CN116685622A

CN116685622A - Resin composition, cured product, laminate, method for producing cured product, and semiconductor device

Info

Publication number: CN116685622A
Application number: CN202180087641.3A
Authority: CN
Inventors: 野崎敦靖; 岛田和人
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2020-12-28
Filing date: 2021-12-24
Publication date: 2023-09-01
Also published as: JPWO2022145355A1; TW202234158A; KR20230110589A; WO2022145355A1

Abstract

The present invention provides a resin composition comprising a cyclized resin or a precursor thereof, a radical polymerization initiator, and a radical polymerizable compound, the radical polymerizable compound having a urea bond and containing a compound a having no symmetry axis, the compound a satisfying at least one of the following conditions 1 and 2, the condition 1: the compound A has more than 2 free radical polymerizable groups; condition 2: the compound A has at least 1 selected from the group consisting of a hydroxyl group, an oxyalkylene group, an amide group and a cyano group.

Description

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

Technical Field

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

Background

The cyclized resin such as polyimide is excellent in heat resistance, insulation properties and the like, and therefore is suitable for various applications. The use is not particularly limited, but when a semiconductor device for mounting is exemplified, the use of a material or a protective film as an insulating film or a sealing material can be exemplified. And, it can be used as a base film, a cover film, or the like of a flexible substrate.

For example, in the above-mentioned applications, a cyclized resin such as polyimide is used in the form of a resin composition containing at least one of cyclized resins such as polyimide and precursors of cyclized resins.

Such a resin composition is applied to a substrate by, for example, coating to form a photosensitive film, and then exposed to light, developed, heated, or the like as necessary, whereby a cured product can be formed on the substrate.

The precursor of the cyclized resin such as polyimide precursor is cyclized by heating, for example, and the cured product is formed into a cyclized resin such as polyimide.

Since the resin composition can be applied by a known coating method or the like, it can be said that, for example, the shape, size, application position and the like of the applied resin composition are highly flexible in design and the like when applied, and the resin composition is excellent in manufacturing suitability. In addition to the high performance of cyclized resins such as polyimide, the development of the resin composition in industrial applications is increasingly expected from the viewpoint of excellent suitability for such production.

For example, patent document 1 discloses a photosensitive polyimide precursor composition containing (a) a polymer (a) having a specific structural unit as a main component, (B) a compound (B) having a specific structure, and (c) a photoinitiator and/or a sensitizer and/or a photoreactive monomer.

Patent document 2 describes a negative photosensitive resin composition comprising (a) a polyimide precursor having a specific structural unit: 100 parts by mass of (B) a photopolymerization initiator: 1 to 20 parts by mass of (C) a compound represented by a specific structure or a polymer thereof, and at least 1 compound selected from the compounds represented by a specific structure or the polymers thereof: 0.1 to 30 parts by mass.

Technical literature of the prior art

Patent literature

Patent document 1: japanese patent laid-open No. 6-332178

Patent document 2: japanese patent laid-open publication No. 2011-059656

Disclosure of Invention

Technical problem to be solved by the invention

In a resin composition containing at least one of a cyclized resin such as polyimide and a precursor of the cyclized resin, the obtained cured product is required to have excellent chemical resistance.

The present invention provides a resin composition which can obtain a cured product having excellent drug resistance, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for producing the cured product, and a semiconductor device containing the cured product or the laminate.

Means for solving the technical problems

Examples of representative embodiments of the present invention are shown below.

<1> a resin composition comprising:

cyclizing the resin or its precursor;

a radical polymerization initiator; a kind of electronic device with high-pressure air-conditioning system

A radical-polymerizable compound having a radical-polymerizable group,

the radical polymerizable compound has a urea bond and contains a compound A having no symmetry axis,

the above compound A satisfies at least one of the following conditions 1 and 2,

condition 1: the compound A has more than 2 free radical polymerizable groups;

condition 2: the compound A has at least 1 selected from the group consisting of a hydroxyl group, an oxyalkylene group, an amide group and a cyano group.

<2> the resin composition according to <1>, wherein the cyclized resin or its precursor is at least 1 resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole precursor, polyamideimide and polyamideimide precursor.

<3> the resin composition according to <1> or <2>, wherein the acid value of the cyclized resin or its precursor is 0mmol/g to 1.2mmol/g.

<4> the resin composition according to any one of <1> to <3>, wherein the above compound A contains an aromatic group.

<5> the resin composition according to any one of <1> to <4>, further comprising a compound different from the compound A as the radical polymerizable compound.

<6> the resin composition according to any one of <1> to <5>, wherein the above compound A is a compound represented by the following formula (1-1) or formula (1-2).

[ chemical formula 1]

In the formula (1-1), R ^P1 R is R ^P2 Each independently represents a group comprising at least 1 radical polymerizable group;

in the formula (1-2), R ^P1 Represents a group containing at least 1 radical polymerizable group, and L3 represents a 2-valent linking group.

<7> the resin composition according to any one of <1> to <5>, which is used for forming an interlayer insulating film for a rewiring layer.

<8> a cured product obtained by curing the resin composition according to any one of <1> to <7 >.

<9> a laminate comprising 2 or more layers of the cured product of <8>, and a metal layer between any of the layers of the cured product.

<10> a method for producing a cured product, comprising a film forming step of applying the resin composition according to any one of <1> to <7> to a substrate to form a film.

<11> the method for producing a cured product according to <10>, comprising an exposure step of selectively exposing the film and a development step of developing the film with a developer to form a pattern.

<12> the method for producing a cured product according to <10> or <11>, comprising a heating step of heating the film at 50 to 450 ℃.

<13> a semiconductor device comprising the cured product of <8> or the laminate of <9 >.

Effects of the invention

According to the present invention, there are provided a resin composition capable of obtaining a cured product excellent in drug resistance, a cured product obtained by curing the resin composition, a laminate comprising the cured product, a method for producing the cured product, and a semiconductor device comprising the cured product or the laminate.

Detailed Description

Hereinafter, a main embodiment of the present invention will be described. However, the present invention is not limited to the illustrated embodiments.

In the present specification, a numerical range indicated by the symbol "to" indicates a range in which numerical values before and after the symbol "to" are included as a lower limit value and an upper limit value, respectively.

In the present specification, the term "process" means not only an independent process but also a process which cannot be clearly distinguished from other processes as long as the intended function of the process can be achieved.

Regarding the labeling of groups (radicals) in the present specification, the unsubstituted and substituted labels include both groups (radicals) having no substituent and groups (radicals) having a substituent. For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In this specification, unless otherwise specified, "exposure" includes not only exposure with light but also exposure with a particle beam such as an electron beam or an ion beam. Examples of the light used for exposure include an open line spectrum of a mercury lamp, an extreme ultraviolet ray typified by an excimer laser, an extreme ultraviolet ray (EUV light), an activating ray such as an X-ray or an electron beam, and radiation.

In the present specification, "(meth) acrylate" means either or both of "acrylate" and "methacrylate", "(meth) acrylic" means either or both of "acrylic" and "methacrylic", and "(meth) acryl" means either or both of "acryl" and "methacryl".

In the present specification, me in the structural formula represents methyl, et represents ethyl, bu represents butyl, and Ph represents phenyl.

In the present specification, the total solid component means the total mass of all components except the solvent in all components of the composition. In the present specification, the solid content concentration is the mass percentage of the other components than the solvent with respect to the total mass of the composition.

In the present specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured by a Gel Permeation Chromatography (GPC) method, and are defined as polystyrene conversion values. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained by using HLC-8220GPC (manufactured by TOSOH CORPORATION), and connecting a protection column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION above) in series as a column. Unless otherwise specified, these molecular weights are measured using THF (tetrahydrofuran) as the eluent. Among them, NMP (N-methyl-2-pyrrolidone) can be used even when THP is unsuitable as an eluent, such as when solubility is low. Unless otherwise specified, a 254nm wavelength detector of UV rays (ultraviolet rays) is used for detection in GPC measurement.

In the present specification, when the positional relationship of each layer constituting the laminate is described as "up" or "down", it is sufficient that another layer exists above or below the layer serving as the reference among the layers concerned. That is, the 3 rd layer or element may be further interposed between the layer to be the reference and the other layer, and the layer to be the reference may not be in contact with the other layer. If not specifically described, the direction in which the layers are gradually stacked on the substrate is referred to as "up", or in the case where the resin composition layer is present, the direction from the substrate toward the resin composition layer is referred to as "up", and the opposite direction is referred to as "down". In addition, the vertical direction is set for convenience of description of the present specification, and in actual embodiments, the "upward" direction in the present specification may be different from the vertical upward direction.

In the present specification, unless otherwise specified, each component contained in the composition may contain 2 or more compounds corresponding to the component. Unless otherwise specified, the content of each component in the composition indicates the total content of all the compounds corresponding to the component.

In the present specification, unless otherwise specified, the temperature is 23 ℃, the air pressure is 101,325Pa (1 air pressure), and the relative humidity is 50% RH.

In this specification, a combination of preferred embodiments is more preferred.

(resin composition)

The resin composition of the present invention comprises a cyclized resin or a precursor thereof, a radical polymerization initiator, and a radical polymerizable compound having a urea bond and containing a compound a having no symmetry axis, wherein the compound a satisfies at least one of the following conditions 1 and 2.

Condition 1: the compound A has 2 or more radical polymerizable groups.

The resin composition of the present invention is preferably used for forming a photosensitive film for exposure and development, and more preferably for forming a film for exposure and development using a developer containing an organic solvent.

The resin composition of the present invention can be used for, for example, forming an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like, and is preferably used for forming an interlayer insulating film for a rewiring layer.

The resin composition of the present invention can be used for forming a photosensitive film for negative-type development.

In the present invention, negative development means development in which a non-exposed portion is removed by development during exposure and development, and positive development means development in which an exposed portion is removed by development.

As the method of exposure, the developer, and the method of development, for example, the exposure method described in the exposure step described in the description of the method of producing a cured product, the developer described in the development step, and the development method described in the development step are used.

According to the resin composition of the present invention, a cured product having excellent drug resistance can be obtained.

The mechanism by which the above-described effects can be obtained is not clear, but is presumed to be as follows.

Regarding a composition containing a cyclized resin or a precursor thereof, the use of a radically polymerizable compound having a urea bond has been studied in the literature.

However, when a radical polymerizable compound having a urea bond is used in a resin composition containing a cyclized resin or a precursor thereof, the radical polymerizable compounds are likely to aggregate with each other, and thus the chemical resistance may be lowered.

In particular, a polymerizable compound having 2 or more radical polymerizable groups and having a urea bond, or a polymerizable compound having a polar group such as a hydroxyl group, an oxyalkylene group, an amide group, a cyano group, or the like is likely to aggregate, and if the compound is formed into a composition film and then polymerized, the density of the polymer in the film may be uneven, and the chemical resistance may be lowered.

Accordingly, the present inventors have conducted intensive studies and as a result, have found that compound a, which is a compound having no symmetry axis, is used as a polymerizable compound having 2 or more radical polymerizable groups and having a urea bond, or a polymerizable compound having a polar group such as a hydroxyl group, an oxyalkylene group, an amide group, a cyano group and having a urea bond, thereby improving chemical resistance.

This is presumably because, since the compound a does not have a symmetry axis, aggregation of the polymerizable compound can be suppressed, and thus, when it is polymerized, the compound a exists in a relatively nearly uniform state in the film.

And, it is presumed as follows: polymers of compounds having 2 or more radical polymerizable groups, polymers of compounds having polar groups such as hydroxyl groups, oxyalkylene groups, amide groups, cyano groups, and the like are less likely to be eluted into organic solvents and the like, and such polymers are present in a relatively nearly uniform state in the film, whereby the drug resistance of the cured film obtained is greatly improved.

In addition, since compound a does not have a symmetry axis, aggregation is suppressed as described above, solubility in a developer in an unexposed portion of the film is also improved, and developability is excellent.

And, it is presumed as follows: since the aggregation of the compound a is suppressed as described above, for example, inhibition is suppressed by cyclization of the polymer of the polymerizable compound obtained by ring-closing aggregation of the precursor of the resin, and the obtained cured film is excellent in elongation at break.

Here, patent document 1 and patent document 2 do not describe the use of compound a.

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

< specific resin >

The resin composition of the present invention contains at least 1 resin (specific resin) selected from the group consisting of a cyclized resin and a precursor thereof.

The cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in the main chain structure.

In the present invention, the main chain means a relatively longest bonding chain in a resin molecule.

Examples of the cyclized resin include polyimide, polybenzoxazole, and polyamideimide.

The precursor of the cyclized resin is a resin which becomes a cyclized resin due to a change in chemical structure caused by an external stimulus, and is preferably a resin which becomes a cyclized resin due to a change in chemical structure caused by heat, and more preferably a resin which forms a ring structure to become a cyclized resin due to a heat-induced ring-closure reaction.

Examples of the precursor of the cyclized resin include a polyimide precursor, a polybenzoxazole precursor, and a polyamideimide precursor.

That is, the resin composition of the present invention preferably contains at least 1 resin (specific resin) selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole precursor, polyamideimide and polyamideimide precursor as the specific resin.

The resin composition of the present invention preferably contains polyimide or a polyimide precursor as a specific resin.

The specific resin preferably has a polymerizable group, and more preferably contains a radical polymerizable group.

In the case where the specific resin has a radical polymerizable group, the resin composition of the present invention preferably contains a radical crosslinking agent described later. The composition may contain a sensitizer, as required. For example, a negative photosensitive film is formed from the resin composition of the present invention.

In the case where the specific resin has a polymerizable group, the resin preferably has a molecular chain including a polymerizable group and a urea bond.

The molecular chain is preferably bonded to the main chain of the resin as a side chain, for example.

In the case where the specific resin contains a repeating unit represented by the following formula (2), the molecular chain is preferably R contained in the repeating unit represented by the formula (2), for example ¹¹¹ 、R ¹¹⁵ 、R ¹¹³ R is R ¹¹⁴ At least 1 of (3).

In the case where the specific resin contains a repeating unit represented by the following formula (4), the molecular chain is preferably R contained in the repeating unit represented by the following formula (4), for example ¹³¹ R is R ¹³² At least 1 of (3).

In a specific treeIn the case where the lipid contains a repeating unit represented by the following formula (3), the molecular chain is preferably R contained in the repeating unit represented by the formula (3) ¹²¹ 、R ¹²² 、R ¹²³ R is R ¹²⁴ At least 1 of (3).

In the case where the specific resin contains a repeating unit represented by the following formula (X), the molecular chain is preferably R contained in the repeating unit represented by the formula (X) ¹³³ R is R ¹³⁴ At least 1 of (3).

In the case where the specific resin contains a repeating unit represented by the following formula (PAI-2), the above molecular chain is preferably R contained in the repeating unit represented by the formula (PAI-2), for example ¹¹¹ 、R ¹¹⁷ R is R ¹¹³ At least 1 of (3).

In the case where the specific resin contains a repeating unit represented by the following formula (PAI-3), the above molecular chain is preferably R contained in the repeating unit represented by the formula (PAI-3), for example ¹¹¹ R is R ¹¹⁷ At least 1 of (3).

The acid value of the specific resin is preferably 0mmol/g to 1.2mmol/g, more preferably 0mmol/g to 0.8mmol/g, and even more preferably 0mmol/g to 0.6mmol/g, from the viewpoint of chemical resistance.

The acid value is determined, for example, by JIS K0070: the measurement was performed by the method described in 1992.

[ polyimide precursor ]

The type of polyimide precursor used in the present invention is not particularly limited, but preferably contains a repeating unit represented by the following formula (2).

[ chemical formula 2]

In the formula (2), A ¹ A is a ² Each independently represents an oxygen atom or-NH-, R ¹¹¹ Represents an organic group of valence 2, R ¹¹⁵ Represents an organic group of valence 4, R ¹¹³ R is R ¹¹⁴ Each independently represents a hydrogen atom or a 1-valent organic group.

A in formula (2) ¹ A is a ² Each independently represents an oxygen atom or-NH-, preferably an oxygen atom.

R in formula (2) ¹¹¹ An organic group having a valence of 2. Examples of the 2-valent organic group include a group containing a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, and preferably a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group composed of a combination of these groups, and more preferably a group containing an aromatic group having 6 to 20 carbon atoms. The above-mentioned linear or branched aliphatic group may be substituted with a group containing a heteroatom by a hydrocarbon group in a chain, and the above-mentioned cyclic aliphatic group and aromatic group may be substituted with a group containing a heteroatom by a hydrocarbon group having a ring member. As a preferred embodiment of the present invention, examples thereof include groups represented by-Ar-L-Ar-, particularly preferred are groups represented by-Ar-L-Ar-. Wherein Ar is an aromatic group, L is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ₂ -or-NHCO-, or a group consisting of a combination of 2 or more of the foregoing. The preferred ranges of these are as described above.

R ¹¹¹ Preferably derived from diamines. The diamine used for the production of the polyimide precursor includes linear or branched aliphatic, cyclic aliphatic or aromatic diamines, and the like. The diamine may be used in an amount of 1 or 2 or more.

Specifically, the diamine is preferably a diamine containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group composed of a combination of these, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. The above-mentioned linear or branched aliphatic group may be substituted with a group containing a heteroatom by a hydrocarbon group in a chain, and the above-mentioned cyclic aliphatic group and aromatic group may be substituted with a group containing a heteroatom by a hydrocarbon group having a ring member. Examples of the group containing an aromatic group include the following.

[ chemical formula 3]

Wherein A represents a single bond or a 2-valent linking group, preferably a single bond or a group selected from aliphatic hydrocarbon groups having 1 to 10 carbon atoms, which may be substituted with a fluorine atom, -O-, -C (=O) -, -S-, -SO ₂ -, -NHCO-or a combination of these, more preferably a single bond or an alkylene group selected from the group consisting of C1-3 which may be substituted with a fluorine atom, -O-, -C (=O) -, -S-or-SO ₂ The radicals in (E) -are further preferably-CH ₂ -、-O-、-S-、-SO ₂ -、-C(CF ₃ ) ₂ -or-C (CH) ₃ ) ₂ -。

Wherein, represents the bonding site with other structures.

Specific examples of the diamine include a diamine selected from 1, 2-diaminoethane, 1, 2-diaminopropane, 1, 3-diaminopropane, 1, 4-diaminobutane and 1, 6-diaminohexane; 1, 2-diaminocyclopentane or 1, 3-diaminocyclopentane, 1, 2-diaminocyclohexane, 1, 3-diaminocyclohexane 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 or isophorone diamine; m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4 '-diaminobiphenyl or 3,3' -diaminobiphenyl, 4 '-diaminodiphenyl ether, 3-diaminodiphenyl ether, 4' -diaminodiphenylmethane or 3,3 '-diaminodiphenylmethane 4,4' -diaminodiphenyl sulfone or 3,3 '-diaminodiphenyl sulfone, 4' -diaminodiphenyl sulfide or 3,3 '-diaminodiphenyl sulfide, 4' -diaminobenzophenone or 3,3 '-diaminobenzophenone, 3' -dimethyl-4, 4 '-diaminobiphenyl, and 2,2' -dimethyl-4, 4 '-diaminobiphenyl, 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, 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-p-diphenyl, 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 '-diaminodiphenyl methane 3,3' -dimethyl-4, 4 '-diaminodiphenylmethane, 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' -tetraminobiphenyl, 3', 4' -tetraminodiphenyl ether, 1, 4-diaminoanthraquinone, 1, 5-diaminoanthraquinone, 3-dihydroxy-4, 4 '-diaminobiphenyl, 9' -bis (4-aminophenyl) fluorene, 4,4' -dimethyl-3, 3' -diaminodiphenyl sulfone, 3', 5' -tetramethyl-4, 4' -diaminodiphenyl methane, 2, 4-diaminocumene or 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, bis (p-aminophenyl) octamethylpentasiloxane, 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) fluoro-tetradecyl, 2- (2, 2-bis (4-aminophenyl) hexafluoropropane, 2-bis [ 2, 4-aminophenoxy ] hexafluoropropane, 5-bis (trifluoromethyl) phenyl ] hexafluoropropane, p-bis (4-amino-2-trifluoromethylphenoxy) benzene, 4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4' -bis (4-amino-3-trifluoromethylphenoxy) biphenyl, and 4,4' -bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4' -bis (3-amino-5-trifluoromethylphenoxy) diphenylsulfone, 2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl ] hexafluoropropane, 3', at least 1 diamine selected from the group consisting of 5,5' -tetramethyl-4, 4' -diaminobiphenyl, 4' -diamino-2, 2' -bis (trifluoromethyl) biphenyl, 2', 5', 6' -hexafluoro-tolidine and 4,4' -diaminotetrabiphenyl.

Further, diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International publication No. 2017/038598 are also preferable.

Further, diamines having 2 or more alkylene glycol units in the main chain as described in paragraphs 0032 to 0034 of International publication No. 2017/038598 are also preferably used.

From the viewpoint of flexibility of the obtained organic film, R ¹¹¹ Preferably represented by-Ar-L-Ar-. Wherein Ar is each independently an aromatic group, L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ₂ -or-NHCO-, or a group consisting of a combination of 2 or more of the foregoing. Ar is preferably a phenylene group which is preferably a phenylene group, L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom-O-, -CO-, -S-or-SO ₂ -. The aliphatic hydrocarbon group herein is preferably an alkylene group.

And, from the viewpoint of the i-ray transmittance, R ¹¹¹ The organic group having a valence of 2 represented by the following formula (51) or (61) is preferable. In particular, from the viewpoint of the i-ray transmittance and the availability, the organic group having a valence of 2 represented by formula (61) is preferable.

(51)

[ chemical formula 4]

In the formula (51), R ⁵⁰ ～R ⁵⁷ Each independently is a hydrogen atom, a fluorine atom or a 1-valent organic group, R ⁵⁰ ～R ⁵⁷ At least 1 of which is a fluorine atom, a methyl group or a trifluoromethyl group, each independently represents a bonding site to a nitrogen atom in formula (2).

As R ⁵⁰ ～R ⁵⁷ Examples of the 1-valent organic group 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 5]

In the formula (61), R ⁵⁸ R is R ⁵⁹ Each independently represents a fluorine atom, a methyl group or a trifluoromethyl group, and each independently represents a bonding site to a nitrogen atom in formula (2).

Examples of the diamine having the structure represented by formula (51) or (61) include 2,2 '-dimethylbenzidine, 2' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl, 2' -bis (fluoro) -4,4 '-diaminobiphenyl, and 4,4' -diaminooctafluorobiphenyl. These may be used in 1 kind or in combination of 2 or more kinds.

R in formula (2) ¹¹⁵ Represents a 4-valent organic group. The organic group having a valence of 4 is preferably an organic group having a valence of 4 including an aromatic ring, and more preferably a group represented by the following formula (5) or formula (6).

In the formula (5) or (6), each independently represents a bonding site to another structure.

[ chemical formula 6]

In the formula (5), R ¹¹² A single bond or a 2-valent linking group, preferably a single bond or selected from fluorine-containing groups An aliphatic hydrocarbon group having 1 to 10 carbon atoms which is substituted with an atom, -O-, -CO-, -S-, -SO ₂ -and-NHCO-, and combinations thereof, more preferably a single bond, selected from the group consisting of alkylene groups having 1 to 3 carbon atoms which may be substituted with fluorine atoms, -O-, -CO-, -S-, and-SO ₂ The radicals in are further preferably selected from the group consisting of-CH ₂ -、-C(CF ₃ ) ₂ -、-C(CH ₃ ) ₂ -, -O-, -CO-; -S-and-SO ₂ -a group of valence 2 in (a).

With respect to R ¹¹⁵ Specifically, there may be mentioned a tetracarboxylic acid residue remaining after the acid anhydride group is removed from the tetracarboxylic dianhydride. As a combination with R ¹¹⁵ The polyimide precursor may have a corresponding structure, and may contain only 1 tetracarboxylic dianhydride residue, or may contain 2 or more types.

The tetracarboxylic dianhydride is preferably represented by the following formula (O).

[ chemical formula 7]

In the formula (O), R ¹¹⁵ Represents a 4-valent organic group. R is R ¹¹⁵ Is preferably within the range of R in formula (2) ¹¹⁵ The meaning of (2) is the same and the preferred ranges are also the same.

Specific examples of the tetracarboxylic dianhydride include pyromellitic dianhydride (PMDA), 3',4' -biphenyl tetracarboxylic dianhydride, 3',4,4' -diphenyl sulfide tetracarboxylic dianhydride, 3',4' -diphenyl sulfone tetracarboxylic dianhydride, 3',4,4' -diphenyl sulfide tetracarboxylic dianhydride, 3',4,4' -diphenyl sulfone tetracarboxylic dianhydride, 3',4' -benzophenone tetracarboxylic dianhydride, 4' -oxydiphthalic dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride, 1,4,5, 7-naphthalene tetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride 2, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 1, 3-diphenylhexafluoropropane-3, 4-tetracarboxylic dianhydride, 1,4,5, 6-naphthalene tetracarboxylic dianhydride, 2',3,3' -diphenyltetracarboxylic dianhydride, 3,4,9, 10-perylene tetracarboxylic dianhydride, 1,2,4, 5-naphthalene tetracarboxylic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 1,8,9, 10-phenanthrene tetracarboxylic dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 1, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 1,2,3, 4-benzene tetracarboxylic dianhydride, and alkyl groups having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

Further, preferred examples thereof include tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International publication No. 2017/038598.

In the formula (2), R ¹¹¹ And R is ¹¹⁵ At least one of them can also have an OH group. More specifically, as R ¹¹¹ The residue of a bisaminophenol derivative may be mentioned.

R in formula (2) ¹¹³ R is R ¹¹⁴ Each independently represents a hydrogen atom or a 1-valent organic group. As the organic group having a valence of 1, a linear or branched alkyl group, a cyclic alkyl group, an aromatic group or a polyoxyalkylene group is preferably contained. And, preferably R ¹¹³ R is R ¹¹⁴ At least one of them contains a polymerizable group, and more preferably both contain a polymerizable group. Also preferred is R ¹¹³ R is R ¹¹⁴ At least one of them contains 2 or more polymerizable groups. The polymerizable group is a group that can undergo a crosslinking reaction by the action of heat, radicals, or the like, and is preferably a radical polymerizable group. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group (oxetanyl group), a benzoxazolyl group, a blocked isocyanate group, and an amino group. The radical polymerizable group of the polyimide precursor is preferably a group having an ethylenically unsaturated bond.

Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinyl phenyl group or the like), (meth) acrylamide group, (meth) acryloyloxy group, a group represented by the following formula (I II), and the like, and a group represented by the following formula (III) is preferable.

[ chemical formula 8]

In the formula (III), R ²⁰⁰ Represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, preferably a hydrogen atom or a methyl group.

In formula (III), the bonding sites to other structures are represented.

In the formula (III), R ²⁰¹ Represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH(OH)CH ₂ -, cycloalkylene or polyoxyalkylene.

Preferred R ²⁰¹ Examples of (C) include alkylene such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene and dodecamethylene, 1, 2-butylene, 1, 3-butylene and-CH ₂ CH(OH)CH ₂ -, polyoxyalkylene, more preferably alkylene such as ethylene, propylene and the like, -CH ₂ CH(OH)CH ₂ The term "alkylene group" refers to a group having a carboxyl group.

In the present invention, polyoxyalkylene means that an oxyalkylene group is directly bonded to 2 or more groups. The alkylene groups in the plurality of alkylene oxides contained in the polyoxyalkylene group may be the same or different.

In the case where the polyoxyalkylene group includes a plurality of kinds of oxyalkylene groups having different alkylene groups, the arrangement of the oxyalkylene groups in the polyoxyalkylene group may be random, may be block-containing, or may be alternating or the like.

The number of carbon atoms of the alkylene group (the number of carbon atoms including a substituent in the case where the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, still more preferably 2 to 6, still more preferably 2 to 5, still more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2.

The alkylene group may have a substituent. Preferred substituents include alkyl groups, aryl groups, halogen atoms, and the like.

The number of oxyalkylene groups contained in the polyoxyalkylene group (the number of repeating polyoxyalkylene groups) is preferably 2 to 20, more preferably 2 to 10, and still more preferably 2 to 6.

The polyoxyalkylene group is preferably a polyoxyethylene group, a polyoxypropylene group, a polyoxytrimethylene group, a polyoxytetramethylene group, or a group obtained by bonding a plurality of oxyethylene groups to a plurality of oxypropylene groups, more preferably a polyoxyethylene group or a polyoxypropylene group, and still more preferably a polyoxyethylene group, from the viewpoints of solvent solubility and solvent resistance. Among the groups obtained by bonding the plurality of oxyethylene groups and the plurality of oxypropylene groups, the oxyethylene groups and the oxypropylene groups may be arranged randomly, may be arranged in blocks, or may be arranged in an alternating pattern. The preferable mode of repeating the number of oxyethylene groups and the like in these groups is as described above.

In the formula (2), R is ¹¹³ In the case of hydrogen atoms or in R ¹¹⁴ In the case of a hydrogen atom, the polyimide precursor may form a conjugate base with a tertiary amine compound having an ethylenically unsaturated bond. Examples of such tertiary amine compounds having an ethylenically unsaturated bond include N, N-dimethylaminopropyl methacrylate.

In the formula (2), R ¹¹³ R is R ¹¹⁴ At least one of them may be a polar conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is a group that is decomposed by an acid to generate an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group, but is preferably an acetal group, a ketal group, a silyl ether group, a tertiary alkyl ester group, or the like, and more preferably an acetal group or a ketal group from the viewpoint of sensitivity to exposure.

Specific examples of the acid-decomposable group include t-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, t-butoxycarbonylmethyl, and trimethylsilylether groups. From the viewpoint of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferable.

The polyimide precursor preferably has a fluorine atom in the structure. The fluorine atom content in the polyimide precursor is preferably 10 mass% or more, and more preferably 20 mass% or less.

