CN117203265A

CN117203265A - Resin composition, cured product, laminate, method for producing cured product, semiconductor device, and resin

Info

Publication number: CN117203265A
Application number: CN202280029358.XA
Authority: CN
Inventors: 野崎敦靖
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2021-04-23
Filing date: 2022-04-07
Publication date: 2023-12-08

Abstract

The present invention provides a resin composition which can obtain a cured product excellent in elongation at break, a cured product obtained by curing the resin composition, a laminate comprising the cured product, a method for producing the cured product, a semiconductor device comprising the cured product or the laminate, or a novel resin. The resin composition has at least one of a repeating unit represented by the following formula (1-1) and a repeating unit represented by the following formula (1-2).

Description

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

Technical Field

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

Background

Cyclized resins such as polyimide are excellent in heat resistance, insulation properties, and the like, and therefore can be used for various applications. The use is not particularly limited, and examples of the use include a material or a protective film used as an insulating film or a sealing material when a semiconductor device for mounting is used. Further, the film 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 a precursor of the cyclized resin such as polyimide.

Such a resin composition is applied to a substrate to form a photosensitive film by coating or the like, 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 a polyimide precursor is cyclized by heating, for example, to form a cyclized resin such as polyimide in a cured product.

The resin composition can be applied by a known coating method or the like, and therefore, it can be said that the resin composition is excellent in manufacturing suitability, for example, the shape, size, application position and the like of the applied resin composition are highly free in design and the like when applied. In addition to the high performance of the cyclized resin such as polyimide, the expansion of the application of the resin composition in industry is expected to be remarkable from the viewpoint of excellent suitability for such production.

For example, patent document 1 discloses a polyamic acid ester resin composition comprising a polyimide precursor having a specific structure, a carboxylic acid compound having a specific structure, or an acid anhydride thereof, optionally containing a polymer compound other than the polyimide precursor, and the carboxylic acid compound or the acid anhydride thereof being capable of chemically bonding to the polyimide precursor and/or the polymer compound other than the polyimide precursor.

Patent document 2 describes a resin composition containing a polyimide precursor having a specific repeating unit.

Technical literature of the prior art

Patent literature

Patent document 1: international publication No. 2020/080206

Patent document 2: japanese patent application laid-open No. 2012-224755

Disclosure of Invention

Technical problem to be solved by the invention

In a resin composition containing a resin such as a polyimide precursor, the obtained cured product is required to have excellent elongation at break.

The present invention provides a resin composition which can obtain a cured product having excellent elongation at break, 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 or a novel resin comprising 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:

a resin having at least one of a repeating unit represented by formula (1-1) and a repeating unit represented by formula (1-2); a kind of electronic device with high-pressure air-conditioning system

The solvent is used for the preparation of the aqueous solution,

[ chemical formula 1]

In the formula (1-1) or the formula (1-2), W ¹ Represents a 2-valent organic group, X ¹ Represents a 4-valent organic group, R ¹ ～R ³ Each independently represents a group represented by the following formula (3-1) or a group represented by the formula (3-2), W ² Represents a 2-valent organic group, X ² Represents a 3-valent organic group, the resin comprising a compound selected from the group consisting of those represented by the formula (1-1) and R ¹ R is R ² At least one of them is a repeating unit of a group represented by the formula (3-1), and R is represented by the formula (1-2) ³ At least 1 kind of repeating units among repeating units of the group represented by the formula (3-1),

[ chemical formula 2]

In the formula (3-1) and the formula (3-2), Z ¹ Z is as follows ² Each independently represents an organic group, Z ¹ And Z ² Can be bonded to form a ring structure, A ² Represents an oxygen atom or-NH-, R ¹¹³ Represents a hydrogen atom or a monovalent organic group, and represents a bonding site to other structures.

<2> the resin composition according to <1>, wherein,

the group represented by the formula (3-1) is a group represented by the following formula (3-1-1) or formula (3-1-2).

[ chemical formula 3]

In the formula (3-1-1), cy represents an aliphatic ring structure or an aromatic ring structure, represents a bonding site with other structure,

in the formula (3-1-2), Z ³ Z is as follows ⁴ Each independently represents an alkyl group, and represents a bonding site to another structure.

<3> the resin composition according to <1> or <2>, wherein,

the ratio of the molar amount of the group represented by the formula (3-1) to the total molar amount of the group represented by the formula (3-1) and the group represented by the formula (3-2) contained in the resin is 0.1 mol% or more.

<4> the resin composition according to any one of <1> to <3>, wherein,

the ratio of the molar amount of the group represented by formula (3-1) to the total molar amount of the group represented by formula (3-1) and the group represented by formula (3-2) contained in the resin is 99.9 mol% or less.

<5> the resin composition according to any one of <1> to <4>, wherein,

the ratio of the molar amount of the group represented by formula (3-1) to the total molar amount of the group represented by formula (3-1) and the group represented by formula (3-2) contained in the resin is 80 mol% or more.

<6> the resin composition according to any one of <1> to <5>, wherein,

r in formula (3-2) ¹¹³ Is a group having a polymerizable group.

<7> the resin composition according to any one of <1> to <6>, wherein,

w in formula (1-1) ¹ And W in formula (1-2) ² Comprising a group represented by any one of the formulae (5) to (7).

[ chemical formula 4]

In the formula (5), Y ¹ Represents a single bond or a 2-valent linking group, each represents a bonding site to another structure, in formula (6), Y ² Represents a single bond or a 2-valent linking group, each represents a bonding site to another structure, and in formula (7), each represents a bonding site to another structure.

<8> the resin composition according to any one of <1> to <7>, wherein,

the weight average molecular weight of the resin is 10,000 or more.

<9> the resin composition according to any one of <1> to <8>, wherein,

the acid value of the resin is 0-1 mmol/g.

<10> the resin composition according to any one of <1> to <9>, further comprising a polymerization initiator.

<11> the resin composition according to any one of <1> to <10>, further comprising a polymerizable compound.

<12> the resin composition according to <11>, wherein the polymerizable compound has at least 1 group selected from the group consisting of an imide group, a urea group and a urethane group.

<13> the resin composition according to any one of <1> to <12>, further comprising a compound B which is at least 1 compound selected from the group consisting of a compound having a maleimide structure and a precursor of a compound having a maleimide structure.

<14> the resin composition according to <13>, further comprising a compound C which is a compound having a group capable of reacting with a maleimide structure.

<15> the resin composition according to <14>, wherein the group capable of reacting with maleimide structure in the above-mentioned compound C is at least 1 group selected from the group consisting of an ethylenically unsaturated group, a hydroxyl group, an epoxy group and an amino group.

<16> the resin composition according to any one of <1> to <15>, which is used for forming an interlayer insulating film for a rewiring layer.

<17> a cured product obtained by curing the resin composition according to any one of <1> to <16 >.

<18> a laminate comprising 2 or more layers of the cured product of <17>, wherein at least 1 metal layer is included between the layers of the cured product.

<19> a method for producing a cured product comprising a film formation step of applying the resin composition according to any one of <1> to <16> to a substrate to form a film.

<20> the method for producing a cured film according to <19>, comprising an exposure step of exposing the film and a developing step of developing the film.

<14> the method for producing a cured product according to <19> or <20>, comprising a heating step of heating the film at 50 to 450 ℃.

<22> a semiconductor device comprising the cured product of <17> or the laminate of <18 >.

<23> a resin having at least one of the repeating unit represented by the formula (1-1) and the repeating unit represented by the formula (1-2).

[ chemical formula 5]

In the formula (1-1) or the formula (1-2), W ¹ Represents a 2-valent organic group, X ¹ Represents a 4-valent organic group, R ¹ ～R ³ Each independently represents a group represented by the following formula (3-1) or a group represented by the formula (3-2), W ² Represents a 2-valent organic group, X ² Represents a 3-valent organic group, the resin comprising a compound selected from the group consisting of those represented by the formula (1-1) and R ¹ R is R ² At least one of them is a repeating unit of a group represented by the formula (3-1), and R is represented by the formula (1-2) ³ At least 1 kind of repeating units among repeating units of the group represented by the formula (3-1).

[ chemical formula 6]

(3-1)

<24>According to<23>The resin, wherein R in formula (3-2) ¹¹³ Is a group having a polymerizable group.

<25>According to<23>Or (b)<24>The resin, wherein W in formula (1-1) ¹ And W in formula (1-2) ² Comprising a group represented by the following formula (4).

[ chemical formula 7]

In formula (4), each represents a bonding site to another structure.

Effects of the invention

According to the present invention, there are provided a resin composition which can obtain a cured product excellent in elongation at break, 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 or a resin 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, the numerical range indicated by the symbol "to" refers to a range in which numerical values before and after "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.

In the labeling of groups (atomic groups) in the present specification, the label which is not labeled with a substituted or unsubstituted group includes a group (atomic group) having no substituent, and includes a group (atomic group) 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 the present specification, unless otherwise specified, "exposure" includes not only exposure by light but also exposure by 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 active ray such as extreme ultraviolet rays (EUV light), X-rays, and electron beams, and radiation, which are typified by excimer laser light.

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 content refers to the total mass of the components other than the solvent among all the 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 Gel Permeation Chromatography (GPC) and are defined as polystyrene equivalent values. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained by using, for example, 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. These molecular weights were measured using THF (tetrahydrofuran) as an eluent, unless otherwise specified. Among them, NMP (N-methyl-2-pyrrolidone) can be used when THF is not suitable as an eluent, for example, when solubility is low. Further, unless otherwise specified, a UV ray (ultraviolet ray) detector having a wavelength of 254nm 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 the 3 rd element may be further interposed between the layer to be the reference and the other layer, and the layer to be the reference and the other layer do not need to be in contact. If not specifically described, the direction in which the base material layers are stacked is referred to as "up", or the direction from the base material toward the resin composition layer is referred to as "up", and the opposite direction is referred to as "down", when the resin composition layer is present. In addition, these vertical directions may be set for convenience in the present specification, and in a practical embodiment, the "upward" direction in the present specification may be oriented differently from the vertical 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 means the total content of all the compounds corresponding to the component.

