyclopentanone for 60 seconds. The smaller the line width of the obtained resin layer (line pattern) is, the more fine the pattern can be formed, and this is a preferable result. Further, the minimum line width that can be formed is less likely to change in response to a variation in exposure amount, and the randomness of the exposure amount in fine pattern formation is increased, which is a preferable result.

A: the line width is less than 10 μm

B: the line width is more than 10 μm and less than 20 μm

C: the line width is 20 μm or more or a pattern of a line width with edge sharpness cannot be obtained.

[ Table 4]

	Resistance to chemicals	Elongation at break	Litho-etch property
				Example 1	A	A	A
Example 2	B	B	A
				Example 3	A	A	B
Example 4	A	B	A
				Example 5	B	A	B
Example 6	A	A	A
				Example 7	B	B	A
Example 8	A	A	A
				Example 9	A	A	A
Example 10	A	A	A
				Example 11	A	A	A
Example 12	A	A	A
				Example 13	A	A	B
Example 14	A	A	B
				Example 15	A	A	A
Example 16	A	A	A
				Example 17	A	A	A
Example 18	A	A	A
				Comparative example 1	C	B	C
Comparative example 2	C	B	A
				Comparative example 3	B	C	A
Comparative example 4	C	C	A
				Comparative example 5	B	C	A

As shown in the table, in the examples, a cured film having good elongation at break and excellent chemical resistance was formed.

Claims (18)

1. A resin composition comprising:

a polyimide precursor,

A thermal alkali-producing agent, and

a thermosetting compound having a plurality of functional groups selected from the group consisting of epoxy groups, oxetane groups, methylol groups, alkoxymethyl groups, phenol groups, maleimide groups, cyanate groups and blocked isocyanate groups.

2. The resin composition according to claim 1, wherein,

the thermosetting compound is a compound represented by the following formula (TC1),

X¹-(Y¹)_n……(TC1)

in the formula (TC1), X¹Represents a linking group of n valence, Y¹Represents an epoxy group, an oxetanyl group, a hydroxymethyl group, an alkoxymethyl group, a phenolic group, a maleimido group, a cyanate group or a blocked isocyanate group, n represents 2 or moreThe above integer.

3. The resin composition according to claim 2, wherein,

x of the formula (TC1)¹Comprising a cyclic structure.

4. 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.

5. 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.

6. The resin composition according to any one of claims 1 to 5, wherein,

the alkali generation temperature of the thermal alkali generator is lower than the curing start temperature of the thermosetting compound.

7. 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 mass% or less based on the total solid content of the resin composition.

8. The resin composition according to any one of claims 1 to 7, wherein,

the polyimide precursor includes a radical polymerizable group.

9. The resin composition according to any one of claims 1 to 8, wherein,

the polyimide precursor has a structural unit represented by the following formula (1),

in the formula (1), A¹And A²Each independently represents an oxygen atom or NH, R¹¹¹Represents a 2-valent organic group, R¹¹⁵Represents a 4-valent organic group, R¹¹³And R¹¹⁴Each independently represents a hydrogen atom or a 1-valent organic group.

10. The resin composition according to claim 9, wherein,

r of the formula (1)¹¹³And R¹¹⁴At least one of them contains a radical polymerizable group.

11. The resin composition according to any one of claims 8 or 10, further comprising a photopolymerization initiator.

12. The resin composition according to any one of claims 1 to 11, which is used for forming an interlayer insulating film for a rewiring layer.

13. A cured film obtained by curing the resin composition according to any one of claims 1 to 12.

14. A laminate having 2 or more cured films of claim 13 with a metal layer between the 2 cured films.

15. A method for producing a cured film, comprising a film-forming step of applying the resin composition according to any one of claims 1 to 12 to a substrate to form a film.

16. The method for producing a cured film according to claim 15, comprising:

an exposure step of exposing the film; and

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 ℃.

18. A semiconductor device having the cured film according to claim 13 or the laminate according to claim 14.