In order to improve adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, as the diamine, there can be mentioned a method using bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, or the like.

The repeating unit represented by the formula (2) is preferably a repeating unit represented by the formula (2-A). That is, at least 1 of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by the formula (2-a). By including the repeating unit represented by the formula (2-a) in the polyimide precursor, the width of the exposure latitude can be further increased.

(2-A)

[ chemical formula 9]

In the formula (2-A), A ¹ A is a ² Represents an oxygen atom, R ¹¹¹ R is R ¹¹² Each independently represents a 2-valent organic group, R ¹¹³ R is R ¹¹⁴ Each independently represents a hydrogen atom or a 1-valent organic group, R ¹¹³ R is R ¹¹⁴ At least one of them is a group containing a polymerizable group, and preferably both are groups containing a polymerizable group.

A ¹ 、A ² 、R ¹¹¹ 、R ¹¹³ R is R ¹¹⁴ Independently of A in formula (2) ¹ 、A ² 、R ¹¹¹ 、R ¹¹³ R is R ¹¹⁴ The meaning of (2) is the same and the preferred ranges are also the same.

R ¹¹² R in formula (5) ¹¹² The meaning of (2) is the same and the preferred ranges are also the same.

The polyimide precursor may contain 1 type of repeating unit represented by the formula (2), or may contain 2 or more types. The structural isomer of the repeating unit represented by formula (2) may be contained. The polyimide precursor may contain a repeating unit of other types, in addition to the repeating unit of the above formula (2).

One embodiment of the polyimide precursor in the present invention is one in which the content of the repeating unit represented by the formula (2) is 50 mol% or more of all the repeating units. The total content is more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all the repeating units in the polyimide precursor other than the terminal may be the repeating unit represented by the formula (2).

The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 ～ 100,000, more preferably 10,000 ～ 50,000, and even more preferably 15,000 ～ 40,000. The number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and still more preferably 4,000 to 20,000.

The molecular weight of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyimide precursor is not particularly limited, and is, for example, preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less.

In the present specification, the dispersity of the molecular weight is a value calculated using a weight average molecular weight/number average molecular weight.

In the case where the resin composition contains a plurality of polyimide precursors as a specific resin, it is preferable that the weight average molecular weight, the number average molecular weight, and the dispersity of at least 1 polyimide precursor be within the above-mentioned ranges. It is also preferable that the weight average molecular weight, the number average molecular weight and the dispersity calculated for the plurality of polyimide precursors as 1 resin are each within the above ranges.

[ polyimide ]

The polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide which is soluble in a developer mainly containing an organic solvent.

In the present specification, the alkali-soluble polyimide means a polyimide in which 0.1g or more, preferably 0.5g or more, more preferably 1.0g or more, of the polyimide is dissolved in 100g of a 2.38 mass% aqueous tetramethylammonium solution at 23 ℃. The upper limit of the amount of the dissolved substance is not particularly limited, but is preferably 100g or less.

Further, from the viewpoints of film strength and insulation properties of the obtained organic film, polyimide is preferably polyimide having a plurality of imide structures in the main chain.

In the present specification, "main chain" means a relatively longest bonding chain among molecules of a polymer compound constituting a resin, and "side chain" means other bonding chains.

Fluorine atom-

From the viewpoint of film strength of the obtained organic film, polyimide is also preferable to have fluorine atoms.

The fluorine atom is preferably R contained in the repeating unit represented by the following formula (4) ¹³² Or R in the repeating unit represented by the following formula (4) ¹³¹ More preferably, R is contained as a fluorinated alkyl group in the repeating unit represented by the following formula (4) ¹³² Or R in the repeating unit represented by the following formula (4) ¹³¹ Is a kind of medium.

The amount of fluorine atoms is preferably 5 mass% or more, and preferably 20 mass% or less, relative to the total mass of the polyimide.

Silicon atom-

From the viewpoint of film strength of the obtained organic film, polyimide is also preferable to have silicon atoms.

The silicon atom is preferably R contained in the repeating unit represented by the following formula (4) ¹³¹ More preferably, R is contained as the structure of the organic modified (poly) siloxane described later in the repeating unit represented by the following formula (4) ¹³¹ Is a kind of medium.

The silicon atom or the organic modified (poly) siloxane structure may be contained in a side chain of the polyimide, but is preferably contained in a main chain of the polyimide.

The amount of silicon atoms is preferably 1 mass% or more, more preferably 20 mass% or less, relative to the total mass of the polyimide.

Ethylenic unsaturation

From the viewpoint of the film strength of the obtained organic film, polyimide preferably has an ethylenically unsaturated bond.

The polyimide may have an ethylenically unsaturated bond at the terminal of the main chain or may have an ethylenically unsaturated bond in the side chain, but preferably has an ethylenically unsaturated bond in the side chain.

The ethylenically unsaturated bond is preferably radically polymerizable.

The ethylenically unsaturated bond is preferably R contained in the repeating unit represented by the following formula (4) ¹³² Or R in the repeating unit represented by the following formula (4) ¹³¹ More preferably, R is contained as a group having an ethylenically unsaturated bond in the repeating unit represented by the following formula (4) ¹³² Or R in the repeating unit represented by the following formula (4) ¹³¹ Is a kind of medium.

Among these, R contained in the repeating unit represented by the following formula (4) is preferable ¹³¹ More preferably, R is contained as a group having an ethylenically unsaturated bond in the repeating unit represented by the following formula (4) ¹³¹ Is a kind of medium.

Examples of the group having an ethylenically unsaturated bond include a group having a vinyl group which may be substituted by direct bonding to an aromatic ring, such as a vinyl group, an allyl group, and a vinylphenyl group, (meth) acryl, (meth) acryloyloxy, and a group represented by the following formula (IV).

[ chemical formula 10]

In the formula (IV), R ²⁰ Represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, preferablyA hydrogen atom or a methyl group.

In the formula (IV), R ²¹ Represents an alkylene group having 2 to 12 carbon atoms, -O-CH ₂ CH(OH)CH ₂ -, -C (=O) O-, -O (C=0) NH-, a (poly) oxyalkylene group having 2 to 30 carbon atoms (the number of carbon atoms of the alkylene group is preferably 2 to 12, more preferably 2 to 6, particularly preferably 2 or 3, the number of repetition is preferably 1 to 12, more preferably 1 to 6, particularly preferably 1 to 3), or a combination of these is 2 or more.

The alkylene group having 2 to 12 carbon atoms may be any of a linear, branched, cyclic, or a combination thereof.

The alkylene group having 2 to 12 carbon atoms is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.

Among these, R ²¹ The group represented by any one of the following formulas (R1) to (R3) is preferable, and the group represented by the formula (R1) is more preferable.

[ chemical formula 11]

In the formulae (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly) oxyalkylene group having 2 to 30 carbon atoms, or a group obtained by bonding these groups together in an amount of 2 or more, X represents an oxygen atom or a sulfur atom, X represents a bonding site to another structure, and R represents a group represented by formula (IV) ²¹ Bonding sites for the bonded oxygen atoms.

In the formulae (R1) to (R3), a preferable mode of the alkylene group having 2 to 12 carbon atoms or the (poly) oxyalkylene group having 2 to 30 carbon atoms in L is the same as the above-mentioned R ²¹ The preferred mode of the alkylene group having 2 to 12 carbon atoms or the (poly) oxyalkylene group having 2 to 30 carbon atoms is the same.

In the formula (R1), X is preferably an oxygen atom.

The meanings of formulae (R1) to (R3) are the same as those of formula (IV), and preferred modes are also the same.

The structure represented by the formula (R1) is obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanate group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate or the like).

The structure represented by the formula (R2) is obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate or the like).

The structure represented by the formula (R3) is obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate or the like).

In formula (IV), the bond site to other structure is preferably a bond site to the main chain of polyimide.

The amount of the ethylenic unsaturated bond is preferably 0.0001 to 0.1mol/g, more preferably 0.0005 to 0.05mol/g, relative to the total mass of the polyimide.

Polymerizable groups other than those having an ethylenically unsaturated bond

The polyimide may have a polymerizable group other than the group having an ethylenically unsaturated bond.

Examples of the polymerizable group other than the group having an ethylenically unsaturated bond include a cyclic ether group such as an epoxy group and an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a hydroxymethyl group.

The polymerizable group other than the group having an ethylenically unsaturated bond is preferably, for example, R contained in the repeating unit represented by the following formula (4) ¹³¹ Is a kind of medium.

The amount of the polymerizable group other than the group having an ethylenically unsaturated bond is preferably 0.0001 to 0.1mol/g, more preferably 0.001 to 0.05mol/g, relative to the total mass of the polyimide.

Polar conversion group-

The polyimide may have a polar conversion group such as an acid-decomposable group. Acid-decomposable groups in polyimide and R in the above formula (2) ¹¹³ R is R ¹¹⁴ Is a Chinese style of instituteThe acid-decomposable groups described are the same, and the preferable modes are also the same.

The polarity-converting group is, for example, R contained in the repeating unit represented by the following formula (4) ¹³¹ 、R ¹³² In the terminal of polyimide, etc.

Acid number-

When the polyimide is subjected to alkaline development, the acid value of the polyimide is preferably 30mgKOH/g or more, more preferably 50mgKOH/g or more, and still more preferably 70mgKOH/g or more, from the viewpoint of improving the developability.

The acid value is preferably 500mgKOH/g or less, more preferably 400mgKOH/g or less, and still more preferably 200mgKOH/g or less.

When the polyimide is subjected to development using a developer containing an organic solvent as a main component (for example, the "solvent development" described later), the acid value of the polyimide is preferably 1 to 35mgKOH/g, more preferably 2 to 30mgKOH/g, and still more preferably 5 to 20mgKOH/g.

The acid value is measured by a known method, for example, by JIS K0070: the measurement was performed by the method described in 1992.

The acid value of the polyimide is preferably 0mmol/g to 1.2mmol/g, more preferably 0mmol/g to 0.8mmol/g, and even more preferably 0mmol/g to 0.6mmol/g, from the viewpoint of chemical resistance.

Further, as the acid group contained in the polyimide, an acid group having a pKa of 0 to 10 is preferable, and an acid group having a pKa of 3 to 8 is more preferable from the viewpoint of both storage stability and developability.

pKa refers to the value whose equilibrium constant Ka is expressed in terms of its negative common logarithmic pKa, taking into account the dissociation reaction of hydrogen ions released from the acid. In the present specification, unless otherwise specified, pKa is set to a calculated value based on ACD/ChemSketch (registered trademark). Alternatively, reference may be made to the values disclosed in the Japanese society of chemistry "revised 5 th edition of chemical handbook foundation".

In the case where the acid group is a polybasic acid such as phosphoric acid, the pKa is a first dissociation constant.

As such an acid group, the polyimide preferably contains at least 1 selected from a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

Phenolic hydroxyl radical-

From the viewpoint of making the development speed by the alkaline developer appropriate, polyimide preferably has phenolic hydroxyl groups.

The polyimide may have a phenolic hydroxyl group at the terminal of the main chain or may have a phenolic hydroxyl group in a side chain.

The phenolic hydroxyl group is preferably R contained in the repeating unit represented by the following formula (4) ¹³² Or R in the repeating unit represented by the following formula (4) ¹³¹ Is a kind of medium.

The amount of the phenolic hydroxyl groups is preferably 0.1 to 30mol/g, more preferably 1 to 20mol/g, relative to the total mass of the polyimide.

The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but preferably contains a repeating unit represented by the following formula (4).

[ chemical formula 12]

/>

In the formula (4), R ¹³¹ Represents an organic group of valence 2, R ¹³² Represents a 4-valent organic group.

In the case of having a polymerizable group, the polymerizable group may be located at R ¹³¹ R is R ¹³² At least one of the above may be located at the terminal of polyimide as shown in the following formula (4-1) or formula (4-2).

(4-1)

[ chemical formula 13]

In the formula (4-1), R ¹³³ The other groups are the same as those of formula (4).

(4-2)

[ chemical formula 14]

R ¹³⁴ R is R ¹³⁵ At least one of them is a polymerizable group, and if not, an organic group, and the other groups have the same meaning as in formula (4).

Examples of the polymerizable group include the group containing an ethylenically unsaturated bond and a crosslinkable group other than the group having an ethylenically unsaturated bond.

R ¹³¹ An organic group having a valence of 2. As the organic group having a valence of 2, R in the formula (2) can be exemplified ¹¹¹ The same groups, preferred ranges are also the same.

And as R ¹³¹ The diamine residue remaining after removal of the amino group of the diamine may be mentioned. Examples of the diamine include aliphatic, cyclic aliphatic and aromatic diamines. Specific examples thereof include R in formula (2) of polyimide precursor ¹¹¹ Is an example of (a).

R is from the viewpoint of more effectively suppressing warpage upon calcination ¹³¹ Diamine residues having at least 2 alkylene glycol units in the backbone are preferred. More preferably, the diamine residues each containing 2 or more ethylene glycol chains, propylene glycol chains, or both in total in one molecule, and still more preferably, the diamine residues each containing no aromatic ring are diamine residues.

Examples of diamines containing 2 or more ethylene glycol chains, propylene glycol chains, or both in total in one molecule include JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (trade name, manufactured by HUNTSMAN CORPORATION), 1- (2- (2- (2-aminopropoxy) ethoxy) propoxy) propan-2-amine, 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propan-2-amine, and the like, but are not limited thereto.

R ¹³² Represents a 4-valent organic group. As a 4-valentThe organic group of (2) may be exemplified as R in the formula (2) ¹¹⁵ The same groups, preferred ranges are also the same.

For example, as R ¹¹⁵ And 4 linkers of the exemplified 4-valent organic groups are bonded to 4-C (=o) -moieties in the above formula (4) to form condensed rings.

And R is ¹³² Examples thereof include tetracarboxylic acid residues remaining after removal of the acid anhydride group from the tetracarboxylic dianhydride. Specific examples thereof include R in formula (2) of polyimide precursor ¹¹⁵ Is an example of (a). From the viewpoint of the strength of the organic film, R ¹³² Preferably an aromatic diamine residue having 1 to 4 aromatic rings.

Also preferred is R ¹³¹ And R is ¹³² At least one of them having an OH group. More specifically, as R ¹³¹ Examples of the preferable examples include 2, 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, and the above-mentioned (DA-1) to (DA-18) as R ¹³² As more preferable examples, (DAA-1) to (DAA-5) mentioned above are given.

The polyimide also preferably has a fluorine atom in the structure. The content of fluorine atoms in the polyimide is preferably 10 mass% or more, and preferably 20 mass% or less.

In order to improve adhesion to the substrate, polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, and the like.

In order to improve the storage stability of the resin composition, it is preferable to seal the main chain end of the polyimide with a blocking agent such as monoamine, acid anhydride, monocarboxylic acid, monochloride compound, or monoactive ester compound. Among these, monoamines are more preferably used, and preferable examples of monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4-dihydroxypyrimidine, 2-hydroxy-5-aminophenol, 3-aminophenol, and thiophenol. These may be used in an amount of 2 or more, and a plurality of different terminal groups may be introduced by reacting a plurality of capping agents.

Imidization ratio (ring closure ratio)

The imidization ratio (also referred to as "ring closure ratio") of the polyimide is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more from the viewpoints of film strength, insulation property, and the like of the obtained organic film.

The upper limit of the imidization ratio is not particularly limited as long as it is 100% or less.

The imidization ratio is measured, for example, by the following method.

The infrared absorption spectrum of polyimide was measured to obtain 1377cm as the absorption peak derived from the imide structure ^-1 A nearby peak intensity P1. Next, after the polyimide was subjected to a heat treatment at 350℃for 1 hour, the infrared absorption spectrum was measured again to obtain 1377cm ^-1 A nearby peak intensity P2. Using the obtained peak intensities P1 and P2, the imidization ratio of polyimide can be obtained according to the following formula.

Imidization ratio (%) = (peak intensity P1/peak intensity P2) ×100

The polyimide may all contain 1 kind of R ¹³¹ Or R is ¹³² The repeating unit represented by the above formula (4) may contain at least 2R of different types ¹³¹ Or R is ¹³² The repeating unit represented by the above formula (4). Further, the polyimide is represented by the above formula (4) Other types of repeating units may be included in addition to the repeating units represented. Examples of the other types of repeating units include repeating units represented by the above formula (2).

Polyimide can be synthesized by, for example, the following method: a method in which a tetracarboxylic dianhydride is reacted with a diamine (a capping agent having a part replaced with a monoamine) at a low temperature; a method of reacting a tetracarboxylic dianhydride (a capping agent in which a part is substituted with an acid anhydride or a monochloride compound or a monoactive ester compound) with a diamine at a low temperature; a method in which a diester is obtained by tetracarboxylic dianhydride and alcohol, and then reacted with a diamine (a capping agent having a part replaced with monoamine) in the presence of a condensing agent; a method in which a diester is obtained by a tetracarboxylic dianhydride and an alcohol, and then the remaining dicarboxylic acid is subjected to chlorination and reacted with a diamine (a capping agent having a part replaced with a monoamine), to obtain a polyimide precursor, and then the polyimide precursor is fully imidized by a known imidization method; alternatively, a method of stopping the imidization reaction halfway and introducing a part of the imide structure; and a method of introducing a part of imide structure by mixing a completely imidized polymer and the polyimide precursor. Other known polyimide synthesis methods can be applied.

The polyimide preferably has a weight average molecular weight (Mw) of 5,000 ～ 100,000, more preferably 10,000 ～ 50,000, and even more preferably 15,000 ～ 40,000. By setting the weight average molecular weight to 5,000 or more, the folding endurance of the cured film can be improved. In order to obtain an organic film excellent in mechanical properties (for example, elongation at break), the weight average molecular weight is particularly preferably 15,000 or more.

The number average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.

The molecular weight of the polyimide is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyimide is not particularly limited, and is, for example, preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less.

In the case where the resin composition contains a plurality of polyimides as the specific resin, it is preferable that the weight average molecular weight, the number average molecular weight and the dispersity of at least 1 polyimide are within the above-mentioned ranges. The weight average molecular weight, the number average molecular weight and the dispersity calculated for the plurality of polyimides as 1 resin are also preferably within the above ranges.

[ polybenzoxazole precursors ]

The structure of the polybenzoxazole precursor used in the present invention is not particularly limited, but preferably includes a repeating unit represented by the following formula (3).

[ chemical formula 15]

In the formula (3), R ¹²¹ Represents an organic group of valence 2, R ¹²² Represents an organic group of valence 4, R ¹²³ R is R ¹²⁴ Each independently represents a hydrogen atom or a 1-valent organic group.

In the formula (3), R ¹²³ R is R ¹²⁴ Respectively with R in the formula (2) ¹¹³ The meaning of (2) is the same and the preferred ranges are also the same. That is, at least one of them is preferably a polymerizable group.

In the formula (3), R ¹²¹ An organic group having a valence of 2. The organic group having a valence of 2 is preferably a group containing at least one of an aliphatic group and an aromatic group. The aliphatic group is preferably a straight chain aliphatic group. R is R ¹²¹ Dicarboxylic acid residues are preferred. The dicarboxylic acid residues may be used in an amount of 1 or 2 or more.

The dicarboxylic acid residue is preferably a dicarboxylic acid residue containing an aliphatic group or a dicarboxylic acid residue containing an aromatic group, and more preferably a dicarboxylic acid residue containing an aromatic group.

As the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group is preferable, and a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group and 2-COOH is more preferable. The number of carbon atoms of the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, still more preferably 3 to 20, still more preferably 4 to 15, and particularly preferably 5 to 10. The straight chain aliphatic group is preferably an alkylene group.

As the dicarboxylic acid containing a linear aliphatic group, examples thereof include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2-dimethylsuccinic acid, 2, 3-dimethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, and 3-methylglutaric acid, 2-dimethylglutaric acid, 3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2, 6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, adipic acid hexadecanedioic acid, 1, 9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, ditridecanedioic acid, tetracosanedioic acid, cyclopentadecanedioic acid, hexacosanedioic acid, heptadecanedioic acid, octacosanedioic acid, icosanedioic acid, triacontanedioic acid, tricosanedioic acid, diglycolic acid (diglycolic acid), dicarboxylic acids represented by the following formulas, and the like.

[ chemical formula 16]

(wherein Z is a hydrocarbon group having 1 to 6 carbon atoms and n is an integer of 1 to 6.)

The dicarboxylic acid containing an aromatic group is preferably a dicarboxylic acid having an aromatic group as follows, and more preferably a dicarboxylic acid having only a group having an aromatic group and 2-COOH as follows.

[ chemical formula 17]

Wherein A represents a member selected from the group consisting of-CH ₂ -、-O-、-S-、-SO ₂ -、-CO-、-NHCO-、-C(CF ₃ ) ₂ -and-C (CH) ₃ ) ₂ The groups of valency 2 in (a) independently represent bonding sites with other structures.

Specific examples of the dicarboxylic acid containing an aromatic group include 4,4 '-carbonyldibenzoic acid, 4' -dicarboxydiphenyl ether and phthalic acid.

In the formula (3), R ¹²² Represents a 4-valent organic group. R in the above formula (2) is used as a 4-valent organic group ¹¹⁵ The meaning of (2) is the same and the preferred ranges are also the same.

And R is ¹²² Preferably, a group derived from a bisaminophenol derivative, as a group derived from a bisaminophenol derivative, examples thereof include 3,3 '-diamino-4, 4' -dihydroxybiphenyl, 4 '-diamino-3, 3' -dihydroxybiphenyl, 3 '-diamino-4, 4' -dihydroxydiphenyl sulfone, 4 '-diamino-3, 3' -dihydroxydiphenyl sulfone bis- (3-amino-4-hydroxyphenyl) methane, 2-bis (3-amino-4-hydroxyphenyl) propane, 2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2-bis- (4-amino-3-hydroxyphenyl) hexafluoropropane bis- (4-amino-3-hydroxyphenyl) methane, 2-bis- (4-amino-3-hydroxyphenyl) propane, 4 '-diamino-3, 3' -dihydroxybenzophenone, 3 '-diamino-4, 4' -dihydroxybenzophenone, 4 '-diamino-3, 3' -dihydroxydiphenyl ether, 3 '-diamino-4, 4' -dihydroxydiphenyl ether, 1, 4-diamino-2, 5-dihydroxybenzene, 1, 3-diamino-2, 4-dihydroxybenzene, 1, 3-diamino-4, 6-dihydroxybenzene, and the like. These bisaminophenols may be used alone or in combination.

Among the bisaminophenol derivatives, the following bisaminophenol derivatives having an aromatic group are preferable.

[ chemical formula 18]

Wherein X is ₁ represents-O-, -S-, -C (CF) ₃ ) ₂ -、-CH ₂ -、-SO ₂ -, -NHCO-, and # each represent a bonding site to another structure. R represents a hydrogen atom or a 1-valent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group. And R is ¹²² The structure represented by the above formula is also preferable. At R ¹²² In the case of the structure represented by the above formula, it is preferable that any 2 of the total 4 are R in the formula (3) ¹²² The bonding site of the bonded nitrogen atom and the other 2 are R in the formula (3) ¹²² The bonding site of the bonded oxygen atom is more preferably 2 x is R in formula (3) ¹²² The bonding site of the bonded oxygen atom and 2# are R in formula (3) ¹²² The bonding site of the bonded nitrogen atom, or 2 are R in formula (3) ¹²² The bonding site of the bonded nitrogen atom and 2 # are R in formula (3) ¹²² The bonding site of the bonded oxygen atom is more preferably 2 x is R in formula (3) ¹²² The bonding site of the bonded oxygen atom and 2# are R in formula (3) ¹²² Bonding sites for the bonded nitrogen atoms.

The bisaminophenol derivative is also preferably a compound represented by the formula (A-s).

[ chemical formula 19]

In the formula (A-s), R ₁ Is selected from hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO ₂ -, -CO-, -NHCO-; a single bond or an organic group of the following formula (A-sc). R is R ₂ The hydrogen atom, alkyl group, alkoxy group, acyloxy group, and cyclic alkyl group may be the same or different. R is R ₃ Is hydrogen atom, straight-chain or branched alkyl, alkoxy, acyloxyThe base group and the cyclic alkyl group may be the same or different.

[ chemical formula 20]

(in the formula (A-sc): represents an aromatic ring bond to an aminophenol group of the bisaminophenol derivative represented by the formula (A-s))

In the above formula (A-s), it is considered that the amino group is located at the ortho position to the phenolic hydroxyl group, i.e., at R ₃ The above substituent is particularly preferable in that the distance between the carbonyl carbon of the amide bond and the hydroxyl group is further shortened, and the effect of improving the cyclization ratio at the time of curing at low temperature is further improved.

In the formula (A-s), R ₂ Is alkyl and R ₃ The alkyl group is preferable because it can maintain high transparency to i-rays and has a high cyclization ratio when cured at a low temperature.

In the formula (A-s), R ₁ Further preferred is an alkylene group or a substituted alkylene group. As R ₁ Specific examples of the alkylene group and the substituted alkylene group include a linear or branched alkyl group having 1 to 8 carbon atoms, and more preferably-CH, in terms of obtaining a polybenzoxazole precursor excellent in balance of sufficient solubility in a solvent while maintaining high transparency to i-rays and a high cyclization ratio when cured at a low temperature ₂ -、-CH(CH ₃ )-、-C(CH ₃ ) ₂ -。

Examples of the production method of the bisaminophenol derivative represented by the formula (A-s) include paragraphs 0085 to 0094 and example 1 (0189 to 0190) of JP-A2013-256506, and these are incorporated into the present specification.

Specific examples of the structure of the bisaminophenol derivative represented by the formula (A-s) include those described in paragraphs 0070 to 0080 of Japanese patent application laid-open No. 2013-256506, incorporated herein by reference. Of course, it is needless to say that these are not limiting.

The polybenzoxazole precursor may contain other kinds of repeating units in addition to the repeating unit of the above formula (3).

In order to suppress warpage associated with closed loop, the polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit.

[ chemical formula 21]

In the formula (SL), Z has a structure a and a structure b, R ^1s Is hydrogen atom or hydrocarbon group with 1-10 carbon atoms, R ^2s Is a hydrocarbon group of 1 to 10 carbon atoms, R ^3s 、R ^4s 、R ^5s 、R ^6s At least 1 of them is an aromatic group, and the others are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. Regarding the mole% of the Z moiety, the a structure is 5 to 95 mole%, the b structure is 95 to 5 mole%, and a+b is 100 mole%.

In the formula (SL), preferable Z is R in the b structure ^5s R is R ^6s A hydrocarbon group which is a phenyl group. The molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the molecular weight in the above range, the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure can be reduced more effectively, and the effect of suppressing warpage and the effect of improving solvent solubility can be achieved at the same time.

When the diamine residue represented by the formula (SL) is contained as another type of repeating unit, it is preferable that the diamine residue further contains a tetracarboxylic acid residue remaining after the acid anhydride group is removed from the tetracarboxylic dianhydride as a repeating unit. Examples of such tetracarboxylic acid residues include R in formula (2) ¹¹⁵ Is an example of (a).

The weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably 18,000 ～ 30,000, more preferably 20,000 ～ 29,000, and further preferably 22,000 ～ 28,000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and still more preferably 9,200 to 11,200.

The dispersion degree of the molecular weight of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and further preferably 1.6 or more. The upper limit of the dispersity of the molecular weight of the polybenzoxazole precursor is not particularly limited, and is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, further preferably 2.3 or less, and further preferably 2.2 or less, for example.

In the case where the resin composition contains a plurality of polybenzoxazole precursors as a specific resin, it is preferable that the weight average molecular weight, the number average molecular weight and the dispersity of at least 1 polybenzoxazole precursor are within the above-mentioned ranges. It is also preferable that the weight average molecular weight, the number average molecular weight and the dispersity calculated for the plurality of polybenzoxazole precursors as 1 resin are each within the above ranges.

[ polybenzoxazole ]

The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but is preferably a compound represented by the following formula (X), more preferably a compound represented by the following formula (X) and having a polymerizable group. The polymerizable group is preferably a radical polymerizable group.

[ chemical formula 22]

In the formula (X), R ¹³³ Represents an organic group of valence 2, R ¹³⁴ Represents a 4-valent organic group.

In the case of having a polymerizable group, the polymerizable group may be located at R ¹³³ R is R ¹³⁴ At least one of the compounds may be located at the terminal of polybenzoxazole as shown in the following formula (X-1) or formula (X-2).

(X-1)

[ chemical formula 23]

In the formula (X-1), R ¹³⁵ R is R ¹³⁶ At least one of them is a polymerizable group, and if not, an organic group, and the other groups have the same meaning as in formula (X).

(X-2)

[ chemical formula 24]

In the formula (X-2), R ¹³⁷ The polymerizable group is a substituent, and the other groups have the same meaning as in formula (X).

The polymerizable group has the same meaning as that of the polymerizable group described in the polymerizable group of the polyimide precursor.

R ¹³³ An organic group having a valence of 2. Examples of the 2-valent organic group include an aliphatic group and an aromatic group. Specific examples thereof include R in formula (3) of a polybenzoxazole precursor ¹²¹ Is an example of (a). And, preferred examples thereof are as follows ¹²¹ The same applies.

R ¹³⁴ Represents a 4-valent organic group. Examples of the 4-valent organic group include R in formula (3) of the polybenzoxazole precursor ¹²² Is an example of (a). And, preferred examples thereof are as follows ¹²² The same applies.

For example, as R ¹²² And 4 linkers of the exemplified 4-valent organic groups are bonded to the nitrogen atom and the oxygen atom in the above formula (X) to form a condensed ring. For example, at R ¹³⁴ In the case of the following organic group, the following structure is formed. In the following structures, the bonding sites with nitrogen or oxygen atoms in formula (X) are represented, respectively.