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

In the present specification, a combination of preferred embodiments is a more preferred embodiment.

(resin composition)

The resin composition of the present invention comprises a resin having at least one of a repeating unit represented by the following formula (1-1) and a repeating unit represented by the following formula (1-2), and a solvent.

Hereinafter, a resin having at least one of the repeating unit represented by the following formula (1-1) and the repeating unit represented by the following formula (1-2) is also referred to as a "specific resin".

[ chemical formula 8]

In the formula (1-1) or the formula (1-2), W ¹ Represents a 2-valent organic group, X ¹ Represents a 4-valent organic group, R ¹ ～R3 ^{Dividing into} Independently of each other, a group represented by the following formula (3-1) or a group represented by the formula (3-2), W ² Represents a 2-valent organic group, X ² Represents a 3-valent organic group, the resin comprising a compound selected from the group consisting of those represented by the formula (1-1) and R ¹ R is R ² At least one of them is a repeating unit of a group represented by the formula (3-1), and R is represented by the formula (1-2) ³ At least 1 kind of repeating units among repeating units of the group represented by the formula (3-1).

[ chemical formula 9]

Namely, in the formula (1-1), W ¹ Represents a 2-valent organic group, X ¹ Represents a 4-valent organic group, R ¹ R is R ² Each independently represents a group represented by the following formula (3-1) or a group represented by the formula (3-2), R ¹ R is R ² At least one of them is a group represented by the formula (3-1),

in the formula (1-2), W ² Represents a 2-valent organic group, X ² Represents a 3-valent organic group, R ³ The group represented by the formula (3-1).

The resin composition of the present invention is preferably used for forming a photosensitive film for exposure and development, and is preferably used 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 positive development or for forming a photosensitive film for negative development, and is preferably used for forming a photosensitive film for negative development.

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

As the exposure method, the developing solution, and the developing method, for example, the exposure method described in the exposure step described in the description of the method for producing a cured product, the developing solution described in the developing step, and the developing method described in the developing step can be used.

According to the resin composition of the present invention, a cured product excellent in elongation at break can be obtained.

The mechanism for obtaining the above effects is not clear, but is presumed as follows.

Conventionally, a resin composition containing a polyimide precursor resin or a polyamideimide precursor resin has been used to obtain a cured product.

In addition, it is being studied to lower the temperature at the time of curing by adding a photo-base generator or a thermal base generator to the resin composition to generate a base at the time of exposure or heating to promote cyclization of the polyimide precursor resin or the polyamideimide precursor resin.

In the present invention, by using a resin having a repeating unit represented by the formula (1-1) or the formula (1-2), a secondary amine can be generated from the resin upon heat curing.

In this way, secondary amine can be generated with the ring closure of the resin as the main component, and thus the amount of secondary amine generated can be increased more than in the case of using a thermal base generator.

As a result, it is considered that, by using the resin composition of the present invention, the ring closure of the resin proceeds sufficiently even when heated at a low temperature (for example, 180 ℃) as compared with the case where only the thermal base generator is used in the resin composition, and a cured product excellent in elongation at break can be obtained.

Further, it is considered that even if heated at a low temperature in this way, the ring closure of the resin proceeds sufficiently, and therefore the obtained cured film is excellent in chemical resistance.

In the alkali generating mechanism of the present invention, the residue (carboxylic acid, salt, etc.) of the photo-or thermal alkali generating agent after the alkali generation and the photo-or thermal alkali generating agent itself (not decomposed) are less likely to remain in the composition, and therefore the moisture resistance is also improved.

Here, patent documents 1 and 2 do not describe resins using at least one of the repeating unit represented by the formula (1-1) and the repeating unit represented by the formula (1-2).

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 comprises a resin (specific resin) having at least one of the repeating unit represented by the formula (1-1) and the repeating unit represented by the formula (1-2).

The specific resin preferably contains at least the repeating unit represented by the formula (1-1).

The specific resin is preferably a polyimide precursor or a polyamideimide precursor, and the specific resin is more preferably a polyimide precursor.

[ chemical formula 10]

[ chemical formula 11]

In the formula (1-1), R is ¹ R is R ² In the case of the groups represented by the formula (3-1), R ¹ And R is ² Each of which is a group corresponding to the group represented by the formula (3-1), R ¹ R is R ² May be the same group or may be different groups.

In the formula (1-1), R is ¹ R is R ² In the case of the groups represented by the formula (3-2), R ¹ And R is ² Each of which is a group corresponding to the group represented by the formula (3-2), R ¹ R is R ² May be the same group or may be different groups.

In the formula (1-1), W ¹ Represents a 2-valent organic group. 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, 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, and more preferably a group containing an aromatic group having 6 to 20 carbon atoms. The hydrocarbon group in the chain of the above-mentioned straight chain or branched aliphatic group may be substituted with a heteroatom-containing group, and the hydrocarbon group of the cyclic aliphatic group and the ring member of the aromatic group may be substituted with a heteroatom-containing group. 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, 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 more than 2 of the above. The preferred ranges of these are as described above.

W ¹ Preferably derived from diamines. Examples of the diamine used for producing the specific resin include linear or branched aliphatic, cyclic aliphatic, and aromatic diamines. 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 hydrocarbon group in the chain of the above-mentioned straight chain or branched aliphatic group may be substituted with a heteroatom-containing group, and the hydrocarbon group of the cyclic aliphatic group and the ring member of the aromatic group may be substituted with a heteroatom-containing group. Examples of the group containing an aromatic group include the following groups.

[ chemical formula 12]

Wherein A represents a single bond or a 2-valent group, preferably a single bond or an aliphatic hydrocarbon group selected from the group consisting of C1-10 aliphatic hydrocarbon groups which may be substituted with fluorine atoms, -O-, -C (=O) -, -S-, -SO ₂ -, -NHCO-or a combination of these, more preferably a single bond, selected from the group consisting of an alkylene group having 1 to 3 carbon atoms 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 at least 1 diamine selected from the following: 1, 2-diaminoethane, 1, 2-diaminopropane, 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 6-diaminohexane; 1, 2-or 1, 3-diaminocyclopentane, 1,2-, 1, 3-or 1, 4-diaminocyclohexane, 1,2, 1, 3-or 1, 4-bis (aminomethyl) cyclohexane, bis- (4-aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4 '-diamino-3, 3' -dimethylcyclohexylmethane, isophorone diamine; m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4' -or 3,3' -diaminobiphenyl, 4' -diaminodiphenyl ether, 3-diaminodiphenyl ether, 4' -or 3,3' -diaminodiphenylmethane, 4' -or 3,3' -diaminodiphenylsulfone, 4,4' -or 3,3' -diaminodiphenyl sulfide, 4' -or 3,3' -diaminobenzophenone, 3' -dimethyl-4, 4' -diaminobiphenyl, 2' -dimethyl-4, 4' -diaminobiphenyl, 3' -dimethoxy-4, 4' -diaminobiphenyl, and 2, 2-bis (4-aminophenyl) propane, 2-bis (4-aminophenyl) hexafluoropropane, 2-bis (3-hydroxy-4-aminophenyl) propane, 2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2-bis (3-amino-4-hydroxyphenyl) propane 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 4' -diamino p-diphenyl, 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' -dimethyl-3, 3 '-diaminodiphenyl sulfone, 3',5 '-tetramethyl-4, 4' -diaminodiphenyl methane, 2, 4-and 2, 5-diaminocumene, 2, 5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5, 6-tetramethyl-p-phenylenediamine, 2,4, 6-trimethyl-m-phenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, 2, 7-diaminofluorene, 2, 5-diaminopyridine, 1, 2-bis (4-aminophenyl) ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1, 5-diaminonaphthalene, diaminobenzol, 1, 3-bis (4-aminophenyl) hexafluoropropane, 1, 4-bis (4-aminophenyl) octafluorobutane, 1, 5-bis (4-aminophenyl) decafluoropentane, 1, 7-bis (4-aminophenyl) tetradecanefluoroheptane, 2-bis [4- (3-aminophenyl) hexafiuorophenoxy ] propane, 2-5-diaminophenoxy ] hexafluoropropane, 2, 4-bis [ 2, 3-aminophenyl ] hexafluoropropane For bis (4-amino-2-trifluoromethylphenoxy) benzene, 4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4' -bis (4-amino-3-trifluoromethylphenoxy) biphenyl 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',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 may be preferably used.

From the viewpoint of flexibility of the obtained organic film, W ¹ 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 more than 2 of the above. 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 represented by L is preferably an alkylene group.

Moreover, from the viewpoint of the i-ray transmittance, W ¹ The 2-valent organic group represented by the following formula (51) or (61) is preferable. In particular, from the viewpoint of the i-ray transmittance and the availability, the 2-valent organic group represented by formula (61) is more preferable.

(51)

[ chemical formula 13]

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 the formula (1-1).

As R ⁵⁰ ～R ⁵⁷ Examples of the 1-valent organic group (1) include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

[ chemical formula 14]

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 (1-1).

Examples of the diamine having the structure of 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.

Further, from the viewpoint of moisture resistance and chemical resistance of the obtained cured film, W ¹ The compound preferably contains a group represented by any one of the following formulas (5) to (7), more preferably a group represented by any one of the following formulas (5) to (7).