[ chemical formula 25]

/>

The oxazolization ratio of the polybenzoxazole is preferably 85% or more, more preferably 90% or more. The upper limit is not particularly limited and may be 100%. When the rate of the oxazolization is 85% or more, the film shrinkage due to the closed loop generated when the oxazolization is performed by heating is reduced, and thus the occurrence of warpage can be more effectively suppressed.

The above-mentioned rate of oxazolification is measured, for example, by the following method.

Measurement of the infrared absorption spectrum of polybenzoxazole to obtain 1650cm as the absorption peak of the amide structure derived from the precursor ^-1 A nearby peak intensity Q1. Next, at 1490cm ^-1 The absorption intensity of the aromatic ring found nearby was normalized. After the polybenzoxazole was subjected to heat treatment at 350℃for 1 hour, the infrared absorption spectrum was measured again to obtain 1650cm ^-1 A nearby peak intensity Q2, and at 1490cm ^-1 The absorption intensity of the aromatic ring found nearby was normalized. Using the standard values of the obtained peak intensities Q1, Q2, the oxazolization ratio of the polybenzoxazole can be obtained according to the following formula.

The oxazolification rate (%) = (standard value of peak intensity Q1/standard value of peak intensity Q2) ×100

The polybenzoxazole can all contain 1R ¹³¹ Or R is ¹³² The repeating unit of the above formula (X) may contain at least 2R of different kinds ¹³¹ Or R is ¹³² The repeating unit of formula (X) above. The polybenzoxazole may contain a repeating unit of other types in addition to the repeating unit of the above formula (X).

With respect to polybenzoxazole, for example, by reacting a bisaminophenol derivative with a compound containing R ¹³³ The polycarboxylic acid (c) or a compound selected from the dicarboxylic acid dichlorides (dicarboxylic acid dichloride) and dicarboxylic acid derivatives thereof, etc., is reacted to obtain a polybenzoxazole precursor, and is subjected to an oxazolization reaction by a known method.

In the case of dicarboxylic acid, an active ester-type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1, 2, 3-benzotriazole or the like in advance may be used in order to improve the reaction yield or the like.

The weight average molecular weight (Mw) of the polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, still more preferably 10,000 ～ 30,000. By setting the weight average molecular weight to 5,000 or more, the folding endurance of the cured film can be improved. In order to obtain an organic film excellent in mechanical characteristics, the weight average molecular weight is particularly preferably 20,000 or more. In the case where 2 or more polybenzoxazoles are contained, it is preferable that the weight average molecular weight of at least 1 polybenzoxazole is within the above range.

The number average molecular weight (Mn) of the polybenzoxazole is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and still more preferably 9,200 to 11,200.

The molecular weight of the polybenzoxazole has a dispersity of preferably 1.4 or more, more preferably 1.5 or more, and still more preferably 1.6 or more. The upper limit of the dispersity of the molecular weight of the polybenzoxazole is not particularly limited, and is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, further preferably 2.3 or less, further preferably 2.2 or less, for example.

In the case where the resin composition contains a plurality of polybenzoxazoles as a specific resin, it is preferable that the weight average molecular weight, the number average molecular weight and the dispersity of at least 1 polybenzoxazole be within the above-mentioned ranges. It is also preferable that the weight average molecular weight, the number average molecular weight and the dispersity calculated for the plurality of polybenzoxazoles as 1 resin are each within the above range.

[ Polyamide imide precursor ]

The polyamideimide precursor preferably comprises a repeating unit represented by the following formula (PAI-2).

[ chemical formula 26]

In the formula (PAI-2), R ¹¹⁷ Represents an organic group of valence 3, R ¹¹¹ Represents an organic group of valence 2, A ² Represents an oxygen atom or-NH-, R ¹¹³ Represents a hydrogen atom or a 1-valent organic group.

In the formula (PAI-2), R ¹¹⁷ Examples of the aliphatic group include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, and a group obtained by connecting 2 or more of these groups by a single bond or a linking group, and a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and a group obtained by combining 2 or more of these groups by a single bond or a linking group, and more preferably an aromatic group having 6 to 20 carbon atoms, and a group obtained by combining 2 or more of these groups by a single bond or a linking group.

As the above-mentioned linking group (S), preferably-0-, -S-, -C (=o) -, -S (=o) ₂ -, alkylene halide, arylene, or a linking group formed by bonding 2 or more of these, more preferably-O-, -S-, alkylene halide, arylene, or a linking group formed by bonding 2 or more of these.

The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 4 carbon atoms.

The above-mentioned halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and still more preferably a halogenated alkylene group having 1 to 4 carbon atoms. The halogen atom in the halogenated alkylene group includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, and is preferably a fluorine atom. The above-mentioned halogenated alkylene group may have a hydrogen atom or may have all the hydrogen atoms replaced with halogen atoms, but it is preferable that all the hydrogen atoms are replaced with halogen atoms. Examples of the preferred halogenated alkylene group include (bistrifluoromethyl) methylene.

The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1, 3-phenylene group or a 1, 4-phenylene group.

And R is ¹¹⁷ Preferably from tricarboxylic compounds in which at least 1 carboxyl group can be halogenated. The halogenation is preferably chlorination.

In the present invention, a compound having 3 carboxyl groups is referred to as a tricarboxylic acid compound.

2 carboxyl groups out of 3 carboxyl groups of the above-mentioned tricarboxylic acid compound may be anhydrated.

Examples of the tricarboxylic acid compound which may be halogenated for use in the production of the polyamideimide precursor include branched aliphatic, cyclic aliphatic and aromatic tricarboxylic acid compounds.

Only 1 kind of these tricarboxylic acid compounds may be used, or 2 or more kinds may be used.

Specifically, the tricarboxylic acid compound is preferably a tricarboxylic acid compound containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining 2 or more of these groups by a single bond or a linking group, more preferably an tricarboxylic acid compound containing an aromatic group having 6 to 20 carbon atoms or a group obtained by combining 2 or more of aromatic groups having 6 to 20 carbon atoms by a single bond or a linking group.

Further, specific examples of the tricarboxylic acid compound include a tricarboxylic acid compound obtained by single bond, -O-, -CH ₂ -、-C(CH ₃ ) ₂ -、-C(CF ₃ ) ₂ -、-SO ₂ Or phenylene-linked 1,2, 3-propane tricarboxylic acid, 1,3, 5-pentane tricarboxylic acid, citric acid, trimellitic acid, 2,3, 6-naphthalene tricarboxylic acid, a compound of phthalic acid (or phthalic anhydride) with benzoic acid, and the like.

These compounds may be compounds in which 2 carboxyl groups are acid-anhydrides (for example, trimellitic anhydride), or compounds in which at least 1 carboxyl group is halogenated (for example, trimellitic anhydride chloride).

In the formula (PAI-2), R ¹¹¹ 、A ² 、R ¹¹³ Respectively with R in the above formula (2) ¹¹¹ 、A ² 、R ¹¹³ The meaning of (2) is the same, and the preferred mode is the same.

The polyamideimide precursor may further comprise other repeating units.

Examples of the other repeating unit include a repeating unit represented by the above formula (2), a repeating unit represented by the following formula (PAI-1), and the like.

[ chemical formula 27]

In the formula (PAI-1), R ¹¹⁶ Represents an organic group of valence 2, R ¹¹¹ An organic group having a valence of 2.

In the formula (PAI-1), R ¹¹⁶ Examples of the aliphatic group include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, and a group obtained by connecting 2 or more of these groups by a single bond or a linking group, and a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and a group obtained by combining 2 or more of these groups by a single bond or a linking group, and more preferably an aromatic group having 6 to 20 carbon atoms, and a group obtained by combining 2 or more of these groups by a single bond or a linking group.

As the above-mentioned linking group (S), preferably-O-, -S-; -C (=o) -, -S (=o) ₂ -, alkylene halide, arylene, or a linking group formed by bonding 2 or more of these, more preferably-O-, -S-, alkylene halide, arylene, or a linking group formed by bonding 2 or more of these.

And R is ¹¹⁶ Preferably from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound.

In the present invention, a compound having 2 carboxyl groups is referred to as a dicarboxylic acid compound, and a compound having 2 halogenated carboxyl groups is referred to as a dicarboxylic acid dihalide compound.

The carboxyl group in the dicarboxylic acid dihalide compound may be halogenated, and for example, it is preferably chlorinated. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.

Examples of the dicarboxylic acid compound or dicarboxylic acid dihalide compound which may be halogenated for use in the production of the polyamideimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compound or dicarboxylic acid dihalide compound, and the like.

These dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used in an amount of 1 or 2 or more.

Specifically, the dicarboxylic acid compound or dicarboxylic acid dihalide compound is preferably a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing a straight chain aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining these by 2 or more single bonds or linking groups, more preferably a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing an aromatic group having 6 to 20 carbon atoms or a group obtained by combining aromatic groups having 6 to 20 carbon atoms by 2 or more single bonds or linking groups.

Further, as a specific example of the dicarboxylic acid compound, examples thereof include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2-dimethylsuccinic acid, 2, 3-dimethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, and 2, 2-dimethylglutaric acid, 3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoro adipic acid, 3-methyladipic acid, pimelic acid, 2, 6-tetramethylpimelic acid, suberic acid, dodecafluoro suberic acid, azelaic acid, sebacic acid, hexadecyl sebacic acid, 1, 9-azelaic acid, dodecanedioic acid tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, icosanedioic acid, hencanedioic acid, docanedioic acid, ditetradecanedioic acid, heptadecanedioic acid, octadecanedioic acid, icosanedioic acid, triacontanedioic acid, hendecanedioic acid, triacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4' -biphenylcarboxylic acid, 4' -dicarboxyl diphenyl ether, benzophenone-4, 4' -dicarboxylic acid, and the like.

Specific examples of the dicarboxylic acid dihalide compound include compounds having a structure in which 2 carboxyl groups in the specific examples of the dicarboxylic acid compound are halogenated.

In the formula (PAI-1), R ¹¹¹ R is the same as R in the above formula (2) ¹¹¹ The meaning of (2) is the same, and the preferred mode is the same.

The polyamideimide precursor preferably has a fluorine atom in the structure. The fluorine atom content in the polyamideimide precursor is preferably 10 mass% or more, and preferably 20 mass% or less.

In order to improve the adhesion to the substrate, the polyamideimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, and the like.

One embodiment of the polyamideimide precursor in the present invention includes a repeating unit represented by the formula (PAI-2), a repeating unit represented by the formula (PAI-1), and a repeating unit represented by the formula (2) in a total amount of 50 mol% or more based on all the repeating units. The total content is more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all the repeating units in the polyamideimide precursor other than the terminal may be any of the repeating unit represented by the formula (PAI-2), the repeating unit represented by the formula (PAI-1), and the repeating unit represented by the formula (2).

In another embodiment of the polyamideimide precursor according to the present invention, the total content of the repeating unit represented by the formula (PAI-2) and the repeating unit represented by the formula (PAI-1) is 50 mol% or more of all the repeating units. The total content is more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all the recurring units in the polyamideimide precursor other than the terminal may be any of the recurring unit represented by the formula (PAI-2) or the recurring unit represented by the formula (PAI-1).

The weight average molecular weight (Mw) of the polyamideimide precursor is preferably 2,000 ～ 500,000, more preferably 5,000 ～ 100,000, and even more preferably 10,000 ～ 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.

The molecular weight of the polyamideimide precursor has a dispersity of preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyamideimide precursor is not particularly limited, and is, for example, preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less. In the case where the resin composition contains a plurality of polyamide-imide precursors as a specific resin, it is preferable that the weight average molecular weight, the number average molecular weight, and the dispersity of at least 1 polyamide-imide precursor are within the above-mentioned ranges. It is also preferable that the weight average molecular weight, the number average molecular weight and the dispersity calculated for the plurality of polyamide-imide precursors as 1 resin are each within the above-mentioned ranges.

[ Polyamide imide ]

The polyamideimide used in the present invention may be an alkali-soluble polyamideimide or a polyamideimide which is soluble in a developer mainly containing an organic solvent.

In the present specification, the alkali-soluble polyamideimide means a polyamideimide in which 0.1g or more, preferably 0.5g or more, more preferably 1.0g or more, of the polyamideimide is dissolved in 100g of a 2.38 mass% aqueous tetramethylammonium solution at 23 ℃. The upper limit of the amount of the dissolved substance is not particularly limited, but is preferably 100g or less.

In addition, from the viewpoints of film strength and insulation properties of the obtained organic film, the polyamideimide is preferably a polyamideimide having a plurality of amide bonds and a plurality of imide structures in the main chain.

Fluorine atom-

From the viewpoint of film strength of the obtained organic film, the polyamideimide preferably has fluorine atoms.

The fluorine atom is preferably R contained in the repeating unit represented by the following formula (PAI-3) ¹¹⁷ Or R is ¹¹¹ More preferably, R is contained as a fluorinated alkyl group in a repeating unit represented by the following formula (PAI-3) ¹¹⁷ Or R is ¹¹¹ Is a kind of medium.

The amount of fluorine atoms is preferably 5 mass% or more, and preferably 20 mass% or less, relative to the total mass of the polyamideimide.

Ethylenic unsaturation

From the viewpoint of the film strength of the obtained organic film, the polyamideimide may have an ethylenically unsaturated bond.

The polyamideimide may have an ethylenic unsaturated bond at the terminal of the main chain or may have an ethylenic unsaturated bond in the side chain, but preferably has an ethylenic unsaturated bond in the side chain.

The ethylenically unsaturated bond is preferably radically polymerizable.

The ethylenically unsaturated bond is preferably R contained in the repeating unit represented by the following formula (PAI-3) ¹¹⁷ Or R is ¹¹¹ More preferably, R is contained as a group having an ethylenically unsaturated bond in the repeating unit represented by the following formula (PAI-3) ¹¹⁷ Or R is ¹¹¹ Is a kind of medium.

The preferable mode of the group having an ethylenically unsaturated bond is the same as that of the group having an ethylenically unsaturated bond in the above polyimide.

The amount of the ethylenic unsaturated bond is preferably 0.0001 to 0.1mol/g, more preferably 0.001 to 0.05mol/g, relative to the total mass of the polyamideimide.

Polymerizable group other than ethylenic unsaturated bond

The polyamideimide may have a polymerizable group other than an ethylenically unsaturated bond.

Examples of the polymerizable group other than an ethylenic unsaturated bond in the polyamide imide include the same groups as those of the polymerizable group other than an ethylenic unsaturated bond in the polyimide described above.

The polymerizable group other than an ethylenically unsaturated bond is preferably, for example, R contained in the repeating unit represented by the following formula (PAI-3) ¹¹¹ Is a kind of medium.

The amount of the polymerizable group other than the ethylenic unsaturated bond is preferably 0.05 to 10mol/g, more preferably 0.1 to 5mol/g, relative to the total mass of the polyamideimide.

Polar conversion group-

The polyamideimide may have a polar conversion group such as an acid-decomposable group. Acid-decomposable groups in polyamideimidesR in the above formula (2) ¹¹³ R is R ¹¹⁴ The acid-decomposable groups described in the above are the same, and the preferable modes are also the same.

Acid number-

When the polyamideimide is subjected to alkaline development, the acid value of the polyamideimide is preferably 30mgKOH/g or more, more preferably 50mgKOH/g or more, and still more preferably 70mgKOH/g or more from the viewpoint of improving the developability.

When the polyamideimide is subjected to development using a developer containing an organic solvent as a main component (for example, the solvent development described later), the acid value of the polyamideimide is preferably 2 to 35mgKOH/g, more preferably 3 to 30mgKOH/g, and even more preferably 5 to 20mgKOH/g.

The acid value of the polyamide-imide is preferably 0mmol/g to 1.2mmol/g, more preferably 0mmol/g to 0.8mmol/g, still more preferably 0mmol/g to 0.6mmol/g, from the viewpoint of chemical resistance.

The acid groups contained in the polyamide-imide include the same groups as those contained in the polyimide, and the preferable embodiments are also the same.

Phenolic hydroxyl radical-

From the viewpoint of making the development speed by the alkaline developer appropriate, the polyamideimide preferably has a phenolic hydroxyl group.

The polyamideimide may have a phenolic hydroxyl group at the terminal of the main chain or may have a phenolic hydroxyl group in a side chain.

The phenolic hydroxyl group is preferably R contained in the repeating unit represented by the following formula (PA 1-3) ¹¹⁷ Or R is ¹¹¹ Is a kind of medium.

The amount of the phenolic hydroxyl groups is preferably 0.1 to 30mol/g, more preferably 1 to 20mol/g, relative to the total mass of the polyamideimide.

The polyamideimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure and an amide bond, but preferably contains a repeating unit represented by the following formula (PAI-3).

[ chemical formula 28]

In the formula (PAI-3), R ¹¹¹ R is R ¹¹⁷ Respectively with R in the formula (PAI-2) ¹¹¹ R is R ¹¹⁷ The meaning of (2) is the same, and the preferred mode is the same.

In the case of having a polymerizable group, the polymerizable group may be located at R ¹¹¹ R is R ¹¹⁷ At least one of them may be located at the terminal of the polyamideimide.

In order to improve the storage stability of the resin composition, it is preferable to seal the main chain end of the polyamideimide with a blocking agent such as monoamine, acid anhydride, monocarboxylic acid, monochloride compound, or monoactive ester compound. The preferable mode of the blocking agent is the same as that of the blocking agent in the polyimide described above.

Imidization ratio (ring closure ratio)

The imidization rate (also referred to as "ring closure rate") of the polyamideimide is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more from the viewpoints of film strength, insulation property, and the like of the obtained organic film.

The imidization ratio was measured by the same method as the ring closure ratio of the polyimide.

The polyamideimide may all contain a polymer comprising 1R ¹¹¹ Or R is ¹¹⁷ The repeating unit represented by the above formula (PAI-3) may contain at least 2R of different types ¹³¹ Or R is ¹³² The repeating unit represented by the above formula (PAI-3). And, the polyamideimide is represented by the above formula (PAI-3)Other types of repeating units may be included in addition to the repeating units represented. Examples of the other type of repeating unit include repeating units represented by the above formula (PAI-1) or formula (PAI-2).

The polyamideimide can be synthesized by, for example, the following method: a method of obtaining a polyamideimide precursor by a known method and fully imidizing it using a known imidization reaction method; alternatively, a method of stopping the imidization reaction halfway and introducing a part of the imide structure; and a method of introducing a part of imide structure by mixing a completely imidized polymer and the polyamideimide precursor.

The weight average molecular weight (Mw) of the polyamideimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and further preferably 10,000 ～ 30,000. By setting the weight average molecular weight to 5,000 or more, the folding endurance of the cured film can be improved. In order to obtain an organic film excellent in mechanical characteristics, the weight average molecular weight is particularly preferably 20,000 or more.

The number average molecular weight (Mn) of the polyamideimide is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.

The molecular weight of the polyamideimide is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyamideimide is not particularly limited, and is, for example, preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less.

In the case where the resin composition contains a plurality of polyamide-imides as the specific resin, it is preferable that the weight average molecular weight, the number average molecular weight and the dispersity of at least 1 polyamide-imide are within the above-mentioned ranges. It is also preferable that the weight average molecular weight, the number average molecular weight and the dispersity calculated from the plurality of polyamide-imide as 1 resin are each within the above-mentioned ranges.

[ method for producing polyimide precursor and the like ]

The polyimide precursor and the like can be obtained by, for example, the following methods: a method of reacting a tetracarboxylic dianhydride with a diamine at a low temperature, a method of reacting a tetracarboxylic dianhydride with a diamine at a low temperature to obtain a polyamic acid and esterifying it with a condensing agent or an alkylating agent, a method of obtaining a diester by a tetracarboxylic dianhydride with an alcohol, and then reacting it in the presence of a diamine and a condensing agent, a method of obtaining a diester by a tetracarboxylic dianhydride with an alcohol, and then halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with a diamine, and the like. Among the above production methods, more preferable is a method in which a diester is obtained from a tetracarboxylic dianhydride and an alcohol, and then the remaining dicarboxylic acid is halogenated with a halogenating agent and reacted with a diamine.

Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1, 2-dihydroquinoline, 1-carbonyldioxy-di-1, 2, 3-benzotriazole, N' -disuccinimidyl carbonate (Disuccinimidyl carbonate), and trifluoroacetic anhydride.

Examples of the alkylating agent include N, N-dimethylformamide dimethyl acetal, N-dimethylformamide diethyl acetal, N-dialkylformamide dialkyl acetal, trimethyl orthoformate, triethyl orthoformate and the like.

Examples of the halogenating agent include thionyl chloride, oxalyl chloride, and phosphoryl chloride.

In the method for producing a polyimide precursor or the like, an organic solvent is preferably used in the reaction. The organic solvent may be 1 or 2 or more.

The organic solvent may be appropriately set according to the raw material, but may be exemplified by pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ -butyrolactone.

In the method for producing a polyimide precursor or the like, an alkali compound is preferably added at the time of the reaction. The number of the basic compounds may be 1 or 2 or more.

The basic compound may be appropriately set depending on the starting materials, but triethylamine, diisopropylethylamine, pyridine, 1, 8-diazabicyclo [5.4.0] undec-7-ene, N-dimethyl-4-aminopyridine, and the like may be exemplified.

Blocking agent-

In the method for producing a polyimide precursor or the like, it is preferable to seal a carboxylic anhydride, an acid anhydride derivative or an amino group remaining at the end of a resin such as a polyimide precursor or the like in order to further improve the storage stability. In the case of sealing carboxylic acid anhydrides and acid anhydride derivatives remaining at the ends of the resin, examples of the end-capping agent include monohydric alcohols, phenols, thiols, thiophenols, monoamines, and the like, and from the viewpoints of reactivity and film stability, monohydric alcohols, phenols, and monoamines are more preferably used. Preferred examples of the monohydric alcohol include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, secondary alcohols such as isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol, tertiary alcohols such as tertiary butanol and adamantanol. Preferred examples of the phenols include phenols such as phenol, methoxyphenol, methylphenol, naphthalen-1-ol, naphthalen-2-ol, and hydroxystyrene. Further, preferable examples of monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4, 6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 3-aminophenol, thiophenol, and the like. These may be used in an amount of 2 or more, and a plurality of different terminal groups may be introduced by reacting a plurality of capping agents.

In addition, when the amino group at the end of the resin is sealed, the resin can be sealed with a compound having a functional group capable of reacting with the amino group. Preferred sealants for the amino group are preferably carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, sulfonic acid carboxylic acid anhydrides, and the like, more preferably carboxylic acid anhydrides, carboxylic acid chlorides. Preferred examples of the carboxylic anhydride include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and 5-norbornene-2, 3-dicarboxylic anhydride. Preferred examples of the carboxylic acid chloride include acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, trimethylacetyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearoyl chloride, and benzoyl chloride.

Solid precipitation-

The method for producing a polyimide precursor or the like may include a step of precipitating a solid. Specifically, the water-absorbing by-product of the dehydration condensing agent coexisting in the reaction liquid is filtered out as needed, and then the obtained polymer component is put into a poor solvent such as water, aliphatic lower alcohol or a mixed liquid thereof, and the polymer component is precipitated as a solid and dried, whereby a polyimide precursor or the like can be obtained. In order to improve the degree of purification, the operations of redissolving, reprecipitating, drying, and the like of the polyimide precursor and the like may be repeated. Further, a process of removing ionic impurities using an ion exchange resin may be included.

[ content ]

The content of the specific resin in the resin composition of the present invention is preferably 20 mass% or more, more preferably 30 mass% or more, still more preferably 40 mass% or more, and still more preferably 50 mass% or more, based on the total solid content of the resin composition. The content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, still more preferably 98% by mass or less, still more preferably 97% by mass or less, 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 1 specific resin or may contain 2 or more kinds. When the content is 2 or more, the total amount is preferably within the above range.

Further, the resin composition of the present invention also preferably contains at least 2 resins.

Specifically, the resin composition of the present invention may contain 2 or more specific resins and other resins described later in total, or may contain 2 or more specific resins, but preferably contains 2 or more specific resins.

In the case where the resin composition of the present invention contains 2 or more specific resins, for example, a structure (R as described in the above formula (2)) which is a polyimide precursor and derived from dianhydride is preferably contained ¹¹⁵ ) Different polyimide precursors of 2 or more types.

< other resins >

The resin composition of the present invention may contain the above specific resin and another resin (hereinafter, also simply referred to as "another resin") different from the specific resin.

Examples of the other resin include phenolic resins, polyamides, epoxy resins, resins containing polysiloxane and siloxane structures, (meth) acrylic resins, (meth) acrylamide resins, urethane resins, butyral resins, styrene resins, polyether resins, and polyester resins.

For example, by further adding a (meth) acrylic resin, a resin composition excellent in coatability can be obtained, and a pattern (cured product) excellent in solvent resistance can be obtained.

For example, instead of or in addition to the polymerizable compound described below, a polymerizable group having a weight average molecular weight of 20,000 or less is used as the resin (for example, the polymerizable group in 1g of the resin contains a molar amount of 1X 10 ^-3 The (meth) acrylic resin is added to the resin composition in a molar ratio of at least one mole, whereby the coatability of the resin composition, the solvent resistance of the pattern (cured product), and the like can be improved.

When the resin composition of the present invention contains another resin, the content of the other resin is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, still more preferably 1 mass% or more, still more preferably 2 mass% or more, still more preferably 5 mass% or more, still more preferably 10 mass% or more, based on the total solid content of the resin composition.

The content of the other resin in the resin composition of the present invention is preferably 80 mass% or less, more preferably 75 mass% or less, still more preferably 70 mass% or less, still more preferably 60 mass% or less, still more preferably 50 mass% or less, based on the total solid content of the resin composition.

In addition, as a preferable embodiment of the resin composition of the present invention, the content of the other resin may be low. In the above aspect, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, further preferably 5% by mass or less, further preferably 1% by mass or less, relative to the total solid content of the resin composition. The lower limit of the content is not particularly limited as long as it is 0 mass% or more.

The resin composition of the present invention may contain only 1 kind of other resin or may contain 2 or more kinds. When the content is 2 or more, the total amount is preferably within the above range.

< Compound A >

The resin composition of the present invention has a urea bond and contains, as a radical polymerizable compound, a compound a having no symmetry axis, which satisfies at least one of the following conditions 1 and 2.

Condition 1: the compound A has 2 or more radical polymerizable groups.

Condition 2: the compound a has at least 1 of a hydroxyl group, an oxyalkylene group, an amide group, and a cyano group.

[ symmetry axis ]

The compound a is a compound having a structure not having a symmetry axis.

The compound a does not have a symmetry axis, and means a compound which does not have an axis that generates the same molecule as the original molecule by rotating the whole compound and is asymmetric to the left and right. In the case where the structural formula of the compound a is marked on the paper, the fact that the compound a does not have a symmetry axis means that the structural formula of the compound a cannot be marked in a form having a symmetry axis.

It is considered that by the compound a not having a symmetry axis, aggregation of the compounds a with each other in the composition film can be suppressed.

[ Urea bond ]

The urea bond contained in the compound A means a bond represented by-NR ^N -C(＝O)-NR ^N -the represented key. R is R ^N Each independently represents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, still more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

Compound a may contain 2 or more urea linkages, but a manner of containing only 1 urea linkage is also one of the preferred modes of the present invention.

[ radical polymerizable group ]

The compound A has a radical polymerizable group.

The radical polymerizable group is preferably a group having an ethylenically unsaturated bond.

Examples of the group having an ethylenically unsaturated bond include a group having a vinyl group which is directly bonded to an aromatic ring and which may be substituted, such as a vinyl group, an allyl group, and a vinyl phenyl group, a maleimide group, a (meth) acrylamide group, and a (meth) acryloyloxy group is preferable.

When the above condition 1 is satisfied, the compound a has 2 or more radical polymerizable groups. In this case, 2 or more radical polymerizable groups may have the same structure or may have different structures. The mode in which the structures of the radical polymerizable groups contained in the compound a are all the same is also one of preferred modes of the present invention.

In condition 1, the number of radical polymerizable groups is preferably 2 to 10, more preferably 2 to 4, further preferably 2 or 3, and particularly preferably 2.

In the case where the above condition 2 is satisfied, the compound a contains a radical polymerizable group and at least 1 selected from the group consisting of a hydroxyl group, an oxyalkylene group, an amide group, and a cyano group. In condition 2, the number of radical polymerizable groups contained in the compound a is 1 or more, preferably 1 to 10, more preferably 1 to 4, still more preferably 1 to 3, and particularly preferably 1 or 2.

In the case where the compound a has 2 or more radical polymerizable groups from the viewpoint of chemical resistance, a mode in which at least 1 of the 2 or more radical polymerizable groups and at least 1 other of the 2 or more radical polymerizable groups are linked by a linking group (hereinafter, also referred to as "linking group L") containing a urea bond is also one of preferred modes of the present invention.

The linking group L may be one containing a urea bond, but is preferably one containing a urea bond and a group selected from the group consisting of hydrocarbon groups, -0-, -C (=O) -, -S (=O) ₂ -、-NR ^N -a structure obtained by bonding at least 2 of the groups. R is R ^N As described above.

The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination of these.

The saturated aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, more preferably a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, and still more preferably a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms.

The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and still more preferably a group obtained by removing 2 or more hydrogen atoms from a benzene ring structure.

Of these, it is preferable that both ends of the urea bond are directly bonded to carbon atoms, more preferable that both ends of the urea bond are directly bonded to hydrocarbon groups, and still more preferable that one of both ends of the urea bond is directly bonded to an aromatic hydrocarbon group and the other is directly bonded to a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination of these, and still more preferable that one of both ends of the urea bond is directly bonded to an aromatic hydrocarbon group and the other is directly bonded to a saturated aliphatic hydrocarbon group. The preferred number of carbon atoms of the saturated aliphatic hydrocarbon group or the aromatic hydrocarbon group is as described above.

Specific examples of the linking group L are described below, but the present invention is not limited thereto. In the following specific examples, # and # each represent a bonding site to a radical polymerizable group.