Wherein, from the viewpoint of inhibiting film shrinkage during curing, W ¹ The group represented by the following formula (5) is preferable.

[ chemical formula 15]

In the formulas (5) to (7), Y ¹ Represents a single bond or a 2-valent linking group, Y ² Represents a single bond or a 2-valent linking group, and each represents a bonding site to another structure.

In the formula (5), Y ¹ Preferably a single bond or an aliphatic hydrocarbon group selected from the group consisting of C1-10 aliphatic hydrocarbon groups which may be substituted with a fluorine atom, -O-, -C (=O) -, -S-, -SO) ₂ -、-NR ^N The group in-or a combination of these, more preferably a single bond. R is as described above ^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.

In the formula (6), Y ² Preferably a single bond or an aliphatic hydrocarbon group selected from the group consisting of C1-10 aliphatic hydrocarbon groups which may be substituted with a fluorine atom, -O-, -C (=O) -, -S-, -SO) ₂ -、-NR ^N The group in-or a combination of these, more preferably a single bond. R is as described above ^N As described above.

The group represented by the formula (7) is preferably a group represented by the following formula (7-1).

[ chemical formula 16]

From the viewpoint of suppressing cure shrinkage, wherein W ¹ The compound preferably contains a group represented by the following formula (4), more preferably a group represented by the following formula (4).

[ chemical formula 17]

In formula (4), each represents a bonding site to another structure.

X in formula (1-1) ¹ Represents a 4-valent organic group. The 4-valent organic group is preferably a 4-valent organic group containing an aromatic ring, and more preferably a group represented by the following formula (5) or (6). In the formula (5) or (6), each independently represents other structuresIs bonded to the bonding site of the substrate.

[ chemical formula 18]

In the formula (5), R ¹¹² Is a single bond or a 2-valent linking group, preferably 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 -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 valence 2 group in (a).

Specifically, X ¹ The tetracarboxylic acid residue remaining after the acid anhydride group is removed from the tetracarboxylic dianhydride may be mentioned. As equivalent to X ¹ The specific resin may contain only 1 tetracarboxylic dianhydride residue or may contain 2 or more types of tetracarboxylic dianhydride residues.

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

[ chemical formula 19]

In the formula (O), R ¹¹⁵ Represents a 4-valent organic group. R is R ¹¹⁵ Is preferably within the range of X in formula (1-1) ¹ The meaning is the same, and the preferred ranges are also the same.

Specific examples of tetracarboxylic dianhydrides 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.

As a preferable example, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International publication No. 2017/038598 can be mentioned.

In the formula (1-1), R ¹ R is R ² Each independently represents a group represented by the following formula (3-1) or a group represented by the following formula (3-2).

[ chemical formula 20]

In the formula (3-1), Z ¹ Z is as follows ² Each independently represents an organic group, preferably a hydrocarbon group or a hydrocarbon group and is selected from the group consisting of-O-, -C (=o) -, -S (=o) ₂ -and-NR ^N -a group represented by a combination of at least 1 group of the groups, more preferably a hydrocarbon group or a combination of a hydrocarbon group and-O-. R is R ^N As described above.

The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group, more preferably a saturated aliphatic hydrocarbon group.

The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 8.

The aliphatic hydrocarbon group may have any of a linear, branched, and cyclic structure, or may have a structure represented by a combination of these structures.

The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 10, and still more preferably 6.

The above-mentioned hydrocarbon group may have a known substituent within a range where the effect of the present invention can be obtained.

And Z is ¹ Z is as follows ² The mode in which at least one of them has a polymerizable group is also one of preferred modes of the present invention.

Examples of the polymerizable group include a radical polymerizable group, an epoxy group, an oxetanyl group, a hydroxymethyl group, and an alkoxymethyl group, and a radical polymerizable group is preferable.

The radical polymerizable group is preferably a group having an ethylenically unsaturated group, and examples thereof include a (meth) acryloyloxy group, a (meth) acrylamide group, a vinylphenyl group, a maleimide group, a styryl group, a vinyl group, and a (meth) allyl group.

Among them, (meth) acryloyloxy groups are preferable from the viewpoint of reactivity.

These polymerizable groups may be directly bonded to the nitrogen atom in the formula (3-1), or may be bonded via a linking group such as a hydrocarbon group (e.g., an alkylene group).

In the formula (3-1), Z ¹ Z is as follows ² A ring structure may be formed.

The ring structure may be an aromatic ring structure or an aliphatic ring structure, and is preferably an aliphatic ring structure, and more preferably a saturated aliphatic ring structure.

The cyclic amine having 2 to 10 carbon atoms is preferable, and examples thereof include a pyrrolidine ring, a piperidine ring, a morpholine ring, an octahydroindole ring, a pyrrole ring, a pyridine ring, and the like, and a pyrrolidine ring, a piperidine ring, or a morpholine ring is preferable.

The ring structure may have a substituent within a range where the effect of the present invention can be obtained. Examples of the substituent include a hydrocarbon group and a halogen atom. Examples of the ring structure substituted with a substituent include a dimethylpiperidine ring.

The group represented by the formula (3-1) is preferably a group represented by the following formula (3-1-1) or formula (3-1-2).

[ chemical formula 21]

In the formula (3-1-1), the ring structure represented by Cy is preferably an aliphatic ring structure, more preferably a saturated aliphatic ring structure.

Examples of the ring structure represented by Cy include a pyrrolidine ring, a piperidine ring, a morpholine ring, an octahydroindole ring, a pyrrole ring, a pyridine ring, and the like, and a pyrrolidine ring, a piperidine ring, or a morpholine ring is preferable.

The ring structure represented by Cy may have a substituent within a range in which the effect of the present invention can be obtained. Examples of the substituent include a hydrocarbon group and a halogen atom. Examples of the ring structure substituted with a substituent include a dimethylpiperidine ring.

In the formula (3-1-2), Z ³ Z is as follows ⁴ Each independently represents an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably an alkyl group having 1 to 8 carbon atoms.

The alkyl group may have any of a linear, branched, and cyclic structure, or may have a structure represented by a combination of these structures.

Specific examples of the group represented by the formula (3-1) include, but are not limited to, the following.

[ chemical formula 22]

The specific resin is preferably a resin that generates a base by heating at 250 ℃, more preferably a resin that generates a base by heating at 230 ℃, still more preferably a resin that generates a base by heating at 200 ℃, and particularly preferably generates a base at any one of 120 to 180 ℃.

Whether a specific resin generates a base at a certain temperature X deg.c is judged by the following method.

After heating 1 mol of the specific resin in a closed vessel at 1 air pressure at the above-mentioned X ℃ for 3 hours, the amount of decomposition was quantified by a method such as HPLC (high performance liquid chromatography), whereby it was possible to determine whether or not a base was generated. The amount of the base to be produced is preferably 0.1 mol or more, more preferably 0.5 mol or more. The upper limit of the amount of the base to be produced is not particularly limited, and may be 1000 moles or less, for example.

The molecular weight of the base derived from the specific resin is preferably 40 to 1,000, more preferably 40 to 500, and even more preferably 50 to 400.

The boiling point of the base having the pyridine structure is preferably 50 to 600 ℃, more preferably 50 to 500 ℃, still more preferably 50 to 450 ℃ under 1 atmosphere.

The base to be produced is preferably a base having a pKa of 0 or more, more preferably 3 or more, and still more preferably 6 or more of the conjugate acid. The upper limit of the pKa of the conjugate acid is not particularly limited, but is preferably 30 or less.

pKa is a value whose equilibrium constant Ka is expressed by its negative common logarithmic pKa taking into account the dissociation reaction of the hydrogen ions released by the acid. In the present specification, unless otherwise specified, pKa is set to a calculated value based on ACD/ChemSketch (registered trademark).

When there are a plurality of pKa of the conjugate acid, it is preferable that at least 1 is within the above range.

In the formula (3-2), A ² Preferably an oxygen atom.

R in formula (3-2) ¹¹³ Represents a hydrogen atom or a 1-valent organic group. The 1-valent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkylene oxide group. And R is ¹¹³ Preferably, the polymerizable groups are included, more preferably both of them are included. R is R ¹¹³ It is also preferable to contain 2 or more polymerizable groups. The polymerizable group is a group that can undergo a crosslinking reaction by the action of heat, a radical, 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, a benzoxazolyl group, a blocked isocyanate group, and an amino group. The radical polymerizable group of the specific resin 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 vinylphenyl group or the like), (meth) acrylamide group, (meth) acryloyloxy group, a group represented by the following formula (III), and the like, and a group represented by the following formula (III) is preferable.

[ chemical formula 23]

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 polyalkoxyene groups.

R ²⁰¹ Preferable examples of (C) include an alkylene group such as an ethenyl group, an propenyl group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, or a dodecamethylene group, a 1, 2-butanediyl group, a 1, 3-butanediyl group, and-CH ₂ CH(OH)CH ₂ -, polyalkoxylene, more preferably alkylene such as ethenyl or propenyl, -CH ₂ CH(OH)CH ₂ -, cyclohexyl, polyalkoxy, more preferably alkylene such as ethenyl, propenyl, or the like, or polyalkoxy.

In the present invention, the polyalkoxylene group means a group in which 2 or more alkyleneoxy groups are directly bonded. The alkylene groups in the plurality of alkylene groups contained in the polyalkylene oxide groups may be the same or different, respectively.

When the polyalkylene oxide group contains a plurality of alkylene oxide groups having different alkylene groups, the alkylene oxide groups in the polyalkylene oxide group may be arranged randomly, may have a block or may have an alternating pattern.

The number of carbon atoms of the alkylene group (including the number of carbon atoms of the substituent when 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 alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2 to 20, more preferably 2 to 10, and further preferably 2 to 6.

The polyalkylene oxide group is preferably a group in which a polyethylene oxide group, a polypropylene oxide group, a polytrimethylene group, a polytetramethylene group, or a plurality of ethylene oxide groups are bonded to a plurality of propylene oxide groups, more preferably a polyethylene oxide group or a polypropylene oxide group, and still more preferably a polyethylene oxide group, from the viewpoints of solvent solubility and solvent resistance. Among the groups in which the plurality of ethyleneoxy groups and the plurality of propyleneoxy groups are bonded, ethyleneoxy groups and propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in an alternating pattern. Preferred modes of repeating the number of ethyleneoxy groups and the like in these groups are as described above.

In the formula (1-1), R is ¹¹³ In the case of a hydrogen atom, the specific resin 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 (1-1), R ¹¹³ The polar group may be an acid-decomposable group or the like. The acid-decomposable group is not particularly limited as long as it is decomposed by the action of 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 exposure sensitivity.

Specific examples of the acid-decomposable group include a t-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a t-butoxycarbonylmethyl group, and a trimethylsilylether group. Ethoxyl or tetrahydrofuranyl is preferred from the viewpoint of exposure sensitivity.

In the case where the specific resin contains the repeating unit represented by the formula (1-1), the specific resin may also contain other repeating units.

In the case where the specific resin contains the repeating unit represented by the formula (1-1), the content of the repeating unit represented by the formula (1-1) relative to all the repeating units contained in the specific resin is 50 mol% or more, which is also one of the preferable embodiments of the present invention.

The content is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and still more preferably 95 mol% or more.

The upper limit of the content is not particularly limited, and may be 100 mol%.

In the formula (1-2), W ² R is R ³ Respectively with W in the formula (1-1) ¹ R is R ² The meaning is the same, and the preferred mode is the same.

In the formula (1-2), X ² Examples of the group include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, and a group in which these groups are linked by a single bond or a linking group to 2 or more, preferably 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 in which these groups are combined by a single bond or a linking group to 2 or more, more preferably an aromatic group having 6 to 20 carbon atoms, or a group in which aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group to 2 or more.

As the above-mentioned linking group, a compound having a hydroxyl group, preferably-O-, -S-; -C (=o) -, -S (=o) ₂ -, alkylene halide, arylene, or a linking group obtained by bonding 2 or more of these groups, more preferably-O-, -S-, alkylene halide, arylene, or a linking group obtained 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 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 a fluorine atom is preferable. The above-mentioned halogenated alkylene group may have a hydrogen atom, and may be substituted with a halogen atom, preferably with all hydrogen 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 X is ² Preferably from tricarboxylic acid compounds in which at least 1 carboxyl group can be halogenated. As the above halogenation, chlorination is preferable.

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

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

Examples of the tricarboxylic acid compound which may be halogenated for producing the specific resin 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, as the tricarboxylic acid compound, 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 these groups by a single bond or a linking group of 2 or more, and more preferably, a tricarboxylic acid 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 a single bond or a linking group of 2 or more.

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

These compounds may be those obtained by anhydrating 2 carboxyl groups (for example, trimellitic anhydride), or those obtained by halogenating at least 1 carboxyl group (for example, trimellitic anhydride chloride).

The particular resin may also contain other repeating units.

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

[ chemical formula 24]

In the formula (PAI-1), R ¹¹⁶ Represents a 2-valent organic group, R ¹¹¹ Represents a 2-valent organic group.

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

And R is ¹¹⁶ Preferably derived 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 groups in the dicarboxylic acid dihalide compound may be halogenated, for example, 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 can be halogenated for producing the specific resin 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 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, and 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 2 or more aromatic groups having 6 to 20 carbon atoms by a single bond or a linking group.

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, dimethylmethylsuccinic 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, ditridecanedioic acid, ditetradecanedioic acid, heptadecanedioic acid, octadecanedioic acid, icosanedioic acid, triacontanedioic acid, triamcinolone diacid, 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 specific examples of the above dicarboxylic acid compound are halogenated.

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

In the case where the specific resin contains the repeating unit represented by the formula (1-2), the repeating unit represented by the formula (1-1) and the repeating unit represented by the formula (PA 1-1) are contained in an amount of 50 mol% or more based on the total repeating units contained in the specific resin, which is also one of the preferable embodiments of the present invention.

In addition, when the specific resin contains the repeating unit represented by the formula (1-2), the content of the repeating unit represented by the formula (1-2) relative to all the repeating units contained in the specific resin is 50 mol% or more, which is also one of the preferable aspects of the present invention.

The ratio of the total molar amount of the groups represented by the formula (3-1) to the total molar amount of the groups represented by the formula (3-1) and the groups represented by the formula (3-2) contained in the specific resin is preferably 0.1 mol% or more, more preferably 5 mol% or more, and still more preferably 10 mol% or more.

The total molar amount of the groups represented by the above formula (3-2) and the total molar amount of the groups represented by the above formula (3-1) can be calculated by NMR (nuclear magnetic resonance apparatus), for example.

Further, from the viewpoint of improving the drug resistance and the patterning property, the ratio of the molar amount of the group represented by the formula (3-1) to the total molar amount of the group represented by the formula (3-1) and the group represented by the formula (3-2) contained in the specific resin is preferably 99.9 mol% or less, more preferably 95 mol% or less, still more preferably 90 mol% or less, and particularly preferably 80 mol% or less.

Further, from the viewpoint of promoting cyclization of the polyimide precursor resin or the polyamideimide precursor resin, lowering the temperature at the time of curing, and improving the elongation at break, the ratio of the molar amount of the group represented by the formula (3-1) to the total molar amount of the group represented by the formula (3-1) and the group represented by the formula (3-2) contained in the specific resin is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and particularly preferably 98 mol% or more. The mode in which the ratio of the molar amount of the group represented by the formula (3-1) to the total molar amount of the group represented by the formula (3-1) and the group represented by the formula (3-2) contained in the specific resin is 100 mol% is also one of the preferred modes of the present invention.

The molar amount of the compound of formula (3-1) contained in the specific resin is preferably 0.001 to 10mmol/g, more preferably 0.01 to 5mmol/g, and still more preferably 0.1 to 3mmol/g, based on the total mass of the specific resin.

The content of the formula (3-1) contained in the specific resin is preferably 0.1 to 70%, more preferably 0.5 to 40%, and even more preferably 1 to 20% based on the total mass of the specific resin.

The weight average molecular weight (Mw) of the specific resin is preferably 2,000 or more, more preferably 10,000 or more, and further preferably 15,000 or more.

The weight average molecular weight is preferably 200,000 or less, more preferably 50,000 or less, and still more preferably 40,000 or less.

The number average molecular weight (Mn) is preferably 1,000 or more, more preferably 3,000 or more, and further preferably 4,000 or more.

The number average molecular weight is preferably 100,000 or less, more preferably 30,000 or less, and still more preferably 20,000 or less.

The molecular weight of the specific resin 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 dispersity of the molecular weight of the specific resin 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 by weight average molecular weight/number average molecular weight.

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

The acid value of the specific resin is preferably 0 to 1mmol/g or less, more preferably 0 to 0.8mmol/g, and still more preferably 0 to 0.6mmol/g.

The acid number was as per JIS (Japanese Industrial Standards) K0070: 1992, the measurement was performed.

The cured film formed using the resin having an acid value in the above range is less likely to be damaged by an alkaline chemical solution (e.g., tetramethylammonium hydroxide, etc.).

Specific examples of the specific resin include, but are not limited to, SA-1 to SA-18 described in examples described below.

[ method for producing specific resin ]

For example, a specific resin can be obtained by the following method: a method of reacting a tetracarboxylic dianhydride with a diamine at a low temperature; a method in which a tetracarboxylic dianhydride is reacted with a diamine at a low temperature to obtain a polyamic acid, and the polyamic acid is esterified with a condensing agent or an alkylating agent; a method comprising reacting a diamine with a condensing agent after obtaining a diester by using a tetracarboxylic dianhydride and an alcohol; and a method in which a dicarboxylic acid remaining after obtaining a diester from a tetracarboxylic dianhydride and an alcohol is halogenated with a halogenating agent and reacted with a diamine. 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' -disuccinimide 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 specific resin, an organic solvent is preferably used in the reaction. The organic solvent may be 1 or 2 or more.

Examples of the organic solvent include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ -butyrolactone, which are appropriately determined according to the raw materials.

In the method for producing a specific resin, it is preferable to add an alkaline compound at the time of the reaction. The number of the basic compounds may be 1 or 2 or more.

The basic compound can be appropriately determined depending on the starting materials, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1, 8-diazabicyclo [5.4.0] undec-7-ene, N-dimethyl-4-aminopyridine, and the like.

Blocking agent-

In the production of the specific resin, in order to further improve the storage stability, it is preferable to block a carboxylic anhydride, an acid anhydride derivative or an amino group remaining at the resin end of the specific resin. When the carboxylic acid anhydride and acid anhydride derivative remaining at the end of the resin are blocked, examples of the blocking agent include monoalcohols, phenols, thiols, thiophenols, monoamines, and the like, and from the viewpoints of reactivity and film stability, monoalcohols, phenols, and monoamines are more preferably used. Preferred examples of the monoalcohol 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 t-butanol, adamantanol, and the like. Preferred examples of the phenols include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-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, 2-aminophenol, 3-aminophenol, thiophenol, and the like. These may be used in an amount of 2 or more, or may be introduced into a plurality of different terminal groups by reacting a plurality of capping agents.