[ chemical formula 29]

[ chemical formula 30]

[ hydroxy, oxyalkylene, amido or cyano ]

In the case where the above condition 2 is satisfied, the compound a has at least 1 selected from the group consisting of a hydroxyl group, an oxyalkylene group, an amide group, and a cyano group.

The hydroxyl group may be an alcoholic hydroxyl group or a phenolic hydroxyl group from the viewpoint of chemical resistance of the obtained cured film, but is preferably an alcoholic hydroxyl group.

The oxyalkylene group is preferably an oxyalkylene group having 2 to 20 carbon atoms, more preferably an oxyalkylene group having 2 to 10 carbon atoms, still more preferably an oxyalkylene group having 2 to 4 carbon atoms, further preferably an ethylene group or propylene group, and particularly preferably an ethylene group, from the viewpoint of chemical resistance of the obtained cured film.

The oxyalkylene group may be contained as a polyoxyalkylene group in the compound a. The number of repeating alkylene oxide groups in this case is preferably 2 to 10, more preferably 2 to 6.

Amide group means-C (=O) -NR ^N -the represented key. R is R ^N As described above. In the case where the compound a has an amide group, the compound a can be, for example, r—c (=o) -NR ^N The group represented by-, or: -C (=o) -NR ^N -the group represented by R is comprised. R represents a hydrogen atom or a 1-valent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group. Compound A canThe present invention is also one of preferred embodiments of the present invention, in which the structure is selected from the group consisting of a hydroxyl group, an oxyalkylene group (among them, a polyoxyalkylene group in the case of constituting a polyoxyalkylene group), an amide group and a cyano group, and the number of the structures is 2 or more in the molecule.

The hydroxyl group, the oxyalkylene group, the amide group, and the cyano group may be present at any position of the compound a, but in the case where the above condition 2 is satisfied, the case where at least 1 selected from the hydroxyl group, the oxyalkylene group, the amide group, and the cyano group in the compound a is linked to at least 1 radical polymerizable group contained in the compound a through a linking group containing a urea bond (hereinafter, also referred to as "linking group L2-1") is also one of preferred embodiments of the present invention.

In particular, in the case where the compound a contains only 1 radical polymerizable group, it is preferable that at least 1 of the radical polymerizable groups contained in the compound a is linked to at least 1 of the groups selected from the group consisting of a hydroxyl group, an oxyalkylene group, an amide group, and a cyano group through a linking group containing a urea bond (hereinafter, also referred to as "linking group L2-2").

In the case where the compound A contains an oxyalkylene group (wherein the polyoxyalkylene group is constituted) and has the above-mentioned linking group L2-1 or the above-mentioned linking group L2-2, the structure of bonding to the side of the oxyalkylene group (wherein the polyoxyalkylene group is constituted) opposite to the linking group L2-1 or the linking group L2-2 is not particularly limited, but is preferably a hydrocarbon group, a radical polymerizable group or a group represented by a combination of these. The preferred mode of the hydrocarbon group is the same as that of the hydrocarbon group in the above-mentioned linking group L. The preferable mode of the radical polymerizable group is the same as that of the radical polymerizable group in the above-mentioned compound a.

In the case where the compound A contains an amide group and has the above-mentioned linking group L2-1 or the above-mentioned linking group L2-2, the structure of the amide group bonded to the side opposite to the linking group L2-1 or the linking group L2-2 is not particularly limited, but is preferably a hydrocarbon group, a radical polymerizable group or a group represented by a combination of these. The preferred mode of the hydrocarbon group is the same as that of the hydrocarbon group in the above-mentioned linking group L. The preferable mode of the radical polymerizable group is the same as that of the radical polymerizable group in the above-mentioned compound a. In the above embodiment, the carbon atom side of the amide group may be bonded to the linking group L2-1 or the linking group L2-2, and the nitrogen atom side of the amide group may be bonded to the linking group L2-1 or the linking group L2-2.

Specific examples of the linking group L2-1 or L2-2 include the same groups as those of the linking group L. Wherein, # represents a bonding site to a structure comprising at least 1 selected from the group consisting of a hydroxyl group, an oxyalkylene group, an amide group and a cyano group in the case where the structure shown as a specific example does not comprise an oxyalkylene group, and # represents a bonding site to a structure comprising at least 1 selected from the group consisting of a hydroxyl group, an oxyalkylene group, an amide group and a cyano group or a free radical polymerizable group in the case where the structure shown as a specific example comprises an oxyalkylene group.

[ aromatic group ]

From the viewpoint of compatibility with a specific resin or the like, the compound a preferably contains an aromatic group.

The aromatic group is preferably directly bonded to the urea bond contained in the compound a. In the case where the compound a contains 2 or more urea bonds, it is preferable that 1 of the urea bonds is directly bonded to an aromatic group.

The aromatic group may be an aromatic hydrocarbon group, an aromatic heterocyclic group, or a structure in which a condensed ring is formed from these groups, but is preferably an aromatic hydrocarbon group.

The aromatic heterocyclic group is preferably a 5-membered or 6-membered aromatic heterocyclic group. Examples of the aromatic heterocyclic ring in the aromatic heterocyclic group include pyrrole, imidazole, triazole, tetrazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, and triazine. These rings may be further condensed with other rings (e.g. indole, benzimidazole), for example.

The hetero atom contained in the aromatic heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.

The aromatic group is preferably contained in the linking group L or a linking group linking at least 1 selected from the group consisting of a hydroxyl group, an oxyalkylene group, an amide group, and a cyano group, and at least 1 radical polymerizable group contained in the compound a, for example.

[ number of atoms between urea bond and radical polymerizable group (connecting chain length) ]

The number of atoms (link length) between the urea bond and the radical polymerizable group in the compound a is not particularly limited, but is preferably 30 or less, more preferably 2 to 20, and still more preferably 2 to 10.

In the case where the compound a contains 2 or more urea bonds, contains 2 or more radical polymerizable groups, or contains 2 or more urea bonds and contains 2 or more radical polymerizable groups, the smallest of the numbers of atoms (link chain lengths) between the urea bonds and the radical polymerizable groups may be within the above-described range.

In the present specification, the term "number of atoms (link length) between the urea bond and the polymerizable group" means a shortest (minimum number of atoms) chain connecting the 2 atoms or the group of atoms to be connected among the atom chains on the path between the connection targets. For example, in the structure represented by the following formula, the number of atoms (link length) between the urea bond and the radical polymerizable group (methacryloyloxy group) is 2.

[ chemical formula 31]

[ formula (1-1) or formula (1-2) ]

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

[ chemical formula 32]

in the formula (1-2), R ^P1 Represents a group comprising at least 1 radical polymerizable group, L ³ Represents a 2-valent linking group.

In the formula (1-1), R ^P1 R is R ^P2 The number of radical polymerizable groups in (a) is preferably 1 to 10, more preferably 1 to 4, and still more preferably 1 or 2.

R ^P1 R is R ^P2 The preferable mode of the radical polymerizable group in (a) is the same as that of the radical polymerizable group in the above-mentioned compound a.

R ^P1 R is R ^P2 Also preferably, each independently is a group represented by the following formula (RP-1).

[ chemical formula 33]

In the formula (RP-1), L ^RP1 Represents a single bond or a linking group having a valence of m+1, X ^RP1 Represents a radical polymerizable group, m represents an integer of 1 or more, and represents a bonding site to the urea bond in formula (1-1).

In the formula (RP-1), L ^RP1 Preferably a hydrocarbon group, -O-, -C (=O) -, -S (=O) ₂ -、-NR ^N Or those obtained by bonding more than 2, more preferably a hydrocarbon group or a hydrocarbon group with a compound selected from the group consisting of-O-, -C (=o) -, -S (=o) ₂ -and-NR ^N -a group obtained by bonding at least 1 group of the group(s). R is R ^N As described above.

And at L ^RP1 The structure adjacent to the bond site of the urea bond is preferably a hydrocarbon group.

As the L ^RP1 The hydrocarbon group in (a) is preferably a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group or a group represented by a combination of these, more preferably a saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms or a group represented by a combination of these, still more preferably a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a group obtained by removing 2 or more hydrogen atoms from a benzene ring or a group represented by these bonds.

Among these, at L ^RP1 In the case of a 2-valent linking group (m=1), L ^RP1 Preferably an alkylene group, arylene group, oxyalkylene group, alkyleneoxycarbonyl group, alkyleneurethane group, or a group obtained by combining these 2 or more.

The number of carbon atoms of the alkylene group is preferably 2 to 20, more preferably 2 to 10.

The arylene group is preferably an aromatic hydrocarbon group.

The arylene group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and more preferably a phenylene group.

The number of carbon atoms of the alkylene group contained in the oxyalkylene group, the alkyleneoxycarbonyl group or the alkylene urethane group is preferably 2 to 20, more preferably 2 to 10, respectively.

In the formula (RP-1), X ^RP1 The preferable mode of (a) is the same as that of the radical polymerizable group in the above-mentioned compound A.

In the formula (RP-1), m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, further preferably 1 or 2, and particularly preferably 1.

In the formula (1-2), R ^P1 R in formula (1-1) ^P1 The same is preferable.

In the formula (1-2), L ³ Is preferable to L in the formula (RP-1) ^RP1 The preferred manner is the same when the linking group is 2 valent (m=1).

[ molecular weight ]

The molecular weight of the compound a is preferably 100 to 2,000, more preferably 150 to 1500, and even more preferably 200 to 900.

Specific examples of the compound a include, but are not limited to, the following compounds. In the following specific examples, the subscript of the brackets indicates the number of repetitions.

[ chemical formula 34]

[ chemical formula 35]

The content of the compound a is preferably 1 to 40 mass% relative to the total solid content of the resin composition of the present invention. The lower limit is more preferably 2% by mass or more, still more preferably 3% by mass or more, and particularly preferably 5% by mass or more. The upper limit is more preferably 30 mass% or less, and still more preferably 20 mass% or less.

The compound A may be used alone or in combination of 1 or more than 2. When 2 or more kinds are used simultaneously, the total amount thereof is preferably within the above range.

< other polymerizable Compound >

The resin composition of the present invention preferably further comprises a polymerizable compound (hereinafter, also referred to as "other polymerizable compound") different from the above-described compound a.

In particular, the radically polymerizable compound preferably further contains a compound (a radical crosslinking agent described later) different from the compound a.

The other polymerizable compound is a compound having a polymerizable group, and does not correspond to the above-described compound a.

Specifically, the other polymerizable compound may include a compound having a radical polymerizable group and not having a urea bond, a compound having a radical polymerizable group and a urea bond but having a symmetry axis, and a compound having 1 radical polymerizable group and a urea bond but not having any one of a hydroxyl group, an oxyalkylene group, an amide group, and a cyano group.

The other polymerizable compound may be a radical crosslinking agent or another crosslinking agent, and preferably contains a radical crosslinking agent.

[ free radical crosslinking agent ]

The resin composition of the present invention preferably contains a radical crosslinking agent.

The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group containing an ethylenically unsaturated bond. Examples of the group containing an ethylenically unsaturated bond include a group having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, a (meth) acryloyl group, a maleimide group, and a (meth) acrylamide group.

Among these, the group containing an ethylenically unsaturated bond is preferably a (meth) acryloyl group, (meth) acrylamido group or vinylphenyl group, and more preferably a (meth) acryloyl group from the viewpoint of reactivity.

The radical crosslinking agent is preferably a compound having 1 or more ethylenically unsaturated bonds, but more preferably a compound having 2 or more. The radical crosslinking agent may have 3 or more ethylenically unsaturated bonds.

The compound having 2 or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and still more preferably a compound having 2 to 6 ethylenically unsaturated bonds.

Further, from the viewpoint of film strength of the obtained pattern (cured product), the resin composition of the present invention preferably contains a compound having 2 ethylenically unsaturated bonds and a compound having 3 or more ethylenically unsaturated bonds.

The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1, 500 or less, and further preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

Specific examples of the radical crosslinking agent include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters and amides thereof, and preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds and amides of unsaturated carboxylic acids and polyhydric amine compounds. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group, or a sulfanyl group with a monofunctional or polyfunctional isocyanate or epoxy, a dehydration condensation reaction product with a monofunctional or polyfunctional carboxylic acid, or the like may be preferably used. Also, the addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol is preferable, and the substitution reaction product of an unsaturated carboxylic acid ester or amide having a releasable substituent such as a halogen group or a tosyloxy group with a monofunctional or polyfunctional alcohol, amine or thiol is preferable. As another example, a compound group substituted with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an allyl ether, or the like may be used instead of the unsaturated carboxylic acid. For a specific example, reference is made to paragraphs 0113 to 0122 of Japanese patent application laid-open No. 2016-027357, and these are incorporated herein by reference.

The radical crosslinking agent is preferably a compound having a boiling point of 100 ℃ or higher at normal pressure. Examples thereof include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloxypropyl) ether, tris (acryloxyethyl) isocyanurate, glycerol, trimethylolethane, and the like, which are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylating them, and urethane (meth) acrylates described in Japanese patent publication Nos. 48-041708, 50-006034, 51-037193, 48-064183, 49-043191, 52-030490, and the like, as epoxy resin and (meth) acrylic acid, and the like, and epoxy acrylate or a mixture thereof. Further, the compounds described in paragraphs 0254 to 0257 of JP-A2008-292970 are also preferable. Further, a polyfunctional (meth) acrylate obtained by reacting a compound having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth) acrylate with a polyfunctional carboxylic acid, and the like can also be mentioned.

Further, as a preferable radical crosslinking agent other than the above, a compound having a fluorene ring and having 2 or more groups containing an ethylenically unsaturated bond or a cardo (cardo) resin described in japanese unexamined patent publication No. 2010-160418, japanese unexamined patent publication No. 2010-129825, japanese patent publication No. 4364216, and the like can be used.

Further, examples of the compounds include specific unsaturated compounds described in Japanese patent publication No. 46-043946, japanese patent publication No. 01-040337 and Japanese patent publication No. 01-040336, and vinyl phosphonic acid compounds described in Japanese patent publication No. 02-025493. Furthermore, a perfluoroalkyl group-containing compound described in JP-A-61-022048 can also be used. Furthermore, those described in "Journal of the Adhesion Society of Japan" vol.20, no.7, pages 300 to 308 (1984) as photopolymerizable monomers and oligomers can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of 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 are incorporated herein by reference.

In addition, in Japanese patent application laid-open No. 10-062986, a compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylating the resultant compound, which is described as a specific example of the formula (1) and the formula (2), can also be used as a radical crosslinking agent.

Further, the compounds described in paragraphs 0104 to 0131 of Japanese patent application laid-open No. 2015-187211 may be used as the radical crosslinking agent, and these contents are incorporated into the present specification.

The radical crosslinking agent is preferably dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku co., ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku co., ltd.)), a-TMMT (Shin-Nakamura Chemical co., ltd.)), dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku co., ltd.)), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku co., ltd.)), a-DPH (Shin-Nakamura Chemical co., ltd.)), and a-DPH (manufactured by Shin-Nakamura Chemical co.)), and the structures in which these (meth) acryl groups are bonded via a ethylene glycol residue or a propylene glycol residue. These oligomer types can also be used.

Examples of the commercial products of the radical crosslinking agent include SR-494, which is a 4-functional acrylate having 4 ethyleneoxy chains, made by Sartomer Company, inc, sartomer Company, which is a 2-functional methyl acrylate having 4 ethyleneoxy chains, SR-209, 231, 239, nippon Kayaku Co., ltd., DPCA-60, which is a 6-functional acrylate having 6 ethyleneoxy chains, made by Ltd., TPA-330, which is a 3-functional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS-10, UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD), NK ester M-40G, NK ester M-9328 ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., ltd.), UA-306, and PM Kyoei sha chemical-600, made by PMER-600, and so on.

As the radical crosslinking agent, urethane acrylate compounds having an ethylene oxide skeleton as described in Japanese patent application laid-open No. 48-041708, japanese patent application laid-open No. 51-037193, japanese patent application laid-open No. 02-032293, japanese patent application laid-open No. 02-016765, japanese patent application laid-open No. 58-049860, japanese patent application laid-open No. 56-017654, japanese patent application laid-open No. 62-039417, and Japanese patent application laid-open No. 62-039418 are also preferred. Further, as the radical crosslinking agent, a compound having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238 can also be used.

The radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxyl group or a phosphate group. The radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent having an acid group by reacting a non-aromatic carboxylic acid anhydride with unreacted hydroxyl groups of an aliphatic polyhydroxy compound. Particularly preferred is a radical crosslinking agent having an acid group by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound, wherein the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. As commercial products, for example, as TOAGOSEI CO., LTD. Manufactured polyacid modified acrylic oligomers, M-510, M-520 and the like are mentioned.

The radical crosslinking agent having an acid group preferably has an acid value of 0.1 to 300mgKOH/g, particularly preferably 1 to 100mgKOH/g. When the acid value of the radical crosslinking agent is within the above range, the production workability is excellent, and further the developability is excellent. And, the polymerizability is good. Regarding the above acid value, according to JISK0070: 1992.

From the viewpoints of resolution of the pattern and stretchability of the film, the resin composition preferably uses 2-functional methacrylate or acrylate.

Specific examples of the compound include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1, 5-pentanediol diacrylate, 1, 6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, bisphenol a EO (ethylene oxide) adduct diacrylate, bisphenol a EO adduct dimethacrylate, bisphenol a PO (propylene oxide) adduct diacrylate, bisphenol a PO adduct dimethacrylate, 2-hydroxy-3-acryloxypropyl methacrylate, isocyanatoEO modified diacrylate, isocyanatomodified dimethacrylate, 2-functional acrylate having other urethane bonds, and 2-functional methacrylate having urethane bonds. These may be used in combination of 2 or more kinds as required.

For example, PEG200 diacrylate refers to polyethylene glycol diacrylate, and the formula weight of the polyethylene glycol chain is about 200.

In the resin composition of the present invention, a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent from the viewpoint of suppressing warpage with control of the elastic modulus of the pattern (cured product). As the monofunctional radical crosslinking agent, N-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and other (meth) acrylic acid derivatives, N-vinyl pyrrolidone, N-vinyl caprolactam and other N-vinyl compounds, allyl glycidyl ether and the like can be preferably used. As the monofunctional radical crosslinking agent, a compound having a boiling point of 100 ℃ or higher at normal pressure is also preferable in order to suppress volatilization before exposure.

In addition, examples of the radical crosslinking agent having 2 or more functions include allyl compounds such as diallyl phthalate and triallyl trimellitate.

When the radical crosslinking agent is contained, the content thereof is preferably more than 0% by mass and 60% by mass or less relative to the total solid content of the resin composition of the present invention. The lower limit is more preferably 5 mass% or more. The upper limit is more preferably 50 mass% or less, and still more preferably 30 mass% or less.

The radical crosslinking agent may be used alone or in combination of 1 or more than 2. When 2 or more kinds are used simultaneously, the total amount thereof is preferably within the above range.

[ other crosslinking Agents ]

The resin composition of the present invention also preferably contains a crosslinking agent other than the radical crosslinking agent described above.

In the present invention, the other crosslinking agent means a crosslinking agent other than the above-mentioned radical crosslinking agent, and is preferably a compound having a plurality of groups in the molecule which promote a reaction of forming covalent bonds with other compounds in the composition or reaction products thereof by sensitization with a photoacid generator, a photobase generator or the like, and more preferably a compound having a plurality of groups in the molecule which promote a reaction of forming covalent bonds with other compounds in the composition or reaction products thereof by the action of an acid or a base.

The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.

The other crosslinking agent is preferably a compound having at least 1 group selected from the group consisting of an acyloxymethyl group, a hydroxymethyl group and an alkoxymethyl group, and more preferably a compound having a structure in which at least 1 group selected from the group consisting of an acyloxymethyl group, a hydroxymethyl group and an alkoxymethyl group is directly bonded to a nitrogen atom.

Examples of the other crosslinking agent include compounds having a structure in which formaldehyde or formaldehyde and an alcohol are reacted with an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, benzoguanamine, or the like to replace a hydrogen atom of the amino group with an acyloxymethyl group, a hydroxymethyl group, or an alkoxymethyl group. The method for producing these compounds is not particularly limited as long as they are compounds having the same structure as the compounds produced by the above method. The oligomer may be one in which methylol groups of these compounds are self-condensed with each other.

The crosslinking agent using melamine as the amino group-containing compound is referred to as a melamine-based crosslinking agent, the crosslinking agent using glycoluril, urea or alkylene urea is referred to as a urea-based crosslinking agent, the crosslinking agent using alkylene urea is referred to as an alkylene urea-based crosslinking agent, and the crosslinking agent using benzoguanamine is referred to as a benzoguanamine-based crosslinking agent.

Among these, the resin composition of the present invention preferably contains at least 1 compound selected from urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least 1 compound selected from glycoluril-based crosslinking agents and melamine-based crosslinking agents described later.

Examples of the compound containing at least 1 of an alkoxymethyl group and an acyloxymethyl group in the present invention include compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group or a nitrogen atom of the urea structure described below or a triazine.

The alkoxymethyl group or acyloxymethyl group contained in the above-mentioned compound preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms, and still more preferably 2 carbon atoms.

The total number of alkoxymethyl groups and acyloxymethyl groups in the above-mentioned compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.

The molecular weight of the above compound is preferably 1500 or less, and preferably 180 to 1200.

[ chemical formula 36]

R100 represents an alkyl group or an acyl group.

R101 and R102 each independently represent a 1-valent organic group, and may be bonded to each other to form a ring.

Examples of the compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group include various compounds represented by the following general formula.

[ chemical formula 37]

Wherein X represents a single bond or a 2-valent organic group, each R ₁₀₄ Each independently represents an alkyl group or an acyl group, R ₁₀₃ Represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a group which is decomposed by the action of an acid to produce an alkali-soluble group (e.g., a group which is detached by the action of an acid, -C (R) ⁴ ) ₂ COOR ⁵ Represented by the formula (R ⁴ R independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms ⁵ Represents a group that is detached by the action of an acid. )).

R ₁₀₅ Each independently represents an alkyl group or an alkenyl group, a, b and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less.

Regarding the group which is decomposed by the action of an acid to generate an alkali-soluble group, the group which is detached by the action of an acid, -C (R ⁴ ) ₂ COOR ⁵ R in the radicals represented ⁵ For example, there may be mentioned-C (R ₃₆ )(R ₃₇ )(R ₃₈ )、-C(R ₃₆ )(R ₃₇ )(OR ₃₉ )、-C(R ₀₁ )(R ₀₂ )(OR ₃₉ ) Etc.

Wherein R is ₃₆ ～R ₃₉ Each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R is R ₃₆ And R is R ₃₇ Can be bonded to each other to form a ring.

The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.

The alkyl group may be either a straight chain or a branched chain.

The cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and more preferably a cycloalkyl group having 3 to 8 carbon atoms.

The cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring.

The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group.

The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an aralkyl group having 7 to 16 carbon atoms.

The aralkyl group refers to an aryl group substituted with an alkyl group, and the preferable modes of the alkyl group and the aryl group are the same as those of the alkyl group and the aryl group.

The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms.

These groups may have a known substituent within a range where the effect of the present invention can be obtained.

R01 and R02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

The group which is decomposed by the action of an acid to generate an alkali-soluble group or the group which is detached by the action of an acid is preferably a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group or the like. Further preferred is a tertiary alkyl ester group and an acetal group.

Specific examples of the compound having an alkoxymethyl group include the following structures. Examples of the compound having an acyloxymethyl group include compounds in which an alkoxymethyl group of the following compound is changed to an acyloxymethyl group. Examples of the compound having an alkoxymethyl group or an acyloxymethyl group in the molecule include the following compounds, but are not limited thereto.

[ chemical formula 38]

[ chemical formula 39]

As the compound containing at least 1 of an alkoxymethyl group and an acyloxymethyl group, a commercially available compound or a compound synthesized by a known method can be used.

From the viewpoint of heat resistance, a compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring is preferable.

Specific examples of the melamine-based crosslinking agent include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine, and the like.

Specific examples of urea-based crosslinking agents include glycoluril-based crosslinking agents such as monomethylol glycoluril, dimethylol glycoluril, trimethylol glycoluril, tetramethylol glycoluril, monomethoxy methylated glycoluril, dimethoxy methylated glycoluril, trimethoxy methylated glycoluril, tetramethoxy methylated glycoluril, monoethoxy methylated glycoluril, diethoxy methylated glycoluril, triethoxy methylated glycoluril, tetraethoxy methylated glycoluril, monopropoxy methylated glycoluril, dipropoxy methylated glycoluril, tripropoxy methylated glycoluril, tetrapropoxy methylated glycoluril, monobutylox methylated glycoluril, dibutoxy methylated glycoluril, tributoxy methylated glycoluril, or tetrabutoxy methylated glycoluril;

Urea-based crosslinking agents such as dimethoxymethyl urea, diethoxymethyl urea, dipropoxymethyl urea and dibutoxymethyl urea,

Ethylene urea crosslinking agents such as monocrystaline ethylene urea or dimethylol ethylene urea, monomethoxy methylated ethylene urea, dimethoxy methylated ethylene urea, monoethoxy methylated ethylene urea, diethoxy methylated ethylene urea, monopropoxy methylated ethylene urea, dipropoxy methylated ethylene urea, monobutyl oxy methylated ethylene urea or dibutoxy methylated ethylene urea,

Propylene urea cross-linking agents such as monocrystaline propylene urea, dimethylol propylene urea, monomethoxy methylated propylene urea, dimethoxy methylated propylene urea, monoethoxy methylated propylene urea, diethoxy methylated propylene urea, monopropy methylated propylene urea, dipropoxy methylated propylene urea, monobutyl oxymetylated propylene urea or dibutoxy methylated propylene urea,

1, 3-bis (methoxymethyl) -4, 5-dihydroxy-2-imidazolidinone, 1, 3-bis (methoxymethyl) -4, 5-dimethoxy-2-imidazolidinone, and the like.

Specific examples of the benzoguanamine-based crosslinking agent include monomethylol benzoguanamine, dimethylol benzoguanamine, trimethylol benzoguanamine, tetramethylol benzoguanamine, monomethylol benzoguanamine, dimethoxymethyl benzoguanamine, trimethoxy methyl benzoguanamine, tetramethoxymethyl benzoguanamine, monoethoxymethyl benzoguanamine, diethoxymethyl benzoguanamine, triethoxymethyl benzoguanamine, tetraethoxymethyl benzoguanamine, monopropoxymethyl benzoguanamine, dipropoxymethyl benzoguanamine, tripropoxymethyl benzoguanamine, tetrapropoxymethyl benzoguanamine, monobutyloxymethyl benzoguanamine, dibutoxymethyl benzoguanamine, tributoxymethyl benzoguanamine, tetrabutoxymethyl benzoguanamine, etc.

In addition, as the compound having at least 1 group selected from the group consisting of hydroxymethyl and alkoxymethyl, a compound in which at least 1 group selected from the group consisting of hydroxymethyl and alkoxymethyl is directly bonded to an aromatic ring (preferably a benzene ring) may be preferably used.

Specific examples of such compounds include xylylene glycol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, hydroxymethyl phenyl hydroxymethyl benzoate, bis (hydroxymethyl) biphenyl, dimethyl bis (hydroxymethyl) biphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxybenzene, bis (methoxymethyl) diphenyl ether, bis (methoxymethyl) benzophenone, methoxymethyl phenyl methoxymethylbenzoate, bis (methoxymethyl) biphenyl, dimethyl bis (methoxymethyl) biphenyl, 4',4 "-ethylenetris [2, 6-bis (methoxymethyl) phenol ], 5' - [2, 2-trifluoro-1- (trifluoromethyl) ethylene ] bis [ 2-hydroxy-1, 3-benzenedimethanol ], 3', 5' -tetrakis (methoxymethyl) -1,1 '-biphenyl-4, 4' -diol, and the like.

As the other crosslinking agent, a commercially available product may be used, and as a preferable commercially available product, 46 DMOS, 46 DMOS (manufactured by ASAHI YUKIZAI CORPORATION above), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34-X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisc-P, DMOM-PC, DMM-PTBP, DMM-MBPC, triML-P, triML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPA, TML-BPAF, TMOM-BPAP, HML-TPBA, HML-TPOM-PHOM, HMOM-TPOM, PHOM-67, HMOM-TPO, PHOM-TPO (manufactured by HMP, PHOM-67) and PHO-TPO may be mentioned. Ltd), NIKALAC (registered trademark, the same as follows) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (manufactured above is Sanwa Chemical co., ltd.) and the like.

The resin composition of the present invention preferably further contains at least 1 compound selected from the group consisting of an epoxy compound, an oxetane compound and a benzoxazine compound as another crosslinking agent.

Epoxy compound (epoxy group-containing compound)

The epoxy compound is preferably a compound having 2 or more epoxy groups in one molecule. The epoxy group undergoes a crosslinking reaction at a temperature of 200 ℃ or less and does not undergo dehydration reaction due to crosslinking, and thus film shrinkage is not easily caused. Therefore, the epoxy compound is effective in suppressing low-temperature curing and warpage of the resin composition of the present invention.

The epoxy compound preferably contains a polyethylene oxide group. Thereby, the elastic modulus is further reduced, and warpage can be suppressed. The polyethylene oxide group represents a group having 2 or more repeating units of ethylene oxide, and preferably has 2 to 15 repeating units.