In addition, when the amino group at the end of the resin is blocked, a compound having a functional group reactive with the amino group can be used for blocking. Preferred capping agents for the amino group are carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, sulfonic acid carboxylic acid anhydrides, and the like, with carboxylic acid anhydrides and carboxylic acid chlorides being more preferred. 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 compounds of carboxylic acid chlorides include acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearoyl chloride, benzoyl chloride, and the like.

Further, as the blocking agent, a compound represented by the formula (T-1) may be used. It is considered that by capping the terminal with these compounds, a structure that easily generates a base can be introduced into the terminal, and thus, even when cured at a low temperature, the elongation at break is easily increased.

[ chemical formula 25]

In the formula (T-1), L ^T Represents a 2-valent organic group, Z ¹ Z is as follows ² Each independently represents an organic group, Z ¹ And Z ² May be bonded to form a ring structure.

In the formula (T-1), L ^T The hydrocarbon group is preferably an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and preferably an aromatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group or a cyclic aliphatic hydrocarbon group.

L ^T The link chain length (i.e., link and L) ^T The minimum number of atoms of the 2 carbonyl groups bonded) is preferably 2 to 4, more preferably 2.

In the formula (T-1), Z ¹ Z is as follows ² And Z in formula (3-1) ¹ Z is as follows ² The meaning is the same, and the preferred mode is the same.

In particular, Z ¹ Z is as follows ² The mode in which at least 1 of them has a polymerizable group is also one of preferred modes of the present invention.

These polymerizable groups may be directly bonded to the nitrogen atom in the formula (T-1), or may be bonded via a linking group such as a hydrocarbon group (e.g., an alkylene group).

Specific examples of the compound represented by the formula (T-1) include CSA-1 to CSA-7 in examples described below, but are not limited thereto.

Solid precipitation-

In the case of producing a specific resin, a step of precipitating solids may be included. Specifically, the water-absorbing by-product of the dehydration condensing agent coexisting in the reaction liquid is filtered as needed, and then the obtained polymer component is poured into a poor solvent such as water, aliphatic lower alcohol or a mixed liquid thereof, and the polymer component is precipitated, whereby the polymer component is precipitated as a solid and dried, whereby a specific resin can be obtained. In order to improve the purification degree, the specific resin may be repeatedly subjected to operations such as redissolution, reprecipitation, precipitation, and drying. The method may further comprise a step of removing ionic impurities using an ion exchange resin.

[ 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, and still more preferably 95% by mass or less, based on the total solid content of the resin composition.

The resin composition of the present invention may contain only 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.

Furthermore, the resin composition of the present invention preferably further comprises at least 2 resins.

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

In the case where the resin composition of the present invention contains 2 or more specific resins, for example, it is preferable to contain a specific resin, i.e., a structure derived from dianhydride (X described in the above formula (1-1) ¹ ) Different 2 or more specific resins.

< 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.

As other resins, there may be mentioned those which are not represented by the formula (1-1) and R ¹ And R is ² At least one of them is a repeating unit of a group represented by the formula (3-1) and R is represented by the formula (1-2) ³ Polyimide precursor having repeating unit of group represented by formula (3-1), not having repeating unit represented by formula (1-1) and R ¹ And R is ² At least one of them is a repeating unit of a group represented by the formula (3-1) and R is represented by the formula (1-2) ³ Polyimide precursor, phenolic resin, polyamide, epoxy resin, polysiloxane, resin containing siloxane structure, (meth) acrylic resin, (meth) acrylamide resin, urethane resin, and the like, which are repeating units of the group represented by the formula (3-1),Butyral resin, styrene resin, polyether resin, polyester resin, and the like.

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, the resin composition may be prepared by adding a resin having a weight average molecular weight of 20,000 or less and a high value of the polymerizable group (for example, 1X 10 in 1g of the resin having a molar amount of the polymerizable group) ^-3 Molar ratio of (meth) acrylic resin of at least one molar ratio), 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, and 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, and still more preferably 50 mass% or less, based on the total solid content of the resin composition.

In addition, as a preferred embodiment of the resin composition of the present invention, the content of other resins may be reduced. 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, and further preferably 1% by mass or less, based on the total solid content of the resin composition. The lower limit of the content is not particularly limited, and may be 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.

< polymerizable Compound >

The resin composition of the present invention preferably contains a polymerizable compound.

Examples of the polymerizable compound include a free-radical crosslinking agent and other crosslinking agents.

The polymerizable compound preferably has at least 1 group selected from the group consisting of an imide group, an urea group and a urethane group, and more preferably has at least 1 group selected from the group consisting of an urea group and a urethane group.

In the present invention, the imide group means-C (=O) NR ^N C (=O) -a group represented by the formula-ureido means-NR ^N C(＝O)NR ^N By carbamate group is meant-OC (=o) NR ^N -. R is as described above ^N As described above. The orientation of these groups is not particularly limited.

It is considered that by containing these groups, the interaction of the specific resins with each other or with other components increases and the moisture resistance further improves for reasons such as hydrogen bonding between these groups or between these groups and other structures.

[ 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 groups 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 them, the group containing an ethylenically unsaturated bond is preferably a (meth) acryloyl group, (meth) acrylamide 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, more preferably a compound having 2 or more ethylenically unsaturated bonds. 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 further comprises a compound having 2 ethylenically unsaturated bonds and the above-mentioned 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 polymerizable compound 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, a sulfanyl group, or the like with a monofunctional or polyfunctional isocyanate or epoxy, a dehydration condensation reaction product with a monofunctional or polyfunctional carboxylic acid, or the like can be preferably used. Further, addition reactants of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, thiols are preferable, and substitution reactants of unsaturated carboxylic acid esters or amides having releasable substituents such as halogeno groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, thiols are more preferable. Further, as another example, a compound group substituted with an unsaturated phosphonic acid, a vinyl benzene 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, refer to the descriptions in paragraphs 0113 to 0122 of Japanese patent application laid-open No. 2016-027357, and these descriptions are incorporated herein.

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, tri (acryloxyethyl) isocyanurate, a compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then subjecting the resultant to (meth) acrylation, and epoxy acrylates or the like as the reaction product of an epoxy resin and (meth) acrylic acid, as described in each of Japanese patent publication Nos. 48-041708, 50-006034, 51-037193, 48-064183, 49-043191 and 52-030490; and mixtures of these. Furthermore, the compounds described in paragraphs 0254 to 0257 of JP-A2008-292970 are also preferred. 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, 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 having an ethylenically unsaturated bond, and a cardo (cardo) resin described in japanese patent application laid-open publication No. 2010-160418, japanese patent application laid-open publication No. 2010-129825, japanese patent application laid-open publication No. 4364216, and the like can also be used.

Further, examples of the unsaturated 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 Japanese patent application laid-open No. 61-022048 can also be used. Furthermore, compounds described as photopolymerizable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol.20, no.7, pages 300 to 308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese patent application laid-open No. 2015-034964 and the compounds described in paragraphs 0087 to 0131 of International publication No. 2015/199219, which are incorporated herein by reference, can be used.

Further, the compounds described in JP-A-10-062986 as the specific examples of the compounds represented by the formulas (1) and (2) can also be used as the radical crosslinking agent, and the compounds are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylating the resultant mixture.

Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese patent application laid-open No. 2015-187211 can also be used as radical crosslinking agents, and these are incorporated herein.

The radical crosslinking agent is preferably dipentaerythritol triacrylate (commercially available as KAYARAD-330 (Nippon Kayaku co., ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (Nippon Kayaku co., ltd.)), a-TMMT (Shin-Nakamura Chemical co., ltd.)), dipentaerythritol penta (commercially available as KAYARAD D-310 (Nippon Kayaku co., ltd.)), dipentaerythritol hexa (commercially available as KAYARAD DPHA (Nippon Kayaku co., ltd.)), a-DPH (Shin-nakamura chemical co., ltd.)) and a structure in which these (meth) acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues.

It is also possible to use these oligomer types.

As commercial products of the radical crosslinking agent, for example, there may be mentioned 4-functional acrylate SR-494 having 4 ethyleneoxy chains manufactured by Sartomer Company, inc, 2-functional methacrylate Sartomer Company having 4 ethyleneoxy chains manufactured by Inc, SR-209, 231, 239, nippon Kayaku Co., ltd., 6-functional acrylate DPCA-60 having 6 ethyleneoxy chains manufactured by Inc., 3-functional acrylate TPA-330 having 3 isobutyleneoxy chains manufactured by Nippon Kayaku, urethane oligomer UAS-10, UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD. Co., ltd.), NK ESTER NK M-40G, NK ESTER 4G, ESTER M-9300, NKESTER A-9300, UA-7200 (Shin-Nakamura Chemical Co., ltd.), DPHA-40H (manufactured by Nippon Kayaku, ltd.), UA-57306-306, UAB-140 (manufactured by UAB.3535 CO., LTD.), NK ESTER M-40G, NK (manufactured by NK. Co., ltd.) and so on, UA-306, UA-35, and so on (manufactured by BLER, LTD. Co., LTD. 600).

As the radical crosslinking agent, urethane acrylates described in Japanese patent publication No. 48-041708, japanese patent application laid-open No. 51-037193, japanese patent application laid-open No. 02-032293, and Japanese patent application laid-open No. 02-016765, urethane compounds having an ethylene oxide skeleton described in Japanese patent publication No. 58-049860, japanese patent publication No. 56-017654, japanese patent publication No. 62-039417, and Japanese patent publication No. 62-039418 are also preferred. Further, as the radical crosslinking agent, a compound having an amino structure or a thioether structure in the molecule described in JP-A-63-277653, JP-A-63-260909 or JP-A-01-105238 can 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 in which an unreacted hydroxyl group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic anhydride to have an acid group. Particularly preferred are the following compounds: in the radical crosslinking agent in which an unreacted hydroxyl group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic anhydride to have an acid group, the aliphatic polyhydroxy compound is a compound of pentaerythritol or dipentaerythritol. Examples of the commercial products include TOAGOSEI CO., LTD. The polyacid-modified acrylic oligomers M-510 and M-520.

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. The acid value of the radical crosslinking agent is within the above range, and therefore, the production workability and further the developability are excellent. Furthermore, the polymerizability was good. The acid value was determined in accordance with JIS K0070: 1992, the measurement was performed.

From the viewpoints of pattern resolution and film stretchability, 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 adduct diacrylate, bisphenol a PO adduct dimethacrylate, 2-hydroxy-3-acryloxypropyl methacrylate, isocyanuric acid diacrylate, isocyanuric acid modified dimethacrylate, other 2-functional methacrylates having urethane bonds, and other 2-functional methacrylates having urethane bonds. These may be used in combination of 2 or more kinds as required.

For example, PEG200 diacrylate refers to a polyethylene glycol diacrylate having a formula weight of about 200 in polyethylene glycol chains.

From the viewpoint of suppressing warpage accompanying control of the elastic modulus of a pattern (cured product), the resin composition of the present invention can preferably use a monofunctional radical crosslinking agent as the radical crosslinking agent. As the monofunctional radical crosslinking agent, there may be preferably used (meth) acrylic acid derivatives such as 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, epoxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allyl glycidyl ether, and the like. 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.

Examples of the radical crosslinking agent having a function of 2 or more 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 in combination, the total amount thereof is preferably within the above range.

[ other crosslinking Agents ]

The resin composition of the present invention preferably further comprises 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 radical crosslinking agent, and is preferably a compound having a plurality of groups in the molecule which promote a reaction with other compounds in the composition or reaction products thereof by the sensitization of the photoacid generator, photobase generator or the like, and preferably a compound having a plurality of groups in the molecule which promote a reaction 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.

As the other crosslinking agent, a compound having at least 1 group selected from the group consisting of an acyloxymethyl group, a hydroxymethyl group, and an alkoxymethyl group is preferable, and 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 is more preferable.

Examples of the other crosslinking agent include compounds having the following structures: and a structure obtained by reacting an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, benzoguanamine, etc., with formaldehyde or formaldehyde and an alcohol 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.

As the above amino group-containing compound, a crosslinking agent using melamine is referred to as a melamine-based crosslinking agent, a crosslinking agent using glycoluril, urea or alkylene urea is referred to as a urea-based crosslinking agent, a crosslinking agent using alkylene urea is referred to as an alkylene urea-based crosslinking agent, and a 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, 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 26]

R ₁₀₀ Represents an alkyl group or an acyl group.

R ₁₀₁ R is R ₁₀₂ Each independently represents a 1-valent organic group, and may be bonded to each other to form a ring.

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

[ chemical formula 27]

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 form 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 groups which are decomposed by the action of an acid to form alkali-soluble groups, the groups which are detached by the action of an acid, -C (R ⁴ ) ₂ COOR ⁵ R in the radicals represented ⁵ For example, there can 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 alkyl, cycloalkyl,Aryl, aralkyl or alkenyl. 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.

Further, these groups may further have a known substituent within a range to obtain the effect of the present invention.

R ₀₁ R is R ₀₂ Each independently represents 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 form 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, but are not limited to, the following compounds.

[ chemical formula 28]

[ chemical formula 29]

The compound containing at least 1 of an alkoxymethyl group and an acyloxymethyl group may be commercially available or may be synthesized by a known method.

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, and hexabutoxybutyl melamine.

Specific examples of urea-based crosslinking agents include glycoluril-based crosslinking agents such as mono-methylolated glycoluril, di-methylolated glycoluril, tri-methylolated glycoluril, tetra-methylolated glycoluril, mono-methoxymethylated glycoluril, di-methoxymethylated glycoluril, trimethoxymethylated glycoluril, tetra-methoxymethylated glycoluril, mono-ethoxymethylated glycoluril, di-ethoxymethylated glycoluril, triethoxymethyl glycoluril, tetra-ethoxymethylated glycoluril, monopropoxy methylated glycoluril, dipropoxy methylated glycoluril, tripropoxy methylated glycoluril, tetrapropoxy methylated glycoluril, monobutyloxy methylated glycoluril, dibutoxy methylated glycoluril, tributoxy methylated glycoluril, or tetrabutoxy methylated glycoluril;

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

vinyl urea crosslinking agents such as mono-methylolated vinyl urea or di-methylolated vinyl urea, mono-methoxymethylated vinyl urea, di-methoxymethylated vinyl urea, mono-ethoxymethylated vinyl urea, di-ethoxymethylated vinyl urea, mono-propoxymethylated vinyl urea, di-propoxymethylated vinyl urea, mono-or di-butoxymethylated vinyl urea;

propylene urea crosslinking agents such as monohydroxymethylene propylene urea, dimethylol propylene urea, monomethoxy methylated propylene urea, dimethoxy methylated propylene urea, monomethoxy methylated propylene urea, diethoxy methylated propylene urea, monopropoxy 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, for example, monomethylol benzoguanamine, dimethylol benzoguanamine, trimethylol benzoguanamine, tetramethylol benzoguanamine, monomethoxyl methylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxy methylated benzoguanamine, tetramethoxymethyl benzoguanamine, and monomethoxymethyl benzoguanamine;

Diethoxymethyl benzoguanamine, triethoxymethyl benzoguanamine, tetraethoxymethyl benzoguanamine, monopropoxymethyl benzoguanamine, dipropoxymethyl benzoguanamine, tripropoxymethyl benzoguanamine, tetrapropoxymethyl benzoguanamine, monobutyloxymethyl benzoguanamine, dibutoxymethyl benzoguanamine, tributoxy methyl benzoguanamine, tetrabutoxymethyl benzoguanamine and the like.

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) can 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 benzene 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 benzene 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 other crosslinking agents, commercially available products may be used, and preferable commercially available products include 46DMOC, 46DMOEP (manufactured by ASAHI YUKIZAI CORPORATION above), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, 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-AF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPOM-TMOM, TMOM-BPOM-Z, DML-BPC, DMLBOC-P, DMOM-PC, DMM-PTBP, TML-PtP, TML-HPL-HPP, HMP, PHOM-TPP, PHP; LTD), NIKALAC (registered trademark, the same as described below) MX-290, NIKALAC MX-28O, NIKALAC MX-27O, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (SANWA CHEMICAL co., LTD) above), and the like.

Further, 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)

As the epoxy compound, a compound having 2 or more epoxy groups in one molecule is preferable. The epoxy group undergoes a crosslinking reaction at 200 ℃ or less and does not cause dehydration reaction due to crosslinking, and thus film shrinkage is less likely to occur. Therefore, by containing the epoxy compound, the low-temperature curing and warpage of the resin composition of the present invention can be effectively suppressed.

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 the number of repeating units is preferably 2 to 15.

Examples of the epoxy compound include bisphenol a epoxy resins; 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, hexylene 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 polymethylsiloxane (glycidoxypropyl) and the like, but are 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), RIKARESIN (registered trademark) BEO-20E, RIKARESIN (registered trademark) BEO-60E, RIKARESIN (registered trademark) HBE-100, RIKARES IN (registered trademark) DME-100, RIKARES IN (registered trademark) L-200 (trade name, new Japan Chemical Co., ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (trade name, ADEKA CORPORATION), CELLOXDE 2021P, CELLOXIDE (registered trademark) 2081, CELLOXDE 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700, EPOLEAD (registered trademark) PB3600 (trade name, daicel Corporation), NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, E CN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (trade name, nippon Kayaku Co., ltd.) and the like. Furthermore, the following compounds may also be preferably used.

[ chemical formula 30]

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

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

Oxetane compounds (compounds having an oxetanyl group)

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

Benzoxazine compound (compound having benzoxazolyl group)

The benzoxazine compound is preferable because it does not outgas during curing due to a crosslinking reaction caused by a ring-opening addition reaction, and further reduces heat shrinkage to suppress warpage.

Preferable examples of the benzoxazine compound include P-d type benzoxazine, F-a type benzoxazine (trade name, manufactured by Shikoku Chemicals Corporation), benzoxazine adducts of polyhydroxystyrene resins, and phenol novolac type dihydrobenzoxazine compounds. These may be used alone, or 2 or more kinds may be mixed.

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, based on 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 thermal crosslinking agent is 2 or more, the total amount is preferably within the above range.

Compound B-

The resin composition of the present invention preferably further contains, as the polymerizable compound, at least 1 compound (hereinafter also referred to as "compound B") selected from the group consisting of a compound having a maleimide structure and a precursor of a compound having a maleimide structure.

Hereinafter, the compound having a maleimide structure will be referred to as "compound B-1" and the precursor of the compound having a maleimide structure will be referred to as "compound B-2".

The specific resins of the present invention produce secondary amines from the resin upon heat curing. It is believed that the secondary amine promotes polymerization of the maleimide structure.

Therefore, it is considered that by using the specific resin of the present invention in combination with the compound B-1 or the compound B-2, the unpolymerized compound B-1 or the unpolymerized compound having a maleimide structure produced from the compound B-2 is hardly remained in the film.

These unpolymerized compounds are considered to volatilize easily, and thus films having a large content of unpolymerized compounds are considered to have large cure shrinkage before and after film curing.

That is, it is considered that, by using the specific resin of the present invention and the compound B in combination, the unpolymerized compound is inhibited from remaining in the film, and as a result, the curing shrinkage before and after the film curing is inhibited.

In the present invention, the maleimide structure refers to a structure represented by the following formula (M-1).