Examples of the epoxy compound include: bisphenol a type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, and the like, or polyhydric alcohol hydrocarbon type epoxy resins; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and epoxy group-containing silicones such as polymethyl (glycidoxypropyl) siloxane, but the present invention is not limited thereto. Specifically, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-830LVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON-665-EXP-S, EPICLON (registered trademark) N-740 (the above are trade names, DIC CORPORATION), rika Resin BEO-20E, rika Resin BEO-60E, rika Resin HBE-100, rika Resin DME-100, rika Resin L-200 (trade name, new Japan chemical Co., ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (trade name, ADEKA CORPORATION), CELLOXIDE 2021P, CELLOXIDE (trade name), CELLOXIDE 2000, EHPE3150, EPOLEAD (trade name) GT401, EPOLEAD (trade name) PB4700, EPOLEAD (trade name) PB3600 (trade name, daicel Corporation), NC-3000-L, NC-3000-H, CELLOXIDE (trade name, ADEKA CORPORATION), CELLOXIDE (trade name), CELLOIDE (trade name) 2021P, CELLOXIDE (trade name), CELLOXIDE) 2000, EPOLEAD (trade name) PB3600 (trade name, NC-3000-H, EPOLEAD (trade name) PB3600 (trade name), NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (trade name, nippon Kayaku Co., ltd.) and the like. Also, the following compounds may also be preferably used.

[ chemical formula 40]

Wherein n is an integer of 1 to 5, and m is an integer of 1 to 20.

In the above structure, from the viewpoint of both heat resistance and improvement of elongation, n is preferably 1 to 2, and m is preferably 3 to 7.

Oxetane compounds (compounds having oxetanyl groups)

Examples of oxetane compounds include compounds having 2 or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1, 4-bis { [ (3-ethyl-3-oxetanyl) methoxy ] methyl } benzene, 3-ethyl-3- (2-ethylhexyl methyl) oxetane, 1, 4-benzenedicarboxylic acid-bis [ (3-ethyl-3-oxetanyl) methyl ] ester, and the like. Specifically, TOAGOSEI CO., LTD. ARON OXETANE series (e.g., OXT-121, OXT-221) may be preferably used, and these may be used singly or in combination of 2 or more.

Benzoxazine compound (compound having benzoxazolyl group)

Regarding the benzoxazine compound, it is preferable because the crosslinking reaction is caused by the ring-opening addition reaction, no degassing is generated at the time of curing, and the heat shrinkage is further reduced to suppress the generation of warpage.

Preferable examples of the benzoxazine compound include P-d type benzoxazine, F-a type benzoxazine, (trade name is Shikoku Chemicals Corporation, above), benzoxazine adducts of polyhydroxystyrene resins, and novolak type dihydrobenzoxazine compounds. These may be used singly or in combination of 2 or more.

The content of the other crosslinking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass, relative to the total solid content of the resin composition of the present invention. The other crosslinking agent may be contained only in 1 kind, or may be contained in 2 or more kinds. When the amount of the other crosslinking agent is 2 or more, the total amount is preferably within the above range.

[ polymerization initiator ]

The resin composition of the present invention contains a radical polymerization initiator. The radical polymerization initiator is preferably a radical polymerization initiator capable of initiating polymerization by light and/or heat. In particular, it is preferable to include a photo radical polymerization initiator.

The photo radical polymerization initiator is not particularly limited, and may be appropriately selected from known photo radical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays ranging from the ultraviolet region to the visible region is preferable. The active agent may be an active agent that generates an active radical by reacting with a photosensitizing agent that is excited by light.

The photo radical polymerization initiator preferably contains at least 1 initiator having a molecular weight of at least about 50 L.mol in the wavelength range of about 240 to 800nm (preferably 330 to 500 nm) ^-1 ·cm ^-1 A compound having a molar absorptivity. The molar absorptivity of the compound can be measured by a known method. For example, it is preferable to conduct the measurement by an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Co.) and using an ethyl acetate solvent at a concentration of 0.01 g/L.

As the photo radical polymerization initiator, a known compound can be arbitrarily used. Examples thereof include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, and the like), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbisimidazole, oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α -amino ketone compounds such as aminoacetophenone, α -hydroxy ketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron arene complexes. For details of these, reference is made to paragraphs 0165 to 0182 of Japanese unexamined patent publication No. 2016-027357 and paragraphs 0138 to 0151 of International publication No. 2015/199219, which are incorporated herein by reference. Examples of the initiator include a compound described in paragraphs 0065 to 0111 of Japanese patent application laid-open No. 2014-130173, a compound described in Japanese patent application laid-open No. 6301489, a peroxide-based photopolymerization initiator described in MATERIAL STAGE to 60p, vol.19, no.3, 2019, a photopolymerization initiator described in International publication No. 2018/221177, a photopolymerization initiator described in International publication No. 2018/110179, a photopolymerization initiator described in Japanese patent application laid-open No. 2019-043864, a photopolymerization initiator described in Japanese patent application laid-open No. 2019-044030, and a peroxide-based initiator described in Japanese patent application laid-open No. 2019-167313, and these are incorporated herein.

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

In one embodiment of the present invention, as the photo radical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be preferably used. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969 or an acylphosphine oxide initiator described in JP-A-4225898 can be used, and this content is incorporated into the present specification.

As the alpha-hydroxyketone initiator, omnitad 184, omnitad 1173, omnitad 2959, omnitad 127 (the above is made by the company of IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127 (trade name: all made by the company of BASF) can be used.

As the α -aminoketone initiator, omnirad 907, omnirad 369E, omnirad 379EG (the above are manufactured by IGM Resins B.V. Co.), IRGACURE 907, IRGACURE 369 and IRGACURE 379 (trade names: all manufactured by BASF Co.) can be used.

As the aminoacetophenone initiator, a compound described in japanese patent application laid-open No. 2009-191179 having a maximum absorption wavelength matching a light source having a wavelength of 365nm or 405nm or the like can be used, and this content is incorporated into the present specification.

Examples of the acylphosphine oxide initiator include 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide and the like. As the catalyst, omnirad 819, omnirad TPO (manufactured by IGM Resins B.V. Co., ltd.), IRGACURE-819 or IRGACURE-TPO (manufactured by BASF Co., ltd.) can be used.

Examples of the metallocene compound include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF corporation), keycure VIS 813 (manufactured by King Brother Chem corporation), and the like.

As the photo radical polymerization initiator, an oxime compound can be more preferably exemplified. By using an oxime compound, exposure latitude can be more effectively improved. The oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also functions as a photocuring accelerator.

Specific examples of the oxime compound include a compound described in Japanese patent application laid-open No. 2001-233836, a compound described in Japanese patent application laid-open No. 2000-080068, a compound described in Japanese patent application laid-open No. 2006-342166, a compound described in J.C.S.Perkin II (1979, pp.1653-1660), a compound described in J.C.S.Perkin II (1979, pp.156-162), and Journal of Photopolymer Science and Technology (1995, 202-232), a compound described in japanese patent application laid-open No. 2000-066385, a compound described in japanese patent application laid-open No. 2004-534797, a compound described in japanese patent application laid-open No. 2017-019766, a compound described in japanese patent application No. 6065596, a compound described in international publication No. 2015/152153, a compound described in international publication No. 2017/051680, a compound described in japanese patent application laid-open No. 2017-198865, a compound described in paragraphs 0025-0038 of international publication No. 2017/164127, a compound described in international publication No. 2013/167515, and the like, and the contents thereof are incorporated into the present specification.

Examples of the preferable oxime compound include 3- (benzoyloxy (imino)) butan-2-one, 3- (acetoxy (imino)) butan-2-one, 3- (propionyloxy (imino)) butan-2-one, 2- (acetoxy (imino)) pentan-3-one, 2- (acetoxy (imino)) -1-phenylpropane-1-one, 2- (benzoyloxy (imino)) -1-phenylpropane-1-one, 3- ((4-toluenesulfonyloxy) imino) butan-2-one, and 2- (ethoxycarbonyloxy (imino)) -1-phenylpropane-1-one having the following structure. In the resin composition of the present invention, an oxime compound (oxime-based photo radical polymerization initiator) is particularly preferably used as the photo radical polymerization initiator. The oxime-based photo-radical polymerization initiator has a linking group of > c=n-O-C (=o) -in the molecule.

[ chemical formula 41]

Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above is manufactured by BASF corporation), and ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, japanese patent application laid-open No. 2012-014052) may be preferably used. In addition, TR-PBG-304, TR-PBG-305 (Changzhou Tronly New Electronic Materials CO., LTD.; manufactured by LTD.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used. Further, DFI-091 (DAITO CHEMIX Co., ltd.) and SpeedCure PDO (SARTOMER ARKEMA) can be used. Furthermore, an oxime compound having the following structure can also be used.

[ chemical formula 42]

As the photo radical polymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include a compound described in japanese patent application laid-open No. 2014-137466 and a compound described in japanese patent No. 6636081, and the contents thereof are incorporated into the present specification.

As the photo radical polymerization initiator, an oxime compound having a skeleton in which at least 1 benzene ring in the carbazole ring becomes a naphthalene ring can also be used. Specific examples of such oxime compounds include those described in international publication No. 2013/083505, which is incorporated herein by reference.

Furthermore, an oxime compound having a fluorine atom can also be used. Specific examples of such oxime compounds include compounds described in JP 2010-26261028A, compounds 24, 36 to 40 described in paragraph 0345 of JP 2014-500852A, and compound (C-3) described in paragraph 0101 of JP 2013-164471A, and the like, and the contents of these compounds are incorporated in the present specification.

As the photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is also preferably provided as a dimer. Specific examples of the oxime compound having a nitro group include compounds described in paragraphs 0031 to 0047 of Japanese patent application laid-open No. 2013-114249, paragraphs 0008 to 0012 of Japanese patent application laid-open No. 2014-137466, and paragraphs 0070 to 0079, and compounds described in paragraphs 0007 to 0025 of Japanese patent application laid-open No. 4223071, and the contents thereof are incorporated herein. Further, as the oxime compound having a nitro group, ADEKA ARKLS NCI-831 (ADEKA CORPORATION) can be mentioned.

As the photo radical polymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples thereof include OE-01 to OE-75 described in International publication No. 2015/036910.

As the photo radical polymerization initiator, an oxime compound in which a substituent having a hydroxyl group is bonded to the carbazole skeleton can also be used. Examples of such photopolymerization initiators include compounds described in international publication No. 2019/088055, and the contents of which are incorporated herein by reference.

As the photopolymerization initiator, an aromatic ring group Ar having an electron withdrawing group introduced into the aromatic ring can also be used ^OX1 An oxime compound (hereinafter, also referred to as oxime compound OX). Ar as the above aromatic ring group ^OX1 Examples of the electron withdrawing group include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group, and an acyl group and a nitro group are preferable, and an acyl group is more preferable, and a benzoyl group is further preferable, since a film excellent in light resistance is easily formed. The benzoyl group may have a substituent. As the substituent, a halogen atom, cyano group, nitro group, hydroxyl group, alkyl group, alkoxy group, and aryl group are preferable A group, aryloxy group, heterocyclic oxy group, alkenyl group, alkylthio group, arylthio group, acyl group or amino group, more preferably an alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group or amino group, still more preferably an alkoxy group, alkylthio group or amino group.

The oxime compound OX is preferably at least 1 selected from the group consisting of a compound represented by the formula (OX 1) and a compound represented by the formula (OX 2), and more preferably a compound represented by the formula (OX 2).

[ chemical formula 43]

Wherein R is ^X1 Represents alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclyl, heterocyclyloxy, alkylthio, arylthio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acyl, acyloxy, amino, phosphono (phosphinoyl), carbamoyl or sulfamoyl,

R ^X2 represents alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclyl, heterocyclyloxy, alkylthio, arylthio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acyloxy or amino,

R ^X ～R ^X14 each independently represents a hydrogen atom or a substituent.

Wherein R is ^X10 ～R ^X14 At least 1 of which is an electron withdrawing group.

In the above formula, R is preferably ^X12 R is an electron withdrawing group ^X10 、R ^X11 、R ^X13 、R ^X14 Is a hydrogen atom.

Specific examples of the oxime compound OX include compounds described in paragraphs 0083 to 0105 of japanese patent No. 4600600, which are incorporated herein by reference.

Examples of the most preferable oxime compound include an oxime compound having a specific substituent shown in japanese patent application laid-open No. 2007-269779, an oxime compound having a thioaryl group shown in japanese patent application laid-open No. 2009-191061, and the like, and this content is incorporated into the present specification.

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

Further preferred photo-radical polymerization initiators are trihalomethyltriazine compounds, α -amino ketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, acetophenone compounds, more preferred at least 1 compound selected from trihalomethyltriazine compounds, α -amino ketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, benzophenone compounds, and even more preferred use of metallocene compounds or oxime compounds.

The photo radical polymerization initiator may be a benzoin ether compound such as benzophenone, N ' -tetramethyl-4, 4' -diaminobenzophenone (Michler's ketone), a benzoin compound such as benzoin, alkyl benzoin, or benzyl derivative such as benzyl dimethyl ketal, or an aromatic ketone such as N, N ' -tetraalkyl-4, 4' -diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinophenone-1, or an alkylanthraquinone formed by shrinking an aromatic ring with an aromatic ring. In addition, a compound represented by the following formula (I) can be used.

[ chemical formula 44]

In the formula (I), R ^I00 Is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by 1 or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by 1 or more oxygen atoms, or a phenyl or biphenyl group substituted by at least 1 of an alkyl group having 1 to 4 carbon atoms, R ^I01 Is a group represented by formula (II) or is a group represented by the formula R ^I00 The same radicals R ^I02 ～R ^I04 Each independently represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.

[ chemical formula 45]

Wherein R is ^I05 ～R ^I07 R is the same as the R of the formula (I) ^I02 ～R ^I04 The same applies.

The photo radical polymerization initiator may be any one described in paragraphs 0048 to 0055 of International publication No. 2015/125469, incorporated herein by reference.

As the photo radical polymerization initiator, a 2-functional or 3-functional or more photo radical polymerization initiator can be used. By using such a photo radical polymerization initiator, 2 or more radicals are generated from 1 molecule of the photo radical polymerization initiator, and thus good sensitivity can be obtained. In addition, when a compound having an asymmetric structure is used, crystallinity is reduced, and solubility in a solvent or the like is improved, and it becomes difficult to deposit with time, so that stability with time of the resin composition can be improved. Specific examples of the 2-functional or 3-functional or more photo-radical polymerization initiator include the photoinitiators described in Japanese patent application publication No. 2010-527339, japanese patent application publication No. 2011-524436, international publication No. 2015/004565, the dimers of oxime compounds described in Japanese patent application publication No. 0407-0412, international publication No. 2017/033680, 0039-0055, the compounds (E) and (G) described in Japanese patent application publication No. 2013-522445, cmpd 1-7 described in International publication No. 2016/034963, the oxime ester photoinitiators described in Japanese patent application publication No. 0007, the photoinitiators described in Japanese patent application publication No. 0020-167399, the photoinitiators described in Japanese patent application publication No. 2017-0033, the photopolymerization initiators (A) described in International publication No. 2017-151342, and the oxime ester photoinitiators described in Japanese patent application publication No. 6469669, and the like, and the disclosure of the initiators are incorporated herein.

The content of the radical polymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.5 to 15% by mass, and still 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 be contained in an amount of 1 or 2 or more. When the photopolymerization initiator is contained in an amount of 2 or more, the total amount is preferably within the above range.

In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, the photopolymerization initiator may be further crosslinked by heating in an oven, a hot plate, or the like.

[ sensitizer ]

The resin composition may include a sensitizer. The sensitizer absorbs a specific active radiation to be in an electron-excited state. The sensitizer in an electron excited state is brought into contact with a thermal radical polymerization initiator, a photo radical polymerization initiator, or the like, thereby causing the effects of electron transfer, energy transfer, heat generation, or the like. Thus, the thermal radical polymerization initiator and the photo radical polymerization initiator cause chemical changes to decompose and generate radicals, acids or bases.

As the sensitizer that can be used, compounds such as benzophenone-based, mi ketone-based, coumarin-based, pyrazole azo-based, anilinoazo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azo methine-based, xanthene-based, phthalocyanine-based, benzopyran-based, and indigo-based can be used.

As a sensitizer, a compound used as a sensitizer, examples thereof include Michler's ketone, 4' -bis (diethylamino) benzophenone, 2, 5-bis (4 '-diethylaminobenzylidene) cyclopentane, 2, 6-bis (4' -diethylaminobenzylidene) cyclohexanone, 2, 6-bis (4 '-diethylaminobenzylidene) -4-methylcyclohexanone, 4' -bis (dimethylamino) chalcone, 4 '-bis (diethylamino) chalcone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenyl-biphenylene) -benzothiazole 2- (p-dimethylaminophenylvinylene) benzothiazole, 2- (p-dimethylaminophenylvinylene) isonaphthothiazole, 1, 3-bis (4' -dimethylaminobenzylidene) propanone, 1, 3-bis (4 '-diethylaminobenzylidene) propanone, 3' -carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7- (diethylamino) coumarin-3-carboxylic acid ethyl ester), N-phenyl-N ' -ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinylbenzophenone, isopentyl dimethylaminobenzoate, isopentyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole, 2- (p-dimethylaminostyryl) naphtho (1, 2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4' -dimethylacetoaniline, and the like.

And, other sensitizing dye may be used.

For details of the sensitizing dye, reference is made to paragraphs 0161 to 0163 of Japanese patent application laid-open No. 2016-027357, which is incorporated herein by reference.

When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass, based on the total solid content of the resin composition. The sensitizer may be used alone or in combination of at least 2 kinds.

[ chain transfer agent ]

The resin composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in pages 683 to 684 of the third edition of the Polymer dictionary (society of Polymer (The Society of Polymer Science, japan) 2005). As the chain transfer agent, for example, a chain transfer agent having-S-, -SO within the molecule can be used ₂ -S-, -N-O-, SH, PH, siH and GeH, dithiobenzoate having a thiocarbonylthio group for RAFT (Reversible Addition Fragmentation chain Transfer: reversible addition fragmentation chain transfer) polymerization, trithiocarbonate, dithiocarbamate, xanthate (Xanthate) compounds, and the like. These low-activity radicals can be supplied with hydrogen to generate radicals or can be able to generate radicals by deprotonation after being oxidized. In particular, a thiol compound can be preferably used.

The chain transfer agent may be any of those described in paragraphs 0152 to 0153 of International publication No. 2015/199219, incorporated herein by reference.

When the resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the total solid content of the resin composition of the present invention. The chain transfer agent may be 1 or 2 or more. When the chain transfer agent is 2 or more, the total amount thereof is preferably within the above range.

< alkaline Forming agent >

The resin composition of the present invention may contain an alkaline generator. Here, the alkaline generator refers to a compound capable of generating a base by physical or chemical action. Examples of the alkali generator which is preferable for the resin composition of the present invention include a thermal alkali generator and a photobase generator.

In particular, in the case where the resin composition contains a precursor of the cyclized resin, the resin composition preferably contains an alkaline generator. By containing the thermal alkaline generator in the resin composition, for example, cyclization reaction of the precursor can be promoted by heating, and mechanical properties and chemical resistance of the cured product are improved, and for example, performance as an interlayer insulating film for a rewiring layer included in a semiconductor package is improved.

The alkaline generator may be an ionic alkaline generator or a nonionic alkaline generator. Examples of the base generated from the alkaline generator include secondary amines and tertiary amines.

The alkaline generator according to the present invention is not particularly limited, and a known alkaline generator can be used. Examples of the known alkaline generator include carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, carboxamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α -aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α -lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, and acyloxyimino compounds.

Specific examples of the nonionic alkaline generator include compounds represented by the formula (B1), the formula (B2) and the formula (B3).

[ chemical formula 46]

Rb in the formulae (B1) and (B2) ¹ 、Rb ² Rb ³ Each independently is an organic group having no tertiary amine structure, a halogen atom or a hydrogen atom. Wherein Rb ¹ Rb ² And not simultaneously become hydrogen atoms. And Rb ¹ 、Rb ² Rb ³ None of them has a carboxyl group. In the present specification, the tertiary amine structure means 3 of nitrogen atoms having a valence of 3The bonds are covalently bonded to hydrocarbon carbon atoms. Therefore, the case where the bonded carbon atom is a carbonyl group-forming carbon atom, that is, an amide group is formed together with a nitrogen atom, is not limited thereto.

Rb in the formulae (B1) and (B2) ¹ 、Rb ² Rb ³ Preferably at least 1 of them comprises a cyclic structure, more preferably at least 2 comprise a cyclic structure. The cyclic structure may be any of a single ring and a condensed ring, and is preferably a condensed ring obtained by condensing a single ring or 2 single rings. The monocyclic ring is preferably a 5-membered ring or a 6-membered ring, more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring and a benzene ring, and more preferably a cyclohexane ring.

More specifically, rb ¹ Rb ² Preferably a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), or an aralkyl group (preferably having 7 to 25 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12 carbon atoms). These groups may have substituents within a range that exerts the effects of the present invention. Rb (Rb) ¹ With Rb ² Can be bonded to each other to form a ring. The ring to be formed is preferably a 4-to 7-membered nitrogen-containing heterocycle. Rb (Rb) ¹ Rb ² Particularly, a linear, branched or cyclic alkyl group which may have a substituent (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), a cycloalkyl group which may have a substituent (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), and a cyclohexyl group which may have a substituent are preferable.

As Rb ³ Examples thereof include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 6 carbon atoms), an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 10 carbon atoms)7 to 12), an aralkenyl group (preferably having 8 to 24 carbon atoms, more preferably 8 to 20 carbon atoms, still more preferably 8 to 16 carbon atoms), an alkoxy group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an aryloxy group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12 carbon atoms) or an aralkoxy group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12 carbon atoms). Among them, 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 aralkoxy groups are preferable. Rb (Rb) ³ Substituents may be further contained within the range where 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 47]

In the formula, rb ¹¹ Rb ¹² And Rb ³¹ Rb ³² Respectively with Rb in formula (B1) ¹ Rb ² Meaning the same.

Rb ¹³ The substituent may be contained in the range of the effect of the present invention, for example, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12). Wherein Rb ¹³ Aralkyl groups are preferred.

Rb ³³ Rb ³⁴ Each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, still more preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), an aralkyl group (preferably having 7 to 23 carbon atoms, still more preferably 7 to 19, more preferably 7 to 11), preferably a hydrogen atom.

Rb ³⁵ The alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), the alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, still more preferably 3 to 8 carbon atoms), the aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12 carbon atoms), the aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12 carbon atoms), and preferably the aryl group.

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

[ chemical formula 48]

Rb ¹¹ Rb ¹² And Rb in formula (B1-1) ¹¹ Rb ¹² Meaning the same.

Rb ¹⁵ Rb ¹⁶ The examples include a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 11 carbon atoms), and a hydrogen atom or a methyl group.

Rb ¹⁷ The aromatic group is preferably an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, still more preferably 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12 carbon atoms), an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12 carbon atoms), or an aryl group.

[ chemical formula 49]

In the formula (B3), L represents a hydrocarbon group which is a 2-valent hydrocarbon group having a saturated hydrocarbon group on the path of a connecting chain connecting adjacent oxygen atoms and carbon atoms, and the number of atoms on the path of the connecting chain is 3 or more. And R is ^N1 R is R ^N2 Each independently represents a 1-valent organic group.

In the present specification, the term "link chain" refers to a chain that connects the connection objects in the shortest (minimum number of atoms) manner among atom chains on a path between 2 atoms or connection atom groups that connect the connection objects. For example, in a compound represented by the following formula, L is composed of a phenylene ethylene group and has an ethylene group as a saturated hydrocarbon group, the connecting chain is composed of 4 carbon atoms, and the number of atoms on the path of the connecting chain (i.e., the number of atoms constituting the connecting chain, hereinafter, also referred to as "connecting chain length" or "connecting chain length") is 4.

[ chemical formula 50]

The number of carbon atoms in L of the formula (B3) (also including carbon atoms other than the carbon atoms in the connecting chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, still more preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. The upper limit of the length of the linking chain of L is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and particularly preferably 5 or less, from the viewpoint of rapidly carrying out the above intramolecular cyclization reaction. In particular, the link chain length of L is preferably 4 or 5, most preferably 4. Specific preferable compounds of the alkaline generator include, for example, those described in paragraphs 0102 to 0168 of International publication No. 2020/066416 and those described in paragraphs 0143 to 0177 of International publication No. 2018/038002.

The alkaline generator preferably also contains a compound represented by the following formula (N1).

[ chemical formula 51]

In the formula (N1), R ^N1 R is R ^N2 Each independently represents a 1-valent organic group, R ^C1 Represents a hydrogen atom or a protecting group, and L represents a 2-valent linking group.

L is a 2-valent linking group, preferably a 2-valent organic group. The length of the linking chain of the linking group is preferably 1 or more, more preferably 2 or more. The upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The link chain length refers to the number of atoms present in the atomic arrangement that becomes the shortest path between 2 carbonyl groups in the formula.

In the formula (N1), R ^N1 R is R ^N2 The organic groups each independently represent a 1-valent organic group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), preferably a hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 10 carbon atoms), specifically, an aliphatic hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 10 carbon atoms) or an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), preferably an aliphatic hydrocarbon group. As R ^N1 R is R ^N2 If an aliphatic hydrocarbon group is used, the alkali generated is preferably highly basic. The aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in the substituent in the aliphatic hydrocarbon chain or in the aromatic ring. In particular, an aliphatic hydrocarbon group having an oxygen atom in a hydrocarbon chain can be exemplified.

As a constituent R ^N1 R is R ^N2 Examples of the aliphatic hydrocarbon group include a linear or branched chain alkyl group, a cyclic alkyl group, a group related to a combination of a chain alkyl group and a cyclic alkyl group, and an alkyl group having an oxygen atom in the chain. The linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms. Examples of the linear or branched alkyl group include methyl methacrylateA group, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl and the like.

The cyclic alkyl group is preferably a group having 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. Examples of the cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.

The group related to the combination of the chain alkyl group and the cyclic alkyl group is preferably a group having 4 to 24 carbon atoms, more preferably 4 to 18, and still more preferably 4 to 12. Examples of the group related to the combination of the chain alkyl group and the cyclic alkyl group include cyclohexylmethyl group, cyclohexylethyl group, cyclohexylpropyl group, methylcyclohexylmethyl group, ethylcyclohexylethyl group, and the like.

The alkyl group having an oxygen atom in the chain is preferably a group having 2 to 12 carbon atoms, more preferably 2 to 6, and still more preferably 2 to 4. The alkyl group having an oxygen atom in the chain may be a chain or a ring, and may be a straight chain or a branched chain.

Wherein R is from the viewpoint of increasing the boiling point of a base formed by decomposition to be described later ^N1 R is R ^N2 Alkyl groups having 5 to 12 carbon atoms are preferable. Among them, in the formulation in which adhesion is important when the layer is laminated with a metal (for example, copper), a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable.

R ^N1 R is R ^N2 Can be connected with each other to form a ring structure. When the cyclic structure is formed, an oxygen atom or the like may be present in the chain. And R is ^N1 R is R ^N2 The cyclic structure may be a single ring or a condensed ring, but is preferably a single ring. The cyclic structure to be formed is preferably a 5-or 6-membered ring containing a nitrogen atom in the formula (N1), and examples thereof include a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolidine ring, a pyrazolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring, and examples thereof include a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring.

R ^C1 Represents a hydrogen atom or a protecting group, preferably a hydrogen atom.

The protecting group is preferably a protecting group which is decomposed by the action of an acid or a base, and examples thereof include protecting groups which are decomposed with an acid.

Specific examples of the protecting group include a chain or cyclic alkyl group or a chain or cyclic alkyl group having an oxygen atom in the chain. Examples of the chain or cyclic alkyl group include methyl, ethyl, isopropyl, t-butyl, and cyclohexyl. The chain alkyl group having an oxygen atom in the chain includes, specifically, an alkyloxyalkyl group, more specifically, a methoxymethyl (MOM) group, an ethoxyethyl (EE) group, and the like. Examples of the cyclic alkyl group having an oxygen atom in the chain include an epoxy group, a glycidyl group, an oxetanyl group, a tetrahydrofuranyl group, and a Tetrahydropyran (THP) group.

The 2-valent linking group constituting L is not particularly limited, but is preferably a hydrocarbon group, and more preferably an aliphatic hydrocarbon group. The hydrocarbon group may have a substituent, and may also have an atom of a kind other than carbon atoms in the hydrocarbon chain. More specifically, the hydrocarbon linking group is preferably a 2-valent hydrocarbon linking group which may have an oxygen atom in the chain, more preferably a 2-valent aliphatic hydrocarbon group which may have an oxygen atom in the chain, a 2-valent aromatic hydrocarbon group, or a group related to a combination of a 2-valent aliphatic hydrocarbon group which may have an oxygen atom in the chain and a 2-valent aromatic hydrocarbon group, and still more preferably a 2-valent aliphatic hydrocarbon group which may have an oxygen atom in the chain. These groups preferably do not have an oxygen atom.

The hydrocarbon linking group having 2 valences is preferably a group having 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and still more preferably 2 to 6 carbon atoms. The aliphatic hydrocarbon group having 2 valences is preferably a group having 1 to 12 carbon atoms, more preferably 2 to 6, and still more preferably 2 to 4. The 2-valent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and still more preferably 6 to 10 carbon atoms. The group (for example, an arylene alkyl group) related to the combination of the aliphatic hydrocarbon group having 2 valences and the aromatic hydrocarbon group having 2 valences is preferably a group having 7 to 22 carbon atoms, more preferably 7 to 18 carbon atoms, and still more preferably 7 to 10 carbon atoms.

The linking group L is specifically preferably a linear or branched chain alkylene group, a cyclic alkylene group, a group related to a combination of a chain alkylene group and a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a linear or branched chain alkenylene group, a cyclic alkenylene group, an arylene group, or an arylene alkylene group.

The linear or branched chain alkylene group is preferably a group having 1 to 12 carbon atoms, more preferably 2 to 6, and still more preferably 2 to 4.

The cyclic alkylene group is preferably a group having 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.

The group related to the combination of the chain alkylene group and the cyclic alkylene group is preferably a group having 4 to 24 carbon atoms, more preferably 4 to 12, and still more preferably 4 to 6.