[ chemical formula 31]

In the formula (M-1), R independently represents a hydrogen atom or a substituent, and represents a bonding site with other structures. R is preferably a hydrogen atom. The substituent for R is not particularly limited, and may have a known substituent, and examples thereof include a hydrocarbon group and the like, and an alkyl group is preferable.

Compounds having a maleimide Structure (Compound B-1)

The compound B-1 preferably has a maleimide structure of 2 or more. The number of maleimide structures is preferably 2 to 10, more preferably 2 to 6, and still more preferably 2 to 4. Furthermore, a system comprising 2 maleimide structures is also one of the preferred embodiments of the present invention.

The compound B-1 is not particularly limited, and is preferably a compound represented by the following formula (M-2).

[ chemical formula 32]

In the formula (M-2), R independently represents a hydrogen atom or a substituent, L represents an n-valent linking group, and n represents an integer of 1 or more.

In the formula (M-2), the preferable mode of R is the same as that of R in the above formula (M-1).

In the formula (M-2), L is preferably a hydrocarbon group, or a hydrocarbon group and a member selected from the group consisting of-O-; -C (=o) -, -S (=o) ₂ -and-NR ^N- More preferably a group represented by a combination of at least 1 groups, more preferably a group represented by a hydrocarbon group, or a combination of a hydrocarbon group and-O-.

The bonding site of L to the nitrogen atom in the maleimide structure of formula (M-2) is preferably a carbon atom, more preferably a hydrocarbon group.

In the formula (M-2), n is preferably an integer of 2 or more, more preferably an integer of 2 to 10, still more preferably an integer of 2 to 6, and particularly preferably an integer of 2 to 4. The mode in which n is 2 is also one of preferred modes of the present invention.

The molecular weight of the compound B-1 is preferably 90 to 2,000, more preferably 100 to 1,000, and still more preferably 150 to 800.

The content of the maleimide structure in the compound B-1 (the molar content of the maleimide structure in the compound B-1 of 1 g) is preferably 0.1 to 20mmol/g, more preferably 1 to 15mmol/g.

Specific examples of the compound B-1 are not particularly limited, and BM-1 to BM-3 in examples described later are given.

Precursor of Compound having maleimide Structure (Compound B-2)

The preferred mode of the compound having a maleimide structure derived from the compound B-2 is the same as that of the compound B-1.

The compound B-2 is preferably a compound which generates a compound having a maleimide structure by heat.

Specifically, the compound B-2 is preferably a compound having a maleimide structure by heating at 230 ℃ for 3 hours, more preferably a compound having a maleimide structure by heating at 200 ℃ for 3 hours, and even more preferably a compound having a maleimide structure by heating at 180 ℃ for 2 hours. The lower limit of the temperature at which the compound having the maleimide structure is produced is not particularly limited, but is preferably 100℃or higher from the viewpoint of storage stability of the composition, for example.

Whether or not a certain compound A shows the property of producing a compound having a maleimide structure at a certain temperature X ℃ is judged by the following method.

When 1 mol of compound a was heated at X ℃ as described above for 3 hours under 1 gas pressure in a sealed container and then the amount of decomposition was quantified by a method such as HPLC (high performance liquid chromatography) to produce 0.01 mol or more of a compound having a maleimide structure, it was determined that compound a produced a compound having a maleimide structure by heating at X ℃. The structure of the resulting compound having a maleimide structure is obtained, for example, by using ¹ H-NMR was confirmed.

The amount of the compound having the maleimide structure to be produced is preferably 0.1 mol or more, more preferably 0.5 mol or more. The upper limit of the amount of the compound having a maleimide structure to be produced is not particularly limited, but can be, for example, 1,000 mol or less.

The compound B-2 is preferably a compound having a structure represented by the following formula (M-2).

The structure represented by the formula (M-2) is heated to form an imide ring, thereby forming a maleimide structure represented by the formula (M-1).

[ chemical formula 33]

In the formula (M-2), R independently represents a hydrogen atom or a substituent, and X represents-O-or-NR ^N2 -，R ^N2 Represents a hydrogen atom or an organic group, R ^N1 Represents a hydrogen atom or an organic group, R ^N1 And R is ^N2 May be bonded to form a ring structure, meaning a bond site with other structures.

In the formula (M-2), R has the same meaning as R in the above formula (M-1), and the preferable mode is the same.

In the formula (M-2), X represents-0-or-NR ^N2 From the viewpoint of base production, it is preferably-NR ^N2 -. Furthermore, from the viewpoint of easy formation of maleimide structure, it is preferably-O-.

In the formula (M-2), R ^N1 Represents a hydrogen atom or an organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group.

In the formula (M-2), R ^N2 Represents a hydrogen atom or an organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group.

In the formula (M-2), R ^N1 And R is ^N2 May be bonded to form a ring structure, and as the formed ring structure, a 5-membered ring or a 6-membered ring is preferable.

The ring structure formed may be an aliphatic ring structure or an aromatic ring structure, and an aliphatic ring structure is preferable.

The ring structure formed above may include a ring structure other than R ^N1 Heteroatoms other than the nitrogen atom bound, not containing other than R ^N1 The manner of the hetero atom other than the bonded nitrogen atom is also one of the preferable manners of the present invention.

The molecular weight of the compound B-2 is preferably 100 to 2,000, more preferably 100 to 1,500, and still more preferably 200 to 1,000.

Specific examples of the compound B-2 are not particularly limited, and BMB-1 to BMB-2 in examples described later are exemplified.

The content of the compound B is preferably 0.1 to 60% by mass, more preferably 0.5 to 40% by mass, still more preferably 1 to 20% by mass, and still more preferably 1 to 7% by mass, relative to the total solid content of the resin composition of the present invention.

Compound C-

Furthermore, in the case where the resin composition contains the compound B, the resin composition also preferably contains a compound having a group capable of reacting with a maleimide structure (also referred to as "compound C").

Examples of the group capable of reacting with the maleimide structure include at least 1 group selected from the group consisting of an ethylenically unsaturated group, a hydroxyl group, an epoxy group and an amino group.

Further, the group capable of reacting with the maleimide structure also includes a group which generates at least 1 group selected from an ethylenically unsaturated group, a hydroxyl group, an epoxy group, and an amino group by heating, and the like which generates an amino group by heating.

Specific examples of the compound having an ethylenically unsaturated group in the compound C include the radical crosslinking agents described above.

Specific examples of the compound having an epoxy group in the compound C include the epoxy compounds described above.

Specific examples of the compound C include compounds described in C-2 to C-4 described in examples described below.

The compound C preferably contains 2 or more groups capable of reacting with the maleimide structure in total. The number of the above groups is preferably 2 to 10, more preferably 2 to 6, and still more preferably 2 to 4.

The content of the compound C is preferably 0.1 to 60% by mass, more preferably 0.5 to 40% by mass, and even more preferably 1 to 20% by mass, based on the total solid content of the resin composition of the present invention.

< Compound D >

It is also preferable that compound D, which is a compound having a ring-opening polymerizable group and a radical polymerizable group, is contained as the polymerizable compound.

By including the compound D, the ring-opening polymerizable group is not yet polymerized at the start of the cyclization of the imide of the specific resin by heating or the like, and the cyclization of the precursor of the cyclized resin due to the crosslinked structure formed after the polymerization can be suppressed from being hindered, and the polymerization of the ring-opening polymerizable group is also performed after heating or the like, so that both a high cyclization ratio and a high crosslinking density can be achieved. As a result, it is considered that the elongation at break and the drug resistance are easily improved.

The ring-opening polymerizable group in the compound D is preferably a ring-opening polymerizable group by heating, more preferably a ring-opening polymerizable group in the case where the film obtained by drying the resin composition of the present invention is heated at 250 ℃ for 3 hours, still more preferably a ring-opening polymerizable group in the case where the film is heated at 230 ℃ for 3 hours, particularly preferably a ring-opening polymerizable group in the case where the film is heated at 200 ℃ for 3 hours, and particularly preferably a ring-opening polymerizable group in the case where the film is heated at 180 ℃ for 2 hours.

The ring-opening polymerizable group in the compound D is preferably a group having at least 1 structure selected from the group consisting of an epoxide structure, an oxetane structure, a lactone structure, a cyclic carbonate structure, and a cyclic amide structure.

Examples of the group having an epoxide structure include an epoxy group and a propylene oxide group.

Examples of the group having an oxetane structure include an oxetanyl group, an oxetanylmethyl group, a (3-methyloxetan-3-yl) methyl group, a (3-ethyloxetan-3-yl) methyl group, and an oxetanylmethoxy group.

Examples of the group having a lactone structure include a β -propiolactone group, a γ -butyrolactone group, and an ε -caprolactone group.

Examples of the group having a cyclic carbonate structure include 2-oxo-1, 3-dioxolan-4-yl group and (2-oxo-1, 3-dioxolan-4-yl) methyl group.

Examples of the group having a cyclic amide structure include 2-oxo azepan (azepan) -1-yl.

The compound D also preferably contains at least 1 structure selected from urea bonds, urethane bonds, and amide bonds not contained in the cyclic structure.

The urea bond in the compound D is-NR ^N -C(＝O)-NR ^N -the represented structure. Preferably, both ends of the urea linkage are bonded to carbon atoms, more preferably to hydrocarbons. R is R ^N Each independently represents a hydrogen atom or a 1-valent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, further preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and particularly preferably a hydrogen atom. And can R ^N Each other or R ^N At least one of which is bonded to other structure bonded to urea bond to form a ring structure.

The above urethane bond in the compound D is-NR ^N- C (=o) -O-, a structure represented by C (=o) -O-. Preferably, both ends of the urethane bond are bonded to a carbon atom, more preferably to a hydrocarbon. R is R ^N R in the urea bond as described above ^N The same applies. And R is ^N May be bonded to other structures bonded to urethane bonds to form a ring structure.