The alkylene group having an oxygen atom in the chain may be a chain or a ring, and may be a straight chain or a branched chain. The alkylene group having an oxygen atom in the chain is preferably a group having 1 to 12 carbon atoms, more preferably 1 to 6, and still more preferably 1 to 3.

The linear or branched alkenyl group is preferably a group having 2 to 12 carbon atoms, more preferably 2 to 6, and still more preferably 2 to 3. The number of c=c bonds of the linear or branched chain alkenylene group is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 3.

The cyclic alkenylene group is preferably a group having 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. The number of c=c bonds of the cyclic alkenylene group is preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 to 2.

The arylene group is preferably a group having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and still more preferably 6 to 10 carbon atoms.

The arylene alkylene group is preferably a group having 7 to 23 carbon atoms, more preferably 7 to 19, and still more preferably 7 to 11.

Among them, preferred are a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkenylene group, an arylene group, and an alkylene group, and more preferred are a 1, 2-ethylene group, a propane diyl group (particularly a 1, 3-propane diyl group), a cyclohexane diyl group (particularly a 1, 2-cyclohexane diyl group), a vinylene group (particularly a cis-vinylene group), a phenylene group (1, 2-phenylene group), a phenylene methylene group (particularly a 1, 2-phenylene methylene group), and an oxyethylene group (particularly a 1, 2-oxyethylene-1, 2-ethylene group).

The following examples are given as examples of the alkaline generator, but the present invention should not be construed as being limited thereby.

[ chemical formula 52]

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

Specific preferable examples of the ionic alkali generator include compounds described in paragraphs 0148 to 0163 of International publication No. 2018/038002.

Specific examples of the ammonium salt include the following compounds, but the present invention is not limited thereto.

[ chemical formula 53]

Specific examples of the imide salt include the following compounds, but the present invention is not limited thereto.

[ chemical formula 54]

In the case where the resin composition of the present invention contains an alkaline generator, the content of the alkaline generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition of the present invention. The lower limit is more preferably 0.3 parts by mass or more, and still more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or may be 4 parts by mass or less.

The alkaline generator can be used in an amount of 1 or 2 or more. When 2 or more types are used, the total amount is preferably within the above range.

< 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 esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, alcohols, and the like.

Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, gamma-butyrolactone, epsilon-caprolactone, delta-valerolactone, alkyl alkoxyacetate (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-alkoxypropionate (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionate (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-ethoxymethyl, ethyl 2-ethoxypropionate)), 2-alkoxy-2-methyl propionate, 2-methyl 2-alkoxypropionate, 2-methyl ethyl 2-ethoxypropionate, 2-methyl 2-ethoxypropionate, etc.), methyl 2-alkoxypropionate, etc. (e.g., methyl 2-ethoxypropionate, etc.), ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl caproate, ethyl heptanoate, dimethyl malonate, diethyl malonate, and the like.

Examples of the ethers include ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, dipropylene glycol dimethyl ether, and the like.

Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-methylcyclohexanone, levoglucosone, and dihydroglucan ketone.

Examples of the cyclic hydrocarbon include aromatic hydrocarbons such as toluene, xylene, anisole, and cyclic terpenes such as limonene.

Examples of the sulfoxide include dimethyl sulfoxide.

The amide may preferably be N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, N-dimethylisobutyramide, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine, or the like.

Preferred examples of the urea include N, N, N ', N' -tetramethylurea and 1, 3-dimethyl-2-imidazolidone.

Examples of the alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monoethyl glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monopropylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl glycol monobenzyl ether, ethylene glycol monoethyl glycol monophenyl ether, methyl phenyl methanol, n-amyl alcohol, methyl amyl alcohol, diacetone alcohol, and the like.

The solvent is preferably mixed with 2 or more types from the viewpoint of improvement of the properties of the coated surface.

In the present invention, it is preferable that the solvent be 1 solvent or a mixed solvent of 2 or more solvents selected from 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 acetate, levoglucosan, and dihydroglucosan. It is particularly preferred to use dimethyl sulfoxide and gamma-butyrolactone simultaneously or N-methyl-2-pyrrolidone and ethyl lactate simultaneously.

The solvent content is preferably 5 to 80% by mass, more preferably 5 to 75% by mass, still more preferably 10 to 70% by mass, and still more preferably 20 to 70% by mass, of the total solid content concentration of the resin composition of the present invention from the viewpoint of coatability. The solvent content may be adjusted according to the desired thickness of the coating film and the coating method.

The resin composition of the present invention may contain only 1 solvent, or may contain 2 or more solvents. When the solvent is contained in an amount of 2 or more, the total amount is preferably within the above range.

< Metal adhesion improver >

The resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to a metal material used for an electrode, wiring, or the like. Examples of the metal adhesion improving agent include a silane coupling agent having an alkoxysilyl group, an aluminum-based adhesion promoter, a titanium-based adhesion promoter, a compound having a sulfonamide structure, a compound having a thiourea structure, a phosphoric acid derivative compound, a β -keto ester compound, an amino compound, and the like.

[ silane coupling agent ]

Examples of the silane coupling agent include a compound described in paragraph 0167 of Japanese patent application laid-open 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 patent application laid-open 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. 2014-04264, a compound described in paragraph 0055 of International patent application laid-open No. 2014/097594, and a compound described in paragraphs 0067 to 0078 of Japanese patent application laid-open No. 2018-173573, and these are incorporated into the present specification. Further, as described in paragraphs 0050 to 0058 of JP 2011-128358, it is also preferable to use 2 or more different silane coupling agents. The silane coupling agent is preferably the following compound. In the following formula, me represents methyl group, and Et represents ethyl group.

[ chemical formula 55]

Examples of the other silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylidenepropylamine, N-phenyl-3-aminopropyltrimethoxysilane, triethoxysilyl-3- (trimethoxypropyl) 3-methoxypropyl-ureido-3-methoxypropyltrimethoxysilane, mercapto-propyl-3-ethoxypropyl silane, mercapto-3-propyl-ethoxypropyl silane, 3-trimethoxysilylpropyl succinic anhydride. These can be used singly or in combination of 1 or more than 2.

[ aluminum series adhesive auxiliary agent ]

Examples of the aluminum-based adhesive auxiliary agent include aluminum tris (ethylacetoacetate), aluminum tris (acetylacetonate), aluminum ethylacetoacetate diisopropoxide, and the like.

Further, as other metal adhesion improvers, compounds described in paragraphs 0046 to 0049 of JP-A2014-186186 and sulfide-based compounds described in paragraphs 0032 to 0043 of JP-A2013-072935 can be used, and these are incorporated into the present specification.

The content of the metal adhesion improver is preferably in the range of 0.1 to 30 parts by mass, more preferably in the range of 0.1 to 10 parts by mass, and even more preferably in the range of 0.5 to 5 parts by mass, relative to 100 parts by mass of the specific resin. When the lower limit value is not less than the upper limit value, the adhesiveness between the pattern and the metal layer is good, and when the upper limit value is not more than the upper limit value, the heat resistance and mechanical properties of the pattern are good. The metal adhesion improver may be 1 or 2 or more. When 2 or more kinds are used, the total thereof is preferably within the above range.

< migration inhibitor >

The resin composition of the present invention preferably further comprises a migration inhibitor. By including the migration inhibitor, transfer of metal ions originating from the metal layer (metal wiring) into the film can be effectively suppressed.

The migration inhibitor is not particularly limited, but examples thereof include compounds having a heterocycle (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, triazine ring), compounds having thiourea and sulfanyl groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2, 4-triazole, benzotriazole, 3-amino-1, 2, 4-triazole, and 3, 5-diamino-1, 2, 4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

Alternatively, an ion scavenger that traps anions such as halogen ions may be used.

As other migration inhibitors, rust inhibitors described in paragraph 0094 of japanese patent application laid-open publication No. 2013-015701, compounds described in paragraphs 0073 to 0076 of japanese patent application laid-open publication No. 2009-283711, compounds described in paragraph 0052 of japanese patent application laid-open publication No. 2011-059656, compounds described in paragraphs 0114, 0116 and 0118 of japanese patent application laid-open publication No. 2012-194520, compounds described in paragraph 0166 of international publication No. 2015/199219, and the like can be used, and these are incorporated into the present specification.

Specific examples of migration inhibitors include the following compounds.

[ chemical formula 56]

When the resin composition of the present invention has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass%, more preferably 0.05 to 2.0 mass%, and even more preferably 0.1 to 1.0 mass% relative to the total solid content of the resin composition of the present invention.

The migration inhibitor may be 1 or 2 or more. When the migration inhibitor is 2 or more, the total thereof is preferably within the above range.

< polymerization inhibitor >

The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenol compounds, quinone compounds, amino compounds, N-oxygen radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, and metal compounds.

As specific compounds of the polymerization inhibitor, use is preferably made, for example, of p-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4 '-thiobis (3-methyl-6-tert-butylphenol), 2' -methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenyl hydroxylamine cerium salt, N-nitroso-N-phenyl hydroxylamine aluminum salt, N-nitrosodiphenylamine, N-phenyl naphthylamine, ethylenediamine tetraacetic acid, 1, 2-cyclohexanediamine tetraacetic acid, glycol ether diamine tetraacetic acid, 2, 6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-sulfopropylamino) phenol, N-nitroso-N- (1-naphtyl) hydroxylammonium salt, bis (4-hydroxy-3, 5-tert-butyl-4, 3-hydroxybenzyl) -1, 5H-tri-4, 3-tert-butyl-4-hydroxyphenylmethane, 3H-3, 5-tri-hydroxybenzyl ketone, 4-hydroxy-2, 6-tetramethylpiperidine 1-oxyl, 2, 6-tetramethylpiperidine 1-oxyl, phenothiazine, phenoxazine, 1-diphenyl-2-picrylhydrazine, copper (II) dibutyldithiocarbamate, nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, and the like. The polymerization inhibitor described in paragraph 0060 of Japanese patent application laid-open No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International publication No. 2015/125469 may also be used, and the contents are incorporated herein.

When the resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass, based on the total solid content of the resin composition of the present invention.

The polymerization inhibitor may be 1 or 2 or more. When the polymerization inhibitor is 2 or more, the total thereof is preferably within the above range.

< other additives >

The resin composition of the present invention may contain various additives such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, anticoagulants, phenolic compounds, other polymer compounds, plasticizers, other assistants (e.g., defoamers, flame retardants, etc.) and the like as required within the range that the effects of the present invention can be obtained. By properly containing these components, properties such as film physical properties can be adjusted. For these components, for example, reference can be made to the descriptions of paragraphs 0183 and later (paragraph 0237 of the corresponding U.S. patent application publication No. 2013/0034812) of japanese unexamined patent application publication No. 2012-003225, the descriptions of paragraphs 0101 to 0104 and 0107 to 0109 of japanese unexamined patent application publication No. 2008-250074, and the like, and these contents are incorporated into the present specification. When these additives are blended, the total blending amount is preferably 3 mass% or less of the solid content of the resin composition of the present invention.

[ surfactant ]

As the surfactant, various surfactants such as a fluorine-based surfactant, a silicone-based surfactant, and a hydrocarbon-based surfactant can be used. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

By adding a surfactant to the resin composition of the present invention, the liquid properties (in particular, fluidity) when the resin composition is prepared as a coating liquid can be further improved, and uniformity of the coating thickness and liquid saving can be further improved. That is, when a film is formed using a coating liquid to which a surfactant-containing composition is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced to improve wettability to the surface to be coated, thereby improving coatability to the surface to be coated. Therefore, film formation of uniform thickness with small thickness unevenness can be more preferably performed.

Examples of the fluorine-based surfactant include MEGAFACE F171, MEGAFACE F172, MEGAFACE F B, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, RS-72-K (DIC CORPORATION) and Fluoad FC430, fluoad FC431, fluoad FC171, novec FC4430, novec FC4432 (3M Japanese Limited) and Surflon S-382, surflon SC-101, surflon SC-103, surflon SC-104, surflon SC-105, surflon SC-1068, surfon SC-381, sulon SC-383, surfon S-393, sulon KH-40 (more than 46), liquid PF 29, and PF 20 (more than four times of liquid crystal), and PF 20. The fluorine-based surfactant may be any of those described in paragraphs 0015 to 0158 of JP-A2015-117327 and those described in paragraphs 0117 to 0132 of JP-A2011-132503, and these are incorporated herein by reference. The block polymer may be used as the fluorine-based surfactant, and specific examples thereof include compounds described in JP-A2011-89090, which are incorporated herein.

The fluorine-containing surfactant may preferably be a fluorine-containing polymer compound containing a repeating unit derived from a (meth) acrylate compound having a fluorine atom and a repeating unit derived from a (meth) acrylate compound having 2 or more (preferably 5 or more) oxyalkylene groups (preferably, oxyethylene and oxypropylene groups), and the following compounds may be exemplified as the fluorine-containing surfactant used in the present invention.

[ chemical formula 57]

The weight average molecular weight of the above compound is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.

The fluorine-based surfactant can also use a fluorine-containing polymer having an ethylenically unsaturated group in a side chain as the fluorine-based surfactant. Specific examples thereof include compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP-A2010-164965, which are incorporated into the present specification. Examples of commercial products include MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC CORPORATION.

The fluorine content of the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. The fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of thickness of the coating film and liquid saving property, and also has good solubility in the composition.

Examples of silicone surfactants include Toray Silicone DC PA, toray Silicone SH PA, toray Silicone DC PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH8400 (manufactured by ltd. Above), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive performance Materials inc. Above), KP-341, KF6001, KF6002 (manufactured by Shin-Etsu Chemical co. Above, manufactured by ltd. Above), BYK307, BYK323, BYK330 (manufactured by BYK Chemie GmbH, above), and the like.

Examples of hydrocarbon surfactants include PIONIN A-76, newkalgen FS-3PG, PIONIN B-709, P [ ON [ N B-811-N, P ] ON [ N D-1004, PIONIN D-3104, PIONIN D-3605, PIONIN D-6112, PIONIN D-2104-D, PIONIN D-212, PIONIN D-931, PIONIN D-941, PIONIN D-951, PIONIN E-5310, PIONIN P-1050-B, PIONIN P-1028-P, PIONIN P-4050-T (TAKEMOTO OIL & FAT CO., LTD. Above), and the like.

Examples of the nonionic surfactant include glycerin, trimethylol propane, trimethylol ethane, and ethoxylates and propoxylates thereof (for example, glycerin propoxylate, glycerin ethoxylate, and the like), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, and the like. Examples of the commercial products include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF corporation), tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF corporation), solsperse 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, D-6315 (manufactured by TAKEMOTO OIL & FAT C0., LTD), OLFIN E1010, surfynol 104, 400, 440 (manufactured by Nissin Chemical co., LTD.) and the like.

Specific examples of the cationic surfactant include organosiloxane polymers KP-341 (Shin-Etsu Chemical Co., ltd., (meth) acrylic (co) polymers Polyflow No.75, no.77, no.90, no.95 (KYOEISHA CHEMICAL Co., LTD.,) and WOO1 (Yusho Co., ltd.).

Specific examples of the anionic surfactant include W004, W005, W017 (Yusho co., ltd.), and saldet BL (SANYO KASEI co., ltd.).

The surfactant may be used in an amount of 1 or 2 or more.

The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.

[ higher fatty acid derivative ]

In order to prevent polymerization inhibition due to 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 unevenly present on the surface of the resin composition of the present invention during drying after coating.

The higher fatty acid derivative may be a compound described in paragraph 0155 of International publication No. 2015/199219, which is incorporated herein by reference.

In the case where the resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the resin composition of the present invention. The number of the higher fatty acid derivatives may be 1 or 2 or more. When the number of higher fatty acid derivatives is 2 or more, the total thereof is preferably within the above range.

[ thermal polymerization initiator ]

The resin composition of the present invention may contain a thermal polymerization initiator, and in particular, 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 polymerizability. The addition of the thermal radical polymerization initiator can also cause polymerization of the resin and the polymerizable compound, and thus can further improve solvent resistance. The photopolymerization initiator may have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.

Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063254, and the contents of which are incorporated herein.

When the thermal polymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.5 to 15% by mass, relative to the total solid content of the resin composition of the present invention. The thermal polymerization initiator may be contained in an amount of 1 or 2 or more. When the amount of the thermal polymerization initiator is 2 or more, the total amount is preferably within the above range.

[ inorganic particles ]

The resin composition of the present invention may contain inorganic particles. Specifically, the inorganic particles may include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, and the like.

The average particle diameter of the inorganic particles is preferably 0.01 to 2.0. Mu.m, more preferably 0.02 to 1.5. Mu.m, still more preferably 0.03 to 1.0. Mu.m, particularly preferably 0.04 to 0.5. Mu.m.

The average particle diameter of the fine particles is a primary particle diameter and is a volume average particle diameter. The volume average particle diameter can be measured by a dynamic light scattering method based on Nanotrac WAVE II EX to 150 (manufactured by Nikkiso co., ltd.).

In the case where the above measurement is difficult, the measurement can be performed by a centrifugal sedimentation light transmission method, an X-ray transmission method, or a laser diffraction/scattering method.

[ ultraviolet absorber ]

The compositions of the present invention may comprise an ultraviolet absorber. As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, triazine-based, and other ultraviolet absorbers can be used.

Examples of the salicylate-based ultraviolet light absorber include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate, and examples of the benzophenone-based ultraviolet light absorber include 2,2' -dihydroxy-4-methoxybenzophenone, 2' -dihydroxy-4, 4' -dimethoxybenzophenone, 2', 4' -tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2, 4-dihydroxybenzophenone, and 2-hydroxy-4-octoxybenzophenone. Examples of the benzotriazole-based ultraviolet absorber include 2- (2 '-hydroxy-3', 5 '-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 '-t-butyl-5' -methylphenyl) -5-chlorobenzotriazole, 2- (2 '-hydroxy-3' -t-amyl-5 '-isobutylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 '-isobutyl-5' -methylphenyl) -5-chlorobenzotriazole, 2- (2 '-hydroxy-3' -isobutyl-5 '-propylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 ',5' -di-t-butylphenyl) benzotriazole, 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, and 2- [2 '-hydroxy-5' - (1, 3-tetramethyl) phenyl ] benzotriazole.

Examples of the substituted acrylonitrile ultraviolet absorber include ethyl 2-cyano-3, 3-diphenylacrylate and 2-ethylhexyl 2-cyano-3, 3-diphenylacrylate. Examples of the triazine-based ultraviolet light absorber include: mono (hydroxyphenyl) triazine compounds such as 2- [4- [ (2-hydroxy-3-dodecyloxypropyl) oxy ] -2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2- [4- [ (2-hydroxy-3-tridecyloxypropyl) oxy ] -2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2- (2, 4-dihydroxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine and the like; bis (hydroxyphenyl) triazine compounds such as 2, 4-bis (2-hydroxy-4-propoxyphenyl) -6- (2, 4-dimethylphenyl) -1,3, 5-triazine, 2, 4-bis (2-hydroxy-3-methyl-4-propoxyphenyl) -6- (4-methylphenyl) -1,3, 5-triazine, and 2, 4-bis (2-hydroxy-3-methyl-4-hexyloxyphenyl) -6- (2, 4-dimethylphenyl) -1,3, 5-triazine; tris (hydroxyphenyl) triazine compounds such as 2, 4-bis (2-hydroxy-4-butoxyphenyl) -6- (2, 4-dibutoxyphenyl) -1,3, 5-triazine, 2,4, 6-tris (2-hydroxy-4-octyloxyphenyl) -1,3, 5-triazine, and 2,4, 6-tris [ 2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl ] -1,3, 5-triazine.

In the present invention, 1 kind of the above-mentioned various ultraviolet absorbers may be used alone, or 2 or more kinds may be used in combination.

The composition of the present invention may or may not contain an ultraviolet absorber, but in the case of containing the ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.001 mass% or more and 1 mass% or less, more preferably 0.01 mass% or more and 0.1 mass% or less, relative to the mass of the total solid content of the composition of the present invention.

[ organic titanium Compound ]

The resin composition of the present embodiment may contain an organic titanium compound. By containing the organic titanium compound in the resin composition, a resin layer excellent in chemical resistance can be formed even when curing is performed at a low temperature.

Examples of the usable organic titanium compound include compounds in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.

Specific examples of the organic titanium compound are shown in the following I) to VII):

i) Titanium chelate compound: among them, a titanium chelate compound having 2 or more alkoxy groups is more preferable from the viewpoint of good storage stability of the resin composition and good cured pattern. Specific examples are diisopropanolbis (triethanolamine) titanium, di (n-butanol) bis (2, 4-pentanedione) titanium, diisopropanolbis (tetramethyl heptanedione) titanium, diisopropanolbis (ethyl acetoacetate) titanium, and the like.

II) a titanium tetraalkoxide compound: examples of the titanium include titanium tetra (n-butoxide), titanium tetra (2-ethylhexoxide), titanium tetra (isobutanol), titanium tetra (isopropanol), titanium tetra (methanol), titanium tetra (methoxypropanol), titanium tetra (methylbenzoate), titanium tetra (n-nonanol), titanium tetra (n-propanol), titanium tetra (stearyl oxide), and titanium tetra [ bis {2,2- (allyloxymethyl) butanol } ].

III) titanocene compound: examples of the compound include pentamethylcyclopentadienyl titanium trimethate, bis (. Eta.5-2, 4-cyclopenta-n-1-yl) bis (2, 6-difluorophenyl) titanium, bis (. Eta.5-2, 4-cyclopenta-n-1-yl) bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium, and the like.

IV) monoalkoxytitanium compounds: for example, titanium tris (dioctyl phosphate) isopropoxide, titanium tris (dodecylbenzenesulfonate) isopropoxide, and the like.

V) titanium oxide compound: examples thereof include titanium oxide bis (pentanedione), titanium oxide bis (tetramethyl heptanedione), and titanium phthalocyanine oxide.

VI) titanium tetra acetylacetonate compound: for example, titanium tetraacetylacetonate.

VII) titanate coupling agent: for example, isopropyl tridecyl benzene sulfonyl titanate, etc.

Among them, the organic titanium compound is preferably at least 1 compound selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxy titanium compound and III) titanocene compound, from the viewpoint of exhibiting more excellent chemical resistance. In particular, bis (ethylacetoacetate) titanium diisopropoxide, titanium tetra (n-butoxide) and bis (. Eta.5-2, 4-cyclopentadienyl-1-yl) bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium are preferred.

In the case of blending the organic titanium compound, the blending amount thereof is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the specific resin. When the amount is 0.05 parts by mass or more, the resulting cured pattern more effectively exhibits good heat resistance and chemical resistance, whereas when the amount is 10 parts by mass or less, the composition is more excellent in storage stability.

[ antioxidant ]

The composition of the present invention may comprise an antioxidant. By containing an antioxidant as an additive, the elongation characteristics of the cured film and the adhesion to a metal material can be improved. Examples of the antioxidant include phenol compounds, phosphite compounds, and thioether compounds. As the phenol compound, any phenol compound known as a phenol-based antioxidant can be used. Preferred examples of the phenol compound include hindered phenol compounds. Preferably, the compound has a substituent at a position adjacent to the phenolic hydroxyl group (ortho position). The substituent is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms. The antioxidant is also preferably a compound having a phenol group and a phosphite group in the same molecule. In addition, a phosphorus antioxidant can be preferably used as the antioxidant. Examples of the phosphorus antioxidant include tris [2- [ [2,4,8, 10-tetrakis (1, 1-dimethylethyl) dibenzo [ d, f ] [1,3,2] dioxaphosphepin-6-yl ] oxy ] ethyl ] amine, tris [2- [ (4, 6,9, 11-tetra-t-butyldibenzo [ d, f ] [1,3,2] dioxaphosphepin-2-yl) oxy ] ethyl ] amine, and ethylbis (2, 4-di-t-butyl-6-methylphenyl) phosphite. Examples of the commercially available antioxidants include ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50F, ADK STAB AO-60G, ADK STAB AO-80, and ADK STAB AO-330 (manufactured by ADEKA CORPORATION). The antioxidant may be any one of those described in paragraphs 0023 to 0048 of Japanese patent No. 6268967, incorporated herein by reference. Further, the composition of the present invention may contain a latent antioxidant as needed. Examples of the potential antioxidant include a compound having a site which acts as an antioxidant protected by a protecting group, and a compound which acts as an antioxidant by heating at 100 to 250 ℃ or heating at 80 to 200 ℃ in the presence of an acid/base catalyst to release the protecting group. Examples of the potential antioxidant include compounds described in International publication No. 2014/021023, international publication No. 2017/030005, and Japanese patent application laid-open No. 2017-008219, which are incorporated herein by reference. Examples of commercial products of the potential antioxidants include ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION).

Examples of the preferable antioxidant include 2, 2-thiobis (4-methyl-6-t-butylphenol), 2, 6-di-t-butylphenol and a compound represented by formula (3).

[ chemical formula 58]

In the general formula (3), R ⁵ Represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), R ⁶ An alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). R is R ⁷ An alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), and a 1 to 4-valent organic group containing at least one of an oxygen atom and a nitrogen atom. k represents an integer of 1 to 4.

The compound represented by formula (3) inhibits oxidative degradation of the aliphatic group and the phenolic hydroxyl group of the resin. In addition, by the rust prevention effect on the metal material, oxidation of the metal can be suppressed.

Since the resin and the metal material can be simultaneously acted, k is more preferably an integer of 2 to 4. As R ⁷ Examples thereof include alkyl groups, cycloalkyl groups, alkoxy groups, alkyl ether groups, alkylsilyl groups, alkoxysilyl groups, aryl ether groups, carboxyl groups, carbonyl groups, allyl groups, vinyl groups, heterocyclic groups, -O-, -NH-, -NHNH-, groups obtained by combining these groups, and the like, and may have a substituent. Among them, alkyl ether groups and-NH-are preferable from the viewpoints of solubility in a developer and metal adhesion, and-NH-is more preferable from the viewpoints of interaction with a resin and metal adhesion at the time of metal complexation.

The compounds represented by the general formula (3) may be exemplified by the following examples, but are not limited to the following structures.

[ chemical formula 59]

[ chemical formula 60]

[ chemical formula 61]

[ chemical formula 62]

The amount of the antioxidant to be added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on the resin. By setting the addition amount to 0.1 part by mass or more, the effect of improving elongation characteristics or adhesion to a metal material is easily obtained even under a high-temperature and high-humidity environment, and by setting the addition amount to 10 parts by mass or less, for example, the sensitivity of the resin composition is improved by interaction with a photosensitizer. The antioxidant may be used in an amount of 1 or 2 or more. When 2 or more kinds are used, the total amount is preferably within the above range.

[ anti-coagulant ]

The resin composition of the present embodiment may contain an anti-coagulant as necessary. Examples of the anti-caking agent include sodium polyacrylate.

In the present invention, 1 kind of anticoagulant may be used alone, or 2 or more kinds may be used in combination.

The composition of the present invention may or may not contain an anti-coagulant, but in the case of containing the anti-coagulant, the content of the anti-coagulant is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.02% by mass or more and 5% by mass or less, relative to the mass of the total solid content of the composition of the present invention.

[ phenol-based Compound ]

The resin composition of the present embodiment may contain a phenolic compound as needed. Examples of the phenolic compound include Bis-Z, bisP-EZ, tekP-4HBPA, trisP-HAP, trisP-PA, bisOCHP-Z, bisP-MZ, bisP-PZ, bisP-IPZ, bisOCP-IPZ, bisP-CP, bisRS-2P, bisRS-3P, bisP-OCHP, methylene tri-FR-CR, bisRS-26X (trade name, honshu Chemical Industry Co., ltd.), BIP-PC, BIR-PTBP, BIR-BIPC-F (trade name, ASAHI YUKIZAT CORPORATION).

In the present invention, 1 kind of phenolic compound may be used alone, or 2 or more kinds may be used in combination.

The composition of the present invention may or may not contain a phenolic compound, but in the case of containing the phenolic compound, the content of the phenolic compound is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.02% by mass or more and 20% by mass or less, relative to the total solid content mass of the composition of the present invention.

[ other Polymer Compounds ]

Examples of the other polymer compound include a silicone resin, a (meth) acrylic polymer obtained by copolymerizing (meth) acrylic acid, a novolak resin, a cresol resin, a polyhydroxystyrene resin, and copolymers thereof. The other polymer compound may be a modified product having a crosslinking group such as a hydroxymethyl group, an alkoxymethyl group, or an epoxy group introduced therein.

In the present invention, 1 or 2 or more other polymer compounds may be used alone or in combination.

The composition of the present invention may or may not contain other polymer compounds, but in the case of containing the other polymer compounds, the content of the other polymer compounds is preferably 0.01 mass% or more and 30 mass% or less, more preferably 0.02 mass% or more and 20 mass% or less, relative to the total solid content mass of the composition of the present invention.

< Properties of resin composition >

The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of the coating film thickness, it is preferably 1,000mm ² /s～12,000mm ² S, more preferably 2,000mm ² /s～10,000mm ² S, more preferably 2,500mm ² /s～8,000mm ² And/s. When the amount is within the above range, a coating film having high uniformity can be easily obtained. If it is 1,000mm ² At least one of the above, for example, the film thickness required as an insulating film for rewiring can be easily applied, and the thickness is 12,000mm ² A coating film having excellent coating surface morphology can be obtained.

< restriction of substances contained in resin composition >

The water content of the resin composition of the present invention is preferably less than 2.0 mass%, more preferably less than 1.5 mass%, and even more preferably less than 1.0 mass%. If the content is less than 2.0%, the storage stability of the resin composition is improved.

Examples of the method for maintaining the moisture content include adjusting the humidity under storage conditions and reducing the void ratio of the storage container during storage.

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 (parts per million)), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of the metal include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, and the like, except for metals contained as complexes of an organic compound and a metal. When a plurality of metals are contained, the total of these metals is preferably within the above range.

Further, as a method for reducing metal impurities accidentally contained in the resin composition of the present invention, the following method can be mentioned: selecting a raw material having a small metal content as a raw material constituting the resin composition of the present invention; filtering the raw materials constituting the resin composition of the present invention by a filter; polytetrafluoroethylene or the like is lined in the apparatus to carry out distillation or the like under a condition that contamination is suppressed as much as possible.

When the use of the resin composition of the present invention as a semiconductor material is considered, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm from the viewpoint of wiring corrosiveness. Among them, the atom present in the state of 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. Preferably, the total of chlorine atoms and bromine atoms or chlorine ions and bromine ions is within the above range.

As a method for adjusting the halogen atom content, ion exchange treatment and the like are preferable.

As the container for containing the resin composition of the present invention, a conventionally known container can be used. In addition, as the storage container, a multilayer bottle having 6 types of 6 layers of resins constituting the inner wall of the container and a bottle having 6 types of resins in a 7-layer structure are also preferably used in order to prevent impurities from being mixed into the raw material or the resin composition of the present invention. Examples of such a container include those described in Japanese patent application laid-open No. 2015-123351.

< cured product of resin composition >

The resin composition of the present invention is cured to obtain a cured product of the resin composition.

The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention.

The curing of the resin composition is preferably performed by heating, and the heating temperature is more preferably in the range of 120 to 400 ℃, still more preferably in the range of 140 to 380 ℃, and particularly preferably in the range of 170 to 350 ℃. The form of the cured product of the resin composition is not particularly limited, and may be selected from films, rods, spheres, pellets, and the like according to the application. In the present invention, the cured product is preferably in the form of a film. Further, by patterning the resin composition, the shape of the cured product can be selected according to the application such as forming a protective film on the wall surface, forming a through hole (Beer well) for conduction, adjusting the impedance, electrostatic capacity or internal stress, and imparting a heat dissipation function. The film thickness of the cured product (film formed from the cured product) is preferably 0.5 μm or more and 150 μm or less.

The shrinkage rate of the resin composition of the present invention when cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage rate refers to a percentage of a volume change before and after curing of the resin composition, and can be calculated by the following formula.

Shrinkage [% ] =100- (volume after curing ≡volume before curing) ×100

< Property of cured product of resin composition >

The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. If the content is 70% or more, a cured product having excellent mechanical properties may be obtained.

The elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.

The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180℃or higher, more preferably 210℃or higher, and still more preferably 230℃or higher.

< preparation of resin composition >

The resin composition of the present invention can be prepared by mixing the above-described components. The mixing method is not particularly limited, and can be performed by a conventionally known method.

Mixing by stirring blades, mixing by a ball mill, mixing by rotating a tank itself, or the like can be used for the mixing.

The temperature during mixing is preferably 10 to 30 ℃, more preferably 15 to 25 ℃.

In order to remove foreign matters such as dust and particles in the resin composition of the present invention, filtration using a filter is preferably performed. The filter pore size is, for example, 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. When the filter is made of polyethylene, HDPE (high density polyethylene) is more preferable. The filter may be a filter previously washed with an organic solvent. In the filtration step of the filter, a plurality of filters may be connected in series or in parallel. In the case of using a plurality of filters, filters having different pore diameters or materials may be used in combination. As a connection method, for example, a method in which HDPE filters having a pore size of 1 μm are used as the 1 st stage and HDPE filters having a pore size of 0.2 μm are connected in series as the 2 nd stage is used. And, various materials may be filtered multiple times. In the case of multiple filtration, it may be a cyclic filtration. Further, filtration may be performed after pressurization. In the case of pressurizing and filtering, the pressure at which the pressurization is performed is, for example, 0.01MPa or more and 1.0MPa or less, preferably 0.03MPa or more and 0.9MPa or less, more preferably 0.05MPa or more and 0.7MPa or less, and still more preferably 0.05MPa or more and 0.5MPa or less.

In addition to filtration using a filter, impurity removal treatment using an adsorbent may be performed. The filter filtration and the impurity removal treatment using the adsorbent may be combined. 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.

After filtration using a filter, a step of placing the resin composition filled in the bottle in a reduced pressure state and degassing the resin composition may be performed.

(method for producing cured product)

The method for producing a cured product of the present invention preferably includes a film forming step of applying the resin composition to a substrate to form a film.

The method for producing a cured product of the present invention further preferably includes the film formation step, an exposure step of selectively exposing the film formed in the film formation step, and a development step of developing the film exposed in the exposure step with a developer to form a pattern.

The method for producing a cured product according to the present invention preferably includes at least one of the film forming step, the exposing step, the developing step, and a heating step of heating the pattern obtained in the developing step and a post-developing exposing step of exposing the pattern obtained in the developing step.

The production method of the present invention preferably further includes the step of forming the film and the step of heating the film.

The details of each step will be described below.

< film Forming Process >

The resin composition of the present invention can be used in a film forming step for forming a film on a substrate.

[ substrate ]

The type of the substrate can be appropriately set according to the application, but is not particularly limited, and examples thereof include semiconductor production substrates such as silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, etc., metal substrates such as quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, reflective films, ni, cu, cr, fe, etc. (for example, any of substrates made of metal and substrates having a metal layer formed by, for example, electroplating or vapor deposition), papers, SOG (Spin On Glass), TFT (thin film transistor) array substrates, mold substrates, electrode plates of Plasma Display Panels (PDP), etc. In the present invention, a semiconductor production substrate is particularly preferable, and a silicon substrate, a Cu substrate, and a mold substrate are more preferable.

Further, the surface of these substrates may be provided with an adhesion layer made of Hexamethyldisilazane (HMDS) or the like, an oxide layer or the like.

The shape of the base material is not particularly limited, and may be circular or rectangular.

The size of the base material is, for example, 100 to 450mm, preferably 200 to 450mm in diameter when it is circular. In the case of rectangular, for example, the length of the short side is 100 to 1000mm, preferably 200 to 700mm.

As the base material, for example, a plate-shaped base material (substrate) preferably a panel-shaped base material can be used.

When a film is formed by applying a resin composition to the surface of a resin layer (for example, a layer formed of a cured product) or the surface of a metal layer, the resin layer or the metal layer serves as a base material.

As a method for applying the resin composition of the present invention to a substrate, coating is preferable.

Specific examples of the method to be applied include dip coating, air knife coating, curtain coating, bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and ink jet coating. The spin coating method, the slit coating method, the spray coating method, or the inkjet method is more preferable from the viewpoint of uniformity of the film thickness, and the spin coating method and the slit coating method are preferable from the viewpoint of uniformity of the film thickness and productivity. The solid content concentration of the resin composition or the coating conditions are adjusted according to the method, whereby a film having a desired thickness can be obtained. The coating method may be appropriately selected according to the shape of the substrate, and in the case of a circular substrate such as a wafer, spin coating, spray coating, or ink jet method is preferable, and in the case of a rectangular substrate, slit coating, spray coating, or ink jet method is preferable. In the case of spin coating, for example, a spin speed of 500 to 3 and 500rpm is applied for about 10 seconds to 3 minutes.

The method of transferring the coating film formed by the above-described application method to the temporary support onto the substrate can also be applied.

As the transfer method, the production methods described in paragraphs 0023, 0036 to 0051 and 0096 to 0108 of JP 2006-047592 can be preferably used in the present invention.

Further, a step of removing an excess film from the end portion of the base material may be performed. Examples of such a step include bead washing (EBR) and Back washing (Back ring).

In addition, a pre-wetting step of applying various solvents to the substrate before applying the resin composition to the substrate, and then applying the resin composition after improving the wettability of the substrate may be employed.

< drying Process >

The film may be subjected to a step (drying step) of drying the film (layer) formed for removing the solvent after the film forming step (layer forming step).

That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed by the film forming step.

The drying step is preferably performed after the film formation step and before the exposure step.

The drying temperature of the film in the drying step is preferably 50 to 150 ℃, more preferably 70 to 130 ℃, and even more preferably 90 to 110 ℃. Drying may also be performed by reducing the pressure. The drying time may be exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

< Exposure procedure >

The film may be used in an exposure step of selectively exposing the film.

That is, the method for producing a cured product of the present invention may include an exposure step of selectively exposing the film formed by the film forming step.

Selective exposure means exposing a portion of the film. And, by selectively exposing, an exposed region (exposed portion) and an unexposed region (non-exposed portion) are formed on the film.

The exposure amount is not particularly limited as long as the resin composition of the present invention can be cured, and is preferably 50 to 10,000mJ/cm, for example, in terms of an exposure energy conversion at a wavelength of 365nm ² More preferably 200 to 8,000mJ/cm ² 。

The exposure wavelength can be appropriately set in the range of 190 to 1,000nm, preferably 240 to 550nm.

The exposure wavelength is described in relation to the light source, Examples thereof include (1) semiconductor lasers (wavelength 830nm, 532nm, 488nm, 405nm, 375nm, 355nm etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), i-rays (wavelength 365 nm), wide (g-, h-, 3-wavelengths of i-rays), (4) excimer lasers, krF excimer lasers (wavelength 248 nm), arF excimer lasers (wavelength 193 nm), and F ₂ Excimer laser (wavelength 157 nm), (5) extreme ultraviolet; EUV (wavelength 13.6 nm), (6) electron beam, (7) second harmonic 532nm, third harmonic 355nm of YAG laser, etc. With respect to the resin composition of the present invention, exposure based on a high-pressure mercury lamp is particularly preferable, and among them, exposure based on i-rays is preferable. Thus, particularly high exposure sensitivity can be obtained.

The method of exposure is not particularly limited as long as at least a part of the film formed from the resin composition of the present invention is exposed, but exposure using a photomask, exposure by a laser direct imaging method, and the like may be mentioned.

< post-exposure heating Process >

The film may be subjected to a step of heating after exposure (post-exposure heating step).

That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the film exposed in the exposure step.

The post-exposure heating step may be performed after the exposure step and before the development step.

The heating temperature in the post-exposure heating step is preferably 50 to 140 ℃, more preferably 60 to 120 ℃.

The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.

The heating rate in the post-exposure heating step is preferably 1 to 12 ℃/min, more preferably 2 to 10 ℃/min, and even more preferably 3 to 10 ℃/min, from the temperature at the start of heating to the maximum heating temperature.

The temperature rise rate may be changed as appropriate during the heating process.

The heating means in the post-exposure heating step is not particularly limited, and a known heating plate, oven, infrared heater, or the like can be used.

It is also preferable to perform the heating in an environment of low oxygen concentration by flowing inert gas such as nitrogen, helium, or argon.

< developing Process >

The film after exposure can be used in a developing step of developing with a developer to form a pattern.

That is, the method for producing a cured product of the present invention may include a developing step of developing the film exposed in the exposing step with a developer to form a pattern. One of the exposed portion and the non-exposed portion of the film is removed by development, and a pattern is formed.

Here, the development of the non-exposed portion from which the film is removed by the development step is referred to as negative development, and the development of the exposed portion from which the film is removed by the development step is referred to as positive development.

[ developer solution ]

As the developer used in the developing step, an alkaline aqueous solution or a developer containing an organic solvent can be mentioned.

When the developer is an aqueous alkaline solution, examples of the alkaline compound that can be contained in the aqueous alkaline solution include inorganic bases, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts, preferably TMAH (tetramethyl ammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyl diethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide (Tetrapropylammonium Hydroxide), tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methylttripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethyl bis (2-hydroxyethyl) ammonium hydroxide, trimethylphenyl ammonium hydroxide, trimethylbenzyl ammonium hydroxide, triethylbenzyl ammonium hydroxide, pyrrole, and piperidine, and more preferably TMAH. For example, in the case of using TMAH, the content of the alkaline compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and still more preferably 0.3 to 3% by mass based on the total mass of the developer.

When the developer contains an organic solvent, examples of the organic solvent include preferably 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, epsilon-caprolactone, delta-valerolactone, and alkyl alkoxyacetate (examples: methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-alkoxypropionate (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionate (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), methyl 2-alkoxy-2-methylpropionate, ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), ethyl 2-alkoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like, and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol Monomethyl Ether (PGME), propylene glycol monomethyl ether acetate (PGMFA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and the like, and as cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, anisole, and the like, cyclic terpenes such as limonene, as sulfoxides, and as alcohols, and the like, methyl sulfoxide, and the like, and as alcohols, methyl alcohol, ethanol, isopropanol, methyl propanol, N-propanol, methyl propanol, N-butyl alcohol, methyl-pyrrolidone, and the like, are preferable examples.

In the case where the developer contains an organic solvent, 1 or 2 or more organic solvents can be used in combination. In the present invention, in particular, a developer containing at least 1 selected from the group consisting of cyclopentanone, γ -butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is preferable, a developer containing at least 1 selected from the group consisting of cyclopentanone, γ -butyrolactone, and dimethyl sulfoxide is more preferable, and a developer containing cyclopentanone is most preferable.

When the developer contains an organic solvent, the content of the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more, relative to the total mass of the developer. The content may be 100% by mass.

The developer may further contain other components.

Examples of the other components include a known surfactant and a known defoaming agent.

[ method for supplying developer ]

The method of supplying the developer is not particularly limited as long as a desired pattern can be formed, and there are a method of immersing the substrate on which the film is formed in the developer, and a method of supplying the developer to the film formed on the substrate by using a nozzle to perform spin-on immersion development or continuously supplying the developer. The type of the nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, a spray nozzle, and the like.

The method of supplying the developer using a straight nozzle or the method of continuously supplying the developer using a spray nozzle is preferable from the viewpoints of the permeability of the developer, the removability of the non-image portion, and the efficiency in production, and the method of supplying the developer using a spray nozzle is more preferable from the viewpoints of the permeability of the developer to the image portion.

Further, a step of rotating the substrate to remove the developer from the substrate after continuously supplying the developer using the straight nozzle, and a step of rotating the substrate to remove the developer from the substrate after continuously supplying the developer again using the straight nozzle after spin-drying may be adopted, or the step may be repeated a plurality of times.

As a method for supplying the developer in the developing step, a step of continuously supplying the developer to the substrate, a step of holding the developer in a substantially stationary state on the substrate, a step of vibrating the developer on the substrate by ultrasonic waves or the like, a step of combining these, and the like can be employed.

The development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developing solution at the time of development is not particularly limited, and is preferably 10 to 45 ℃, more preferably 18 to 30 ℃.

In the developing step, after the treatment with the developer, the pattern may be further cleaned (rinsed) with the rinse solution. Further, a method of supplying a rinse solution or the like before the developer in contact with the pattern is not completely dried may be employed.

[ flushing liquid ]

In the case where the developer is an alkaline aqueous solution, water can be used as the rinse liquid, for example. In the case where the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (for example, water or an organic solvent different from the organic solvent contained in the developer) can be used as the rinse liquid.

Examples of the organic solvent in the case where the rinse liquid contains an organic solvent include esters, preferably include 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, and alkyl alkoxyacetate (examples: methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-alkoxypropionate (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionate (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), methyl 2-alkoxy-2-methylpropionate, ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), ethyl 2-alkoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like, and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol Monomethyl Ether (PGME), propylene Glycol Monomethyl Ether Acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and the like, and as cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, anisole, and the like, cyclic terpenes such as limonene, as sulfoxides, and as alcohols, and the like, methyl sulfoxide, and the like, and as alcohols, methyl alcohol, ethanol, isopropanol, methyl propanol, N-propanol, methyl propanol, N-butyl glycol, N-pyrrolidone, methyl-pyrrolidone, and the like, are preferable examples.

When the rinse liquid contains an organic solvent, 1 or 2 or more organic solvents can be used in combination. In the present invention, cyclopentanone, γ -butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferable, cyclopentanone, γ -butyrolactone, dimethyl sulfoxide, PGMEA, and PGME are more preferable, and cyclohexanone and PGMEA are further preferable.

When the rinse liquid contains an organic solvent, it is preferable that 50 mass% or more of the rinse liquid is an organic solvent, more preferably 70 mass% or more is an organic solvent, and still more preferably 90 mass% or more is an organic solvent. Further, 100 mass% of the rinse solution may be an organic solvent.

The rinse solution may further comprise other ingredients.

[ method for supplying rinse solution ]

The method of supplying the rinse liquid is not particularly limited as long as a desired pattern can be formed, and there are a method of immersing the substrate in the rinse liquid, a method of supplying the rinse liquid to the substrate through a liquid tray, a method of supplying the rinse liquid to the substrate in a spray form, and a method of continuously supplying the rinse liquid to the substrate through a mechanism such as a straight nozzle.

From the viewpoints of the permeability of the rinse liquid, the removability of the non-image portion, and the efficiency in production, there are methods of supplying the rinse liquid using a spray nozzle, a straight nozzle, a spray nozzle, or the like, and a method of continuously supplying the rinse liquid using a spray nozzle is preferable, and from the viewpoints of the permeability of the rinse liquid to the image portion, a method of supplying the rinse liquid using a spray nozzle is more preferable. The type of the nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, a spray nozzle, and the like.

That is, the rinsing step is preferably a step of supplying or continuously supplying a rinsing liquid to the exposed film through a straight nozzle, and more preferably a step of supplying a rinsing liquid through a spray nozzle.

As a method for supplying the rinse liquid in the rinsing step, a step of continuously supplying the rinse liquid to the substrate, a step of holding the rinse liquid in a substantially stationary state on the substrate, a step of vibrating the rinse liquid on the substrate by ultrasonic waves or the like, a step of combining these, and the like can be employed.

The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinse liquid at the time of rinsing is not particularly limited, and is preferably 10 to 45 ℃, more preferably 18 to 30 ℃.

< heating Process >

The pattern obtained by the development process (the pattern after the rinsing in the case of performing the rinsing process) may be subjected to a heating process for heating the pattern obtained by the development.

That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained by the developing step.

The method for producing a cured product of the present invention may further include a heating step of heating the pattern obtained by another method or the film obtained by the film forming step without performing the developing step.

In the heating step, a resin such as a polyimide precursor is cyclized to form a resin such as a polyimide.

Further, crosslinking of unreacted crosslinkable groups in the specific resin or the crosslinking agent other than the specific resin is also performed.

The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450 ℃, more preferably 150 to 350 ℃, still more preferably 150 to 250 ℃, still more preferably 160 to 250 ℃, and particularly preferably 160 to 230 ℃.

The heating step is preferably a step of heating and accelerating the cyclization reaction of the polyimide precursor in the pattern by the action of a base or the like generated from the alkaline generator.

The heating in the heating step is preferably performed at a heating rate of 1 to 12 ℃/min from the temperature at the start of heating to the maximum heating temperature. The temperature rise rate is more preferably 2 to 10℃per minute, and still more preferably 3 to 10℃per minute. The rate of temperature rise is set to 1 ℃/min or more, whereby the productivity can be ensured and excessive volatilization of the acid or solvent can be prevented, and the rate of temperature rise is set to 12 ℃/min or less, whereby the residual stress of the cured product can be relaxed.

In the case of an oven capable of rapid heating, the heating from the temperature at the start of heating to the highest heating temperature is preferably performed at a heating rate of 1 to 8 ℃/sec, more preferably 2 to 7 ℃/sec, and still more preferably 3 to 6 ℃/sec.

The temperature at the start of heating is preferably 20 to 150 ℃, more preferably 20 to 130 ℃, still more preferably 25 to 120 ℃. The temperature at the start of heating is the temperature at the start of the step of heating to the highest heating temperature. For example, in the case where the resin composition of the present invention is applied to a substrate and then dried, the temperature of the film (layer) after drying is preferably increased from a temperature lower by 30 to 200 ℃ than the boiling point of the solvent contained in the resin composition of the present invention.

The heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, still more preferably 15 to 240 minutes.

In particular, when forming a multilayer laminate, the heating temperature is preferably 30 ℃ or higher, more preferably 80 ℃ or higher, still more preferably 100 ℃ or higher, and particularly preferably 120 ℃ or higher, from the viewpoint of adhesion between layers.

The upper limit of the heating temperature is preferably 350℃or lower, more preferably 250℃or lower, and still more preferably 240℃or lower.

The heating may be performed stepwise. As an example, the following procedure may be performed: the temperature was raised from 25 ℃ to 120 ℃ at 3 ℃/min and held at 120 ℃ for 60 minutes, and from 120 ℃ to 180 ℃ at 2 ℃/min and held at 180 ℃ for 120 minutes. Further, as described in U.S. Pat. No. 9159547, it is also preferable to perform the treatment while irradiating ultraviolet rays. By such a pretreatment step, the film characteristics can be improved. The pretreatment step may be performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be 2 or more steps, for example, the pretreatment step of the 1 st step may be performed at 100 to 150 ℃, and the pretreatment step of the 2 nd step may be performed at 150 to 200 ℃.

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

In order to prevent decomposition of the specific resin, the heating step is preferably performed in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon under reduced pressure. The oxygen concentration is preferably 50ppm (volume ratio) or less, more preferably 20ppm (volume ratio) or less.

The heating means in the heating step is not particularly limited, and examples thereof include a heating plate, an infrared oven, an electric oven, a hot air oven, and an infrared oven.

< post-development exposure Process >

Instead of or in addition to the heating step, the pattern obtained by the developing step (the pattern after the rinsing step in the case of performing the rinsing step) may be subjected to a post-development exposure step of exposing the pattern after the developing step.

That is, the method for producing a cured product of the present invention may include a post-development exposure step of exposing the pattern obtained by the development step. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step.

In the post-development exposure step, for example, a reaction of cyclizing a polyimide precursor or the like by the sensitization of the photobase generator can be promoted.

In the post-development exposure step, at least a part of the pattern obtained in the development step may be exposed, but it is preferable to expose all of the pattern.

The exposure amount in the post-development exposure step is preferably 50 to 20,000mJ in terms of exposure energy at a wavelength at which the photosensitive compound has sensitivity/cm ² More preferably 100 to 15,000mJ/cm ² 。

The post-development exposure step can be performed using, for example, the light source in the exposure step, and preferably using broadband light.

< Metal layer Forming Process >

The pattern obtained by the development step (preferably, the pattern to be supplied to at least one of the heating step and the post-development exposure step) may be supplied to a metal layer forming step of forming a metal layer on the pattern.

That is, the method for producing a cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on a pattern (preferably a pattern to be supplied to at least one of a heating step and a post-development exposure step) obtained by the development step.

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, tungsten, tin, silver, and alloys containing these metals, more preferably copper and aluminum, and still more preferably copper.

The method for forming the metal layer is not particularly limited, and a conventional method can be applied. For example, the methods described in Japanese patent application laid-open No. 2007-157879, japanese patent application laid-open No. 2001-521288, japanese patent application laid-open No. 2004-214501, japanese patent application laid-open No. 2004-101850, U.S. Pat. No. 7888181B2, and U.S. Pat. No. 9177926B2 can be used. For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electrolytic plating, electroless plating, etching, printing, a method combining these, and the like can be considered. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electrolytic plating can be cited. A preferred embodiment of the plating includes electrolytic plating using a copper sulfate or copper cyanide plating solution.

The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm, at the portion having the thickest thickness.

< use >

Examples of the field to which the method for producing a cured product of the present invention or the cured product of the present invention can be applied include an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like. In addition, a sealing film, a substrate material (a base film or a cover film of a flexible printed circuit board, an interlayer insulating film), a case where an insulating film for the above-described mounting use is etched to form a pattern, and the like can be given. For these uses, for example, reference can be made to science & Technology co., ltd, "high functionalization of polyimide and application Technology of application", 4 th year, yo-yo/prison, CMC Technology library "basis and development of polyimide materials", release 11 th year 2011, japan polyimide/aromatic polymer research institute/code "latest polyimide basis and application", NTS, 8 th year 2010, and the like.

The method for producing a cured product of the present invention and the cured product of the present invention can also be used for producing a plate surface such as an offset plate surface or a screen plate surface, for etching a molded component, for producing a protective varnish and a dielectric layer in an electron, particularly in a microelectronic.

(laminate and method for producing laminate)

The laminate of the present invention is a structure having a plurality of layers formed from the cured product of the present invention.

The laminate of the present invention is a laminate including 2 or more layers of cured products, and may be a laminate in which 3 or more layers are laminated.

At least 1 of the 2 or more layers of the cured product included in the laminate is a layer of the cured product of the present invention, and from the viewpoint of suppressing shrinkage of the cured product, deformation of the cured product due to the shrinkage, and the like, it is also preferable that all of the layers of the cured product included in the laminate are layers of the cured product of the present invention.

That is, the method for producing a laminate of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes the step of repeating the method for producing a cured product of the present invention a plurality of times.

The laminate of the present invention includes 2 or more layers of the cured product, and preferably includes a metal layer between any of the layers of the cured product. The metal layer is preferably formed by the metal layer forming step.

That is, the method for producing a laminate of the present invention preferably further includes a metal layer forming step of forming a metal layer on a layer formed of a cured product, between the methods for producing a cured product that are performed a plurality of times. The preferable mode of the metal layer forming step is as described above.

The laminate preferably includes a laminate having a layer structure in which at least 3 layers, i.e., a layer formed of a first cured product, a metal layer, and a layer formed of a second cured product, are laminated in this order.

The layer formed of the first cured product and the layer formed of the second cured product are preferably both layers formed of the cured product of the present invention. The resin composition of the present invention for forming the layer formed of the first cured product and the resin composition of the present invention for forming the layer formed of the second cured product may have the same composition or may have different compositions. The metal layer in the laminate of the present invention can be preferably used as a metal wiring such as a rewiring layer.

< lamination Process >

The method for producing a laminate of the present invention preferably includes a lamination step.

The lamination step is a series of steps including performing at least one of (a) a film formation step (layer formation step), (b) an exposure step, (c) a development step, (d) a heating step, and a post-development exposure step again in this order on the surface of the pattern (resin layer) or the metal layer. In this case, at least one of the film forming step (a) and the heating step (d) and the post-development exposure step may be repeated. Further, after at least one of the heating step and the post-development exposure step, the method may further include a step of forming a metal layer. The lamination step may, of course, further include the drying step and the like as appropriate.

When the lamination step is further performed after the lamination step, the surface activation treatment step may be further performed after the exposure step, after the heating step, or after the metal layer forming step. As the surface activation treatment, a plasma treatment can be exemplified. Details of the surface activation treatment will be described later.

The lamination step is preferably performed 2 to 20 times, more preferably 2 to 9 times.

For example, as the resin layer/metal layer/resin layer/metal layer, the resin layer is preferably set to a structure of 2 layers or more and 20 layers or less, and more preferably set to a structure of 2 layers or more and 9 layers or less.

The composition, shape, film thickness, etc. of the layers may be the same or different.

In the present invention, it is particularly preferable that the cured product (resin layer) of the resin composition of the present invention is formed so as to further cover the metal layer after the metal layer is provided. Specifically, there may be mentioned a method in which at least one of (a) a film forming step, (b) an exposure step, (c) a development step, (d) a heating step and a post-development exposure step, and (e) a metal layer forming step are sequentially repeated, or a method in which at least one of (a) a film forming step, (d) a heating step and a post-development exposure step, and (e) a metal layer forming step are sequentially repeated. The resin composition layer (resin layer) and the metal layer of the present invention can be alternately laminated by alternately performing the lamination step of laminating the resin composition layer (resin layer) and the metal layer formation step of the present invention.

(surface-activating treatment step)

The method for producing a laminate of the present invention preferably includes a surface activation treatment step of surface-activating at least a part of the metal layer and the resin composition layer.

The surface activation treatment step is usually performed after the metal layer formation step, but the metal layer formation step may be performed after the surface activation treatment step is performed on the resin composition layer after the development step (preferably after at least one of the heating step and the post-development exposure step).

The surface activation treatment may be performed only on at least a part of the metal layer, may be performed only on at least a part of the resin composition layer after exposure, or may be performed on at least a part of both the metal layer and the resin composition layer after exposure. It is preferable to surface-activate at least a part of the metal layer, and it is more preferable to surface-activate a part or all of the region of the metal layer where the resin composition layer is formed on the surface. In this way, by performing the surface activation treatment on the surface of the metal layer, the adhesion with the resin composition layer (film) provided on the surface thereof can be improved.

It is preferable that a part or the whole of the resin composition layer (resin layer) after exposure is also subjected to a surface activation treatment. In this way, by performing the surface activation treatment on the surface of the resin composition layer, adhesion between the metal layer provided on the surface subjected to the surface activation treatment and the resin layer can be improved. In particular, when the resin composition layer is cured in the case of performing negative development or the like, the resin composition layer is less likely to be damaged by the surface treatment, and adhesion is easily improved.

Specifically, the surface activation treatment is selected from plasma treatment of various source gases (oxygen, hydrogen, argon, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, CF-based treatment, and the like ₄ /O ₂ 、NF ₃ /O ₂ 、SF ₆ 、NF ₃ 、NF ₃ /O ₂ The etching treatment of (a) the surface treatment by an Ultraviolet (UV) ozone method, the dipping treatment in an organic surface treating agent containing a compound having at least 1 amino group and thiol group after dipping in an aqueous hydrochloric acid solution to remove an oxide film, and the mechanical roughening treatment using a brush are preferably plasma treatment, particularly preferably oxygen plasma treatment using oxygen as a raw material gas. In the case of corona discharge treatment, the energy is preferably 500 to 200,000I/m ² More preferably 1000 to 100,000I/m ² Most preferably from 10,000 to 50,000I/m ² 。

(semiconductor device and method for manufacturing the same)

The present invention also discloses a semiconductor device comprising the cured product of the present invention or the laminate of the present invention.

The present invention also discloses a method for manufacturing a semiconductor device including the method for manufacturing a cured product of the present invention or the method for manufacturing a laminate of the present invention. As a specific example of a semiconductor device in which the resin composition of the present invention is used for formation of an interlayer insulating film for a re-wiring layer, reference is made to the descriptions in paragraphs 0213 to 0218 and the description in fig. 1 of japanese patent application laid-open publication 2016-027357, and these are incorporated herein by reference.

Examples

The present invention will be described more specifically with reference to the following examples. The materials, amounts used, proportions, treatment contents, treatment orders and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are mass references.

< Synthesis of Compound A >

[ Synthesis of CS-1 ]

In a flask equipped with a stirrer and a condenser, 27.44g (200 mmol) of 2- (4-aminophenyl) ethanol (Tokyo Chemical Industry co., ltd.) and 0.03g of p-methoxyphenol (Tokyo Chemical Industry co., ltd.) were dissolved in 250mL of tetrahydrofuran, and cooled to 0 ℃. Next, 29.48g (190 mmol) of Karenz MOI (manufactured by SHOWA DENKO K.K.) was added dropwise over 1 hour, and the mixture was stirred at 0℃to 10℃for 1 hour, then heated to 25℃and stirred for 2 hours. Then, the mixture was crystallized into a solution of 800mL of ethyl acetate/200 mL of hexane, and the solution was filtered. Subsequently, the filtrate was stirred with 500mL of ethyl acetate for 1 hour, and was filtered. It was dried at 45℃for 24 hours, whereby 45g of CS-1 was obtained. From the slave ¹ The H-NMR spectrum was found to be CS-1. The structure of CS-1 is shown in the following formula (CS-1).

[ chemical formula 63]

[ Synthesis of CS-2 to CS-4 ]

CS-2 to CS-4 were synthesized by the same method. The structures of CS-2 to CS-4 are shown in the following formulas (CS-2) to (CS-4).

[ chemical formula 64]

[ Synthesis of CS-5 ]

In a flask equipped with a stirrer and a condenser, 14.6g (50 mmol) of CS-1 synthesized in the above, 0.005g of p-methoxyphenol (Tokyo Chemical Industry Co., ltd.) and 4.75g of pyridine (Tokyo Chemical Industry Co., ltd.) were dissolved in 80mL of tetrahydrofuran (Tokyo Chemical Industry Co., ltd.) and cooled to 0 ℃. Subsequently, 5.75g (55 mmol) of methacryloyl chloride (Tokyo Chemical Industry co., ltd.) was added dropwise over 1 hour, and after stirring at 0 to 10 ℃ for 1 hour, the temperature was raised to 25 ℃ and stirred for 2 hours. Then, it was dissolved in 800mL of ethyl acetate and transferred to a separating funnel. The extract was washed with 300mL of water, 300mL of diluted hydrochloric acid, 300mL of saturated sodium bicarbonate water and saturated brine, dried over magnesium sulfate, filtered, and then the solvent was removed by an evaporator and dried at 45℃for 24 hours, whereby 15g of CS-5 was obtained. From the slave ¹ The H-NMR spectrum was found to be CS-5. The structure of CS-5 is shown in the following formula (CS-5).

[ chemical formula 65]

[ Synthesis of CS-6 to CS-15 ]

CS-6 to CS-15 were synthesized by the same method except that in the synthesis of CS-5, methacryloyl chloride was changed to other acid halides or isocyanate compounds. The structures of CS-6 to CS-15 are shown in the following formulas (CS-6) to (CS-15).

[ chemical formula 66]

[ Synthesis of CS-16 ]

In a flask equipped with a stirrer and a condenser, 27.42g (200 mmol) of 4-aminobenzoic acid (Tokyo Chemical Industry co., ltd.) and 0.03g of p-methoxyphenol (Tokyo Chemical Industry co., ltd.) were dissolved in 250mL of tetrahydrofuran, and cooled to 0 ℃. Next, 41.83g (210 mmol) of Karenz MOI-EG (manufactured by SHOWA DENKO K.K.) was added dropwise over 1 hour, and after stirring at 0℃to 10℃for 1 hour, the temperature was raised to 25℃and stirred for 2 hours. Then, the mixture was crystallized into 700 mL/300 mL of ethyl acetate and filtered. This was transferred to a flask equipped with a stirrer and a condenser, and dissolved in 250mL of tetrahydrofuran. Subsequently, 30.6g (160 mmol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (Tokyo Chemical Industry co., ltd.) and 19.5g (150 mmol) of 2-hydroxyethyl methacrylate (Tokyo Chemical Industry co., ltd.) and 0.6g (5 mmol) of 4-dimethylaminopyridine (Tokyo Chemical Industry co., ltd.) were added. It was stirred at 25 ℃ for 3 hours to dissolve in 600mL of ethyl acetate and transferred to a separatory funnel. The extract was washed with 300mL of water, 300mL of diluted hydrochloric acid, 500mL of saturated sodium bicarbonate water and saturated brine, dried over magnesium sulfate, filtered, and then the solvent was removed by an evaporator to obtain 40g of CS-16. From the slave ¹ The H-NMR spectrum was confirmed to be CS-16. The structure of CS-16 is shown in the following formula (CS-16).

[ chemical formula 67]

[ Synthesis of CS-17 to CS-24 ]

CS-17 to CS-24 were synthesized by the same method as the synthesis of CS-16. The structures of CS-17 to CS-24 are shown in the following formulas (CS-17) to (CS-24). In the following structure, the subscript of the brackets indicates the number of repetitions.

[ chemical formula 68]

[ Synthesis of CS-25 to CS-27 ]

Trade name: CS-25 to CS-27 were synthesized in the same manner as in CS-1 above except that NEOSTAN U-600 (manufactured by Nitto Kasei Co., ltd.) was used as the bismuth catalyst and the reaction temperature was set to 50 ℃. The structures of CS-25 to CS-27 are shown in the following formulas (CS-25) to (CS-27).

[ chemical formula 69]

[ Synthesis of CS-28 to CS-31 ]

CS-28 was synthesized by the same method as CS-5 described above. CS-29 was synthesized by the same method as that of CS-1 described above. CS-30 to CS-31 were synthesized by the same method as that of CS-16. The structures of CS-28 to CS-31 are shown in the following formulas (CS-28) to (CS-31).

[ chemical formula 70]

[ Synthesis of CS-32 to CS-33 ]

CS-32 to CS-33 were synthesized by the same method as that of CS-1. The structures of CS-32 to CS-33 are shown in the following formulas (CS-32) to (CS-33).

[ chemical formula 71]

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(Synthesis of cyclized resin or precursor thereof)

< synthesis example a-1: synthesis of polybenzoxazole precursor A-1 from 2,2 '-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 4' -oxo-dibenzoyl chloride

28.0g (76.4 mmol) of 2,2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane was stirred and dissolved in 200g of N-methylpyrrolidone. Then, 12.1g (153 mmol) of pyridine was added thereto, and a solution obtained by dissolving 20.7g (70.1 mmol) of 4,4' -oxybenzoyl chloride in 75g of N-methylpyrrolidone was added dropwise over 1 hour while maintaining the temperature at-10 to 0 ℃. After stirring for 30 minutes, 1.00g (12.7 mmol) of acetyl chloride was added and further stirred for 60 minutes. Next, the polybenzoxazole precursor resin was precipitated in 6 liters of water and the water-polybenzoxazole precursor resin mixture was stirred at 500rpm for 15 minutes. The polybenzoxazole precursor resin was removed by filtration, stirred again in 6 liters of water for 30 minutes and again filtered. Next, the obtained polybenzoxazole precursor resin was dried at 45 ℃ for 3 days under reduced pressure, thereby obtaining a polybenzoxazole precursor a-1. The polybenzoxazole precursor a-1 has a weight average molecular weight (Mw) =21500 and a number average molecular weight (Mn) =9500.

The structure of the polybenzoxazole precursor A-1 is presumed to be represented by the following formula (A-1).

[ chemical formula 72]

< synthesis example a-2: synthesis of polyimide ]

In a flask equipped with a condenser and a stirrer, 26.0g (50 mmol) of 4,4'- (4, 4' -isopropylidenediphenoxy) bis (phthalic anhydride) (Tokyo Chemical Industry co., ltd.) and 0.02g of 2, 6-tetramethylpiperidine 1-oxyl (Tokyo Chemical Industry co., ltd.) were dissolved in 120.0g of N-methylpyrrolidone (NMP) while removing water. Next, 11.9g (45 mmol) of diamine (AA-1) described below was added, and the mixture was stirred at 25℃for 3 hours and at 45℃for 3 hours. Subsequently, 15.8g (200 mmol) of pyridine, 12.8g (125 mmol) of acetic anhydride, and 50g of N-methylpyrrolidone (NMP) were added, and the mixture was stirred at 80℃for 3 hours, and 50g of N-methylpyrrolidone (NMP) was added and diluted.

The reaction solution was precipitated in 1 liter of methanol and stirred at 3000rpm for 15 minutes. The resin was removed by filtration, stirred in 1 liter of methanol for 30 minutes again and filtered again. The obtained resin was dried at 40℃for 1 day under reduced pressure, thereby obtaining polyimide A-2. The molecular weight of a-2 is mw=21,000, mn=9,100.

The structure of polyimide A-2 is assumed to be represented by the following formula (A-2).

[ chemical formula 73]

Synthesis example AA-1: synthesis of diamine AA-1

In a flask equipped with a condenser and a stirrer, 26.0g (0.2 mol) of 2-hydroxyethyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation) and 17.4g (0.22 mol) of dehydrated pyridine (manufactured by FUJIFILM Wako Pure Chemical Corporation) were dissolved in 78g of ethyl acetate, and the mixture was cooled to 5℃or lower. Next, 48.4g (0.21 mol) of 3, 5-dinitrobenzoyl chloride (Tokyo Chemical Industry co., ltd.) was dissolved in 145g of ethyl acetate, and the solution was added dropwise to the flask over 1 hour using a dropping funnel. After the completion of the dropwise addition, stirring was carried out at a temperature of 10℃or lower for 30 minutes, and the temperature was raised to 25℃and stirred for 3 hours. Then, ethyl acetate (CH) ₃ COOEt) 600mL was diluted and transferred to a separating funnel, and washed with 300mL of water, 300mL of saturated sodium bicarbonate water, 300mL of diluted hydrochloric acid, and 300mL of saturated brine in this order. After washing in separate liquid, 30g of magnesium sulfate was dried, and then concentrated and dried in vacuum using an evaporator, thereby obtaining 61.0g of dinitro (A-1).

27.9g (500 mmol) of reduced iron (manufactured by FUJIFILM Wako Pure Chemical Corporation), 5.9g (110 mmol) of ammonium chloride (manufactured by FUJIFILM Wako Pure Chemical Corporation), 3.0g (50 mmol) of acetic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation), and 0.03g of 2, 6-tetramethylpiperidine 1-oxyl (Tokyo Chemical Industry co., manufactured by ltd.) were weighed into a flask equipped with a condenser and a stirrer, and 200mL of isopropyl alcohol (IPA) and 30mL of pure water were added thereto and stirred.

Next, 16.2g of the dinitro (A-1) was added thereto for 1 hour and stirred for 30 minutes. Then, the external temperature was raised to 85 ℃ and stirred for 2 hours, and after cooling to 25 ℃ or lower, filtration was performed using CELITE (registered trademark). The filtrate was concentrated using a rotary evaporator and dissolved in 800mL of ethyl acetate. This was transferred to a separating funnel, washed 2 times with 300mL of saturated sodium bicarbonate water, and washed successively with 300mL of water and 300mL of saturated brine. After washing in a liquid, drying was performed with 30g of magnesium sulfate, concentration and vacuum drying were performed using an evaporator, whereby 11.0g of diamine (AA-1) was obtained.

[ chemical formula 74]

< synthesis example a-3: synthesis of polyimide precursor (A-3)

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

20.0g (64.5 mmol) of 4,4 '-oxydiphthalic dianhydride (obtained by drying at 140℃for 12 hours), 16.8g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 20.4g (258 mmol) of pyridine and 100g of diglyme were mixed and stirred at 60℃for 18 hours, whereby diesters of 4,4' -oxydiphthalic acid and 2-hydroxyethyl methacrylate were produced. Next, the obtained diester was treated with SOCl ₂ After chlorination, the polyimide precursor was converted into a polyimide precursor by the same method as in Synthesis example A-5 using 4,4' -diaminodiphenyl ether, and a polyimide precursor (A-3) was obtained by the same method as in Synthesis example A-5. The polyimide precursor had a weight average molecular weight of 19,600.

The structure of A-3 is assumed to be represented by the following formula (A-3).

[ chemical formula 75]

< synthesis example a-4: synthesis of polyimide precursor (A-4)

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

20.0g (64.5 mmol) of 4,4 '-oxydiphthalic dianhydride (obtained by drying at 140℃for 12 hours), 16.8g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 20.4g (258 mmol) of pyridine and 100g of diglyme were mixed and stirred at 60℃for 18 hours, whereby diesters of 4,4' -oxydiphthalic acid and 2-hydroxyethyl methacrylate were produced. Next, the obtained diester was treated with SOCl ₂ After chlorination, the polyimide precursor was converted into a polyimide precursor by the same method as in Synthesis example A-5 using 4,4 '-diamino-2, 2' -dimethylbiphenyl, and a polyimide precursor (A-4) was obtained by the same method as in Synthesis example A-5. The polyimide precursor had a weight average molecular weight of 23,500.

The structure of A-4 is assumed to be represented by the following formula (A-4).

[ chemical formula 76]

< synthesis example a-5: synthesis of polyimide precursor (A-5)

[ A-5: synthesis of polyimide precursor resin A-5 from oxydiphthalic dianhydride, 4 '-biphthalic anhydride, 2-hydroxyethyl methacrylate and 4,4' -diaminodiphenyl ether

In a dry reactor equipped with a flat bottom joint equipped with a stirrer, a condenser and an internal thermometer, 9.49g (32.25 mmol) of 4,4' -biphthalic anhydride and 10.0g (32.25 mmol) of oxydiphthalic anhydride were suspended in 140mL of diglyme while removing water. 16.8g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 0.05g of pure water and 10.7g (135 mmol) of pyridine were further added and stirred at 60℃for 18 hours. Next, after cooling the mixture to-20 ℃, 16.1g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridine hydrochloride was obtained. Next, after the mixture was warmed to room temperature and stirred for 2 hours, 9.7g (123 mmol) of pyridine and 25mL of N-methylpyrrolidone (NMP) were added, thereby obtaining a transparent solution. Next, 11.8g (58.7 mmol) of 4,4' -diaminodiphenyl ether was added to the obtained transparent solution by dropwise addition over 1 hour and dissolved in 100mL of NMP to obtain the product. Next, 5.6g (17.5 mmol) of methanol and 0.05g of 3, 5-di-t-butyl-4-hydroxytoluene were added, and the mixture was stirred for 2 hours. Next, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at 500rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred in 4 liters of water for 30 minutes again and filtered again. Next, the obtained polyimide precursor resin was dried at 45 ℃ for 3 days under reduced pressure, thereby obtaining a polyimide precursor (a-5). The polyimide precursor A-5 obtained had a weight average molecular weight of 23, 800 and a number average molecular weight of 10, 400.

The structure of A-5 is assumed to be represented by the following formula (A-5).

[ chemical formula 77]

Synthesis example A-6 ]

[ A-6: synthesis of polyimide precursor (A-6: polyimide precursor having radical polymerizable group) from 4,4 '-oxydiphthalic dianhydride, 4' -diaminodiphenyl ether and 2-hydroxyethyl methacrylate

To a separable flask was charged 155.1g of 4,4' -Oxydiphthalic Dianhydride (ODPA), 134.0g of 2-hydroxyethyl methacrylate (HEMA) and 400ml of gamma-butyrolactone. 79.1g of pyridine was added while stirring at room temperature, thereby obtaining a reaction mixture. After the completion of the heat generation based on the reaction, it was cooled to room temperature and left to stand for a further 16 hours.

Then, a solution of 206.3g of Dicyclohexylcarbodiimide (DCC) dissolved in 180ml of γ -butyrolactone was added to the reaction mixture with stirring for 40 minutes under ice cooling. Subsequently, a suspension of 93.0g of 4,4' -diaminodiphenyl ether in 350ml of gamma-butyrolactone was added over 60 minutes with stirring. After stirring for 2 hours at room temperature, 30ml of ethanol was added and stirred for 1 hour. Thereafter, 400ml of gamma-butyrolactone was added. The precipitate produced in the reaction mixture was obtained by filtration, thereby obtaining a reaction solution.

The obtained reaction solution was added to 3 liters of ethanol, thereby producing a precipitate formed from the crude polymer. The crude polymer thus formed was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran, whereby a crude polymer solution was obtained. The obtained crude polymer solution was dropped into 28 liters of water to precipitate a polymer, and the obtained precipitate was collected by filtration and then subjected to vacuum drying, whereby polymer A-6 was obtained in the form of a powder. The weight average molecular weight (Mw) of this polymer A-6 was measured, and as a result, it was 24,000.

Synthesis example A-7 ]

[ Synthesis of polyimide precursor from 3,3', 4' -biphenyltetracarboxylic dianhydride, 4' -diaminodiphenyl ether and 2-hydroxyethyl methacrylate (A-7: polyimide precursor having radical polymerizable group) ]

In Synthesis example 6, a reaction was carried out in the same manner as in Synthesis example A-6 except that 147.1g of 3,3', 4' -biphenyltetracarboxylic dianhydride was used in place of 155.1g of 4,4' -oxydiphthalic dianhydride, thereby obtaining a polymer A-7. The weight average molecular weight (Mw) of this polymer A-7 was measured, and found to be 22,900.

< Synthesis example A-8>

In a flask equipped with a stirrer and a condenser, 19.19g (36.7 mmol) of 4,4'- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride (Tokyo Chemical Industry co., ltd.) was mixed, 0.01g of 4-methoxyphenol (Tokyo Chemical Industry co., ltd.) was mixed with 21.98g (75 mmol) of CS-1 (the above-described synthetic product), 12.92g (163 mmol) of pyridine, 40.0g of diethylene glycol dimethyl ether (Tokyo Chemical Industry co., ltd.) and stirred at 60℃for 6 hours. Next, after the mixture was cooled to-20 ℃, 9.19g (76.3 mmol) of thionyl chloride was added dropwise over 90 minutes, and stirred for 2 hours. Next, 25mL of N-methylpyrrolidone (NMP) was added thereto, and 6.11g (30.5 mmol) of 4,4' -diaminodiphenyl ether was added thereto via 2-hour dropwise, and the mixture was dissolved in 100mL of NMP. Subsequently, 16.9g (367 mmol) of ethanol was added, and the mixture was stirred for 2 hours. Next, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at 500rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred in 4 liters of water for 30 minutes again and filtered again. Next, the obtained polyimide precursor resin was dried at 45 ℃ for 2 days under reduced pressure, thereby obtaining a polyimide precursor (a-8). The polyimide precursor A-8 obtained had a weight average molecular weight of 30, 100 and a number average molecular weight of 13, 800.

The structure of A-8 is assumed to be represented by the following formula (A-8).

[ chemical formula 78]

< Synthesis of comparative Compound C-1 >

In a flask equipped with a stirrer and a condenser, 10.24g (110 mmol) of aniline (Tokyo Chemical Industry co., ltd.) was dissolved in 100g of tetrahydrofuran, and cooled to 10 ℃. Then, phenyl isocyanate (Tokyo ChemicalIndustry co.,11.9g (100 mmol) and stirred at 25℃for 2 hours. This was crystallized into 500mL of a 1N aqueous hydrochloric acid solution, filtered, reslurried with water, and dried at 50℃for 24 hours, thereby obtaining 18g of C-1. From the slave ¹ The H-NMR spectrum was found to be C-1. The structure of C-1 is shown in the following formula (C-1).

[ chemical formula 79]

< examples and comparative examples >

In each example, the components described in the following table were mixed, respectively, to obtain each resin composition. In each comparative example, the components described in the following table were mixed, and each comparative composition was obtained.

Specifically, the content of each component described in the table is set to the amount (parts by mass) described in the column "addition amount" of each column of the table.

The obtained resin composition and the comparative composition were subjected to pressure filtration using a polytetrafluoroethylene filter having a pore width of 0.5. Mu.m.

In the table, "-" indicates that the composition does not contain a corresponding component.

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The details of the components described in the table are as follows.

[ resin (cyclized resin or precursor thereof) ]

A-1 to A-8: a-1 to A-8 synthesized in the above

[ polymerization initiators (all trade names) ]

OXE-01: IRGACURE OXE 01 (manufactured by BASF corporation)

OXE-02: IRGACURE OXE 02 (manufactured by BASF corporation)

[ Compound A ]

CS-1 to CS-33: the above-mentioned synthetic product

C-1: the above-mentioned synthetic product

[ alkaline Forming agent ]

D-1 to D-2: compounds of the structure

D-3: WPBG-027 (FUJIFILM Wako Pure Chemical Corporation)

[ chemical formula 80]

[ migration inhibitor ]

E-1 to E-6: compounds of the structure

[ chemical formula 81]

[ Metal adhesion improver ]

F-1 to F-3: compounds of the structure

[ chemical formula 82]

[ polymerizable Compound (trade name in each case) ]

SR-209: SR-209 (Sartomer Company, manufactured by Inc)

SR-231: SR-231 (Sartomer Company, manufactured by Inc)

SR-239: SR-239 (made by Sartomer Company, inc)

ADPH: dipentaerythritol hexaacrylate (Shin-Nakamura Chemical Co., ltd.)

[ polymerization inhibitor ]

G-1:1, 4-benzoquinone

G-2: 4-methoxyphenol

G-3:1, 4-dihydroxybenzene

G-4: compounds of the structure

[ chemical formula 83]

[ other additives ]

H-1: n-phenyl diethanolamine (Tokyo Chemical Industry Co., ltd.)

[ solvent ]

DMSO: dimethyl sulfoxide

GBL: gamma-butyrolactone

NMP: n-methylpyrrolidone

In the tables, "DMSO/GBL" means that DMSO is used: gbl=80: 20 (mass ratio) of DMSO and GBL.

< evaluation >

[ evaluation of elongation at Break ]

In each of examples and comparative examples, a resin composition or a composition for comparison was applied to a silicon wafer by spin coating, respectively, 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 5 minutes, thereby obtaining a resin composition layer having a uniform thickness of about 15. Mu.m on the silicon wafer.

Using a stepper (Nikon NSR 2005 i9C) and at 500mJ/cm ² The entire surface of the obtained resin composition layer was subjected to i-ray exposure.

The exposed resin composition layer (resin layer) was heated at a temperature rise rate of 10 ℃/min in a nitrogen atmosphere, and after reaching the temperature described in the column "temperature" of "curing conditions" in the table, it was heated for 3 hours. The cured resin layer (cured film) was immersed in a 4.9 mass% aqueous hydrofluoric acid solution, and the cured film was peeled from the silicon wafer. The peeled cured film was punched by a punching machine to prepare a test piece having a sample width of 3mm and a sample length of 30 mm. The obtained test piece was measured for elongation at break in the longitudinal direction thereof by JIS-K6251 using a tensile tester (Tensilon) at a crosshead speed of 300 mm/min under an atmosphere of 25℃and 65% RH (relative humidity). Each of the evaluations was performed 5 times, and an arithmetic average of the elongation at break (elongation at break) of the test piece was used as an index value.

The index values were evaluated according to the following evaluation criteria, and the evaluation results are shown in the column of "elongation at break" in the table. It can be said that the greater the index value, the more excellent the film strength (elongation at break) of the obtained cured film.

(evaluation criterion)

A: the index value is 60% or more.

B: the index value is 55% or more and less than 60%.

C: the index value is 50% or more and less than 55%.

D: the index value is less than 50%.

[ evaluation of drug resistance ]

The respective resin compositions or comparative compositions prepared in the respective examples and comparative examples were applied to a silicon wafer by spin coating, respectively, to thereby form resin composition layers. The silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100℃for 5 minutes, thereby forming a resin composition layer of a uniform thickness of 15. Mu.m on the silicon wafer. Using a stepper (Nikon NSR 2005 i9C) at 500mJ/cm ² The resin composition layer on the silicon wafer was subjected to blanket exposure with the exposure energy, and the exposed resin composition layer (resin layer) was heated at a heating rate of 10 ℃/min under a nitrogen atmosphere, and heated for 180 minutes at a temperature described in the column "temperature" of "curing conditions" of the table, thereby obtaining a cured layer (resin layer) of the resin composition layer.

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

Liquid medicine: dimethyl sulfoxide (DMSO) with 25 mass% aqueous tetramethylammonium hydroxide (TMAH) 90:10 (mass ratio) of the mixture

Evaluation conditions: the resin layer was immersed in the liquid medicine at 75℃for 15 minutes, and the film thicknesses before and after immersion were compared to calculate the dissolution rate (nm/min). The film thickness was measured at 10 points on the coated surface using an ellipsometer (KT-22 manufactured by Foothill Co.) and found as an arithmetic average value.

The evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in the column of "chemical resistance" in the table. It can be said that the smaller the dissolution rate is, the more excellent the chemical resistance is.

Evaluation criterion-

A: the dissolution rate is less than 200 nm/min.

B: the dissolution rate is 200 nm/min or more and less than 300 nm/min.

C: the dissolution rate is 300 nm/min or more and less than 400 nm/min.

D: the dissolution rate is 400 nm/min or more.

[ evaluation of solubility (developability) of developer ]

The evaluation of the solubility of the developer was performed as follows.

The resin compositions prepared in the examples and comparative examples or the comparative compositions were applied to silicon wafers by spin coating, respectively, to form resin composition layers.

The silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100℃for 5 minutes, thereby obtaining a resin composition layer having a uniform thickness of 35. Mu.m on the silicon wafer.

Using a stepper (Nikon NSR 2005 i9C) and passing i-rays at 500mJ/cm ² The resin composition layer on the silicon wafer is exposed to light. The exposure was performed using a binary mask having a 1:1 line and space pattern formed with a width of 50 μm, a width of 70 μm, or a width of 100 μm.

In the example described as "solvent (cyclopentanone)" in the column of "development method (developer)" in the table, the resin composition layer after exposure was subjected to spray development using cyclopentanone at 30 ℃ as a developer, and rinsed with PGMEA (propylene glycol monomethyl ether acetate).

In the example described as "alkali (TMAH)" in the column of "development method (developer)" in the table, the resin composition layer after exposure was developed using a 2.38 mass% aqueous tetramethylammonium hydroxide solution at 30 ℃ as a developer, and rinsed with ion-exchanged water.

At the time of exposure, a 1:1 line-space (L/S) pattern having a width of 100 μm was used, and the minimum time required for dissolution of the unexposed portion at a thickness of 35 μm of the resin composition layer was set as the minimum development time, and evaluated according to the following evaluation criteria. It can be said that the shorter the minimum development time, the more excellent the developer solubility. The evaluation results are shown in the column "developability" of the table.

Evaluation criterion-

A: the minimum development time is within 30 seconds.

B: the minimum development time exceeds 30 seconds and is less than 60 seconds.

C: the minimum development time exceeds 60 seconds and is less than 120 seconds.

D: not completely dissolved within 120 seconds.

From the above results, it was found that the cured film formed from the resin composition according to the present invention was excellent in drug resistance.

The comparative compositions according to comparative examples 1 to 4 did not contain the compound a.

It was found that the cured film formed from such a comparative composition had poor chemical resistance.

< example 101>

The resin composition used in example 1 was applied to the surface of a copper thin layer of a resin substrate having a copper thin layer formed on the surface thereof in a layer form by spin coating, and after drying at 100 ℃ for 4 minutes to form a resin composition layer having a film thickness of 20 μm, exposure was performed using a stepper (Nikon co., ltd. Manufactured by NSR1505 i 6). For exposure, the exposure was carried out at a wavelength of 365nm via a mask (binary mask with a pattern of 1:1 lines and spaces, line width of 10 μm). After exposure, the mixture was heated at 100℃for 4 minutes. After the above heating, the layer was developed with cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds, thereby obtaining a pattern of layers.

Then, the temperature was raised at a temperature rise rate of 10 ℃/min in a nitrogen atmosphere, and after reaching 230 ℃, the temperature was maintained at 230 ℃ for 3 hours, thereby forming an interlayer insulating film for a re-wiring layer. The interlayer insulating film for a rewiring layer is excellent in insulation properties.

Then, a semiconductor device was manufactured using these interlayer insulating films for a rewiring layer, and as a result, normal operation was confirmed.

Claims

1. A resin composition comprising:

cyclizing the resin or its precursor;

A radical-polymerizable compound having a radical-polymerizable group,

the compound A satisfies at least one of the following conditions 1 and 2,

condition 1: the compound A has more than 2 free radical polymerizable groups;

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

the cyclized resin or its precursor is at least 1 resin selected from polyimide, polyimide precursor, polybenzoxazole precursor, polyamideimide and polyamideimide precursor.

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

the acid value of the cyclized resin or the precursor thereof is 0 mmol/g-1.2 mmol/g.

4. The resin composition according to any one of claim 1 to 3, wherein,

the compound a contains an aromatic group.

5. The resin composition according to any one of claims 1 to 4, further comprising a compound different from the compound a as the radical polymerizable compound.

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

the compound A is a compound represented by the following formula (1-1) or formula (1-2),

7. The resin composition according to any one of claims 1 to 5, which is used for forming an interlayer insulating film for a rewiring layer.

8. A cured product obtained by curing the resin composition according to any one of claims 1 to 7.

9. A laminate comprising 2 or more layers formed of the cured product of claim 8, and a metal layer between any of the layers formed of the cured product.

10. A method for producing a cured product, comprising a film forming step of applying the resin composition according to any one of claims 1 to 7 to a substrate to form a film.

11. The method for producing a cured product according to claim 10, comprising an exposure step of selectively exposing the film and a development step of developing the film with a developer to form a pattern.

12. The method for producing a cured product according to claim 10 or 11, comprising a heating step of heating the film at 50 to 450 ℃.

13. A semiconductor device comprising the cured product of claim 8 or the laminate of claim 9.