The amide bond in the compound D is-NR ^N -C (=o) -the structure represented.

Preferably, both ends of the amide bond are bonded to a carbon atom, more preferably to a hydrocarbon. The terminal on the carbonyl side of the amide bond may be directly bonded to the lactone structure, the cyclic carbonate structure, and the cyclic amide structure. R is R ^N R in the urea bond as described above ^N The same applies. The amide bond in the compound B is not contained in the cyclic structure.

Examples of the radical polymerizable group in the compound D include a group having an ethylenically unsaturated bond, 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) acrylamido group, a (meth) acryloyloxy group, a maleimide group, or the like, preferably a group having an aromatic ring directly bonded to a vinyl group, (meth) acrylamido group or (meth) acryloyloxy group, more preferably (meth) acryloyloxy group.

The number of ring-opening polymerizable groups in the compound D is not particularly limited, but is preferably 1 to 10, more preferably 1 to 4, further preferably 1 or 2, and particularly preferably 1.

The number of radical polymerizable groups in the compound D is not particularly limited, but is preferably 1 to 10, more preferably 1 to 4, and further preferably 1 or 2.

In this case, the compound D has only 1 ring-opening polymerizable group and has 1 or 2 radical polymerizable groups, which is also one of the preferred embodiments of the present invention.

In the case where the compound D contains at least 1 structure selected from the group consisting of a urea bond, a urethane bond, and an amide bond not contained in a cyclic structure, the number thereof is preferably 1 to 10, more preferably 1 to 4, further preferably 1 or 2, and particularly preferably 1.

The compound D is preferably a compound having a structure represented by the following formula (D-1).

[ chemical formula 34]

In the formula (D-1), X is independently selected from epoxide structure, oxetane structure, lactone structure, and cyclic carbonAt least 1 of the acid ester structure and the cyclic amide structure, n represents an integer of 1 or more, Z represents a radical polymerizable group, m represents an integer of 1 or more, L represents at least 1 of the structures selected from the group consisting of urea bond, urethane bond and amide bond not contained in the cyclic structure and hydrocarbon group or hydrocarbon group and is selected from the group consisting of-O-, -C (=O) -, -S (=O) ₂ -and-NR ^N N+m-valent linking group represented by a combination of at least 1 structures of (a), R ^N Is a hydrogen atom or a hydrocarbon group.

In the formula (D-1), X is preferably a group having at least 1 structure selected from the group consisting of an epoxide structure and an oxetane structure.

Preferred modes of the group having at least 1 structure selected from the group consisting of epoxide structure, oxetane structure, lactone structure, cyclic carbonate structure and cyclic amide structure in X are as described above.

In the formula (D-1), n represents an integer of 1 or more, 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 (D-1), L is preferably an n+m-valent linking group represented by a combination of at least 1 structure selected from urea bonds, urethane bonds, and amide bonds not included in the cyclic structure, and a hydrocarbon group or a hydrocarbon group and at least 1 structure selected from-O-and-C (=o) -.

The hydrocarbon group in L may be any one of an aromatic hydrocarbon group, an aliphatic hydrocarbon group, and a group represented by a bond thereof, and is preferably an aromatic hydrocarbon group, an aliphatic saturated hydrocarbon group, or a group represented by a bond thereof.

When L contains an aromatic hydrocarbon group, at least 1 structure selected from urea bonds, urethane bonds, and amide bonds not contained in a cyclic structure in L is preferably directly bonded to the aromatic hydrocarbon group.

The aromatic hydrocarbon group in L is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and more preferably a group obtained by removing a plurality of hydrogen atoms from a benzene ring.

The aliphatic hydrocarbon group in L is preferably an aliphatic saturated hydrocarbon group, more preferably an aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms, and still more preferably an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms.

Wherein L preferably comprises a group represented by the following formula (L-1).

[ chemical formula 35]

In the formula (L-1), R ¹ R is R ² Respectively and independently represent a single bond, -NR ^N -or-O-, R ¹ R is R ² At least one of them is-NR ^N -，R ^N Each independently represents a hydrogen atom or a 1-valent organic group, ar represents an aromatic hydrocarbon group, and each of the groups represented by x and # represents a bonding site to another structure.

In the case where L contains a group represented by the formula (L-1), R is preferably ¹ R is R ² Are all-NR ^N -, or R ¹ is-NR ^N -and R ² is-O-.

In the formula (L-1), R ^N The preferred mode of (a) is as described above.

In the formula (L-1), ar is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and more preferably a phenylene group.

When L contains a group represented by formula (L-1), the structure represented by formula (L-1) in formula (B-1) may be bonded to X in formula (B-1) or bonded to Z, and the orientation of the structure represented by formula (L-1) in formula (B-1) is not particularly limited, but is preferably bonded to X.

[ molecular weight ]

The molecular weight of the compound D is preferably 200 to 1,000, more preferably 220 to 800, and still more preferably 240 to 500.

[ specific example ]

Specific examples of the compound D include, but are not particularly limited to, compounds having the following structures. In addition, glycidyl (meth) acrylate, (3-ethyloxetan-3-yl) methyl (meth) acrylate and the like can also be used as the compound D.

[ chemical formula 36]

The content of the compound D is preferably 0.1 to 60% by mass, more preferably 1 to 40% by mass, and even more preferably 3 to 30% by mass, based on the total solid content of the resin composition of the present invention.

[ polymerization initiator ]

The resin composition of the present invention preferably contains a polymerization initiator, preferably contains a radical polymerization initiator. The radical polymerization initiator preferably includes a radical polymerization initiator capable of initiating polymerization by light and/or heat. Particularly preferably, the photo radical polymerization initiator is contained.

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. Moreover, it may be an active agent that exerts some action with the photosensitizing agent that is excited by light and generates active radicals.

The photo radical polymerization initiator preferably contains at least 1 initiator having a molecular weight of at least about 50 L.mol in a 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 measure the content of the organic compound at a concentration of 0.01g/L by using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Co.) using an ethyl acetate solvent.

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, and the like, 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 (Kokai) No. 2016-027357 and paragraphs 0138 to 0151 of International publication (Kokai) No. 2015/199219, which are incorporated herein by reference. Examples of the initiator include a compound described in JP-A-2014-130173 at the stage 0065-0111, JP-A-6301489, MATERIAL STAGE-60 p, vol.19, no.3, 2019, a peroxide-based photopolymerization initiator described in International publication No. 2018/221177, a photopolymerization initiator described in International publication No. 2018/110179, a photopolymerization initiator described in JP-A-2019-043864, a photopolymerization initiator described in JP-A-2019-044030, and a peroxide-based initiator described in JP-A-2019-167313, which are incorporated herein by reference.

Examples of the ketone compound include compounds described in paragraph 0087 of Japanese patent application laid-open No. 2015-087611, incorporated herein by reference. Among the commercial products, KAYACUREDETX-S (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 and an acylphosphine oxide initiator described in JP-A-4225898 can be used, and these are incorporated herein.

As the alpha-hydroxyketone initiator, omnifad 184, omnifad 1173, omnifad 2959, omnifad 127 (manufactured by the above-mentioned IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE127 (manufactured by BASF corporation) can be used.

As the α -aminoketone initiator, omnirad 907, omnirad369E, omnirad 379EG (manufactured by IGM Resins B.V. above), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF corporation) can be used.

As the aminoacetophenone initiator, a compound described in japanese patent application laid-open No. 2009-191179, which matches the maximum absorption wavelength to a light source having a wavelength of 365nm or 405nm, etc., can be used, and these contents are incorporated in 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. above), IRGACURE-819, IRGACURE-TPO (trade name: manufactured by BASF corporation) can be used.

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

As the photo radical polymerization initiator, an oxime compound is more preferably exemplified. By using an oxime compound, the exposure latitude can be further 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. 2001-233846, 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, pages 1653-1660), a compound described in J.C.S. Perkin II (1979, pages 156-162), a compound described in Journal of Photopolymer Science and Technology (1995, pages 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. 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. 2017-865, a compound described in International publication No. 2015-0035, a compound described in International publication No. 2015-2015, a publication No. 2015-0025, and a compound described in International publication No. 2015-0025.

Preferable oxime compounds include, for example, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino1-phenylpropane-1-one, 2-benzoyloxyimino1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxyimino1-phenylpropane-1-one having the following structures. In the resin composition of the present invention, an oxime compound (oxime-based photo radical polymerization initiator) is preferably used as a photo radical polymerization initiator, in particular. The oxime-based photo-radical polymerization initiator has a linking group > c=n-O-C (=o) -, in the molecule.

[ chemical formula 37]

Among the commercial products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (manufactured by BASF corporation as described above), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION), and photo radical polymerization initiator 2 described in 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.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (ADEKA CORPORATION). Further, DFI-091 (manufactured by Daito Chemix Corporation) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can be used. Furthermore, an oxime compound having the following structure can also be used.

[ chemical formula 38]

/>

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. 06636081, which are incorporated herein by reference.

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

Oxime compounds 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, which 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, 0008 to 0012 and 0070 to 0079 of Japanese patent application laid-open No. 2014-137466, and 0007 to 0025 of Japanese patent application laid-open No. 4223071, which are incorporated herein by reference. Further, as the oxime compound having a nitro group, ADEKA ARKLS NCI-831 (ADEKA CORPORATION).

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 a carbazole skeleton can also be used. Examples of such photopolymerization initiators include compounds described in International publication No. 2019/088055, which are incorporated herein by reference.

As the photopolymerization initiator, an aromatic ring group Ar having an electron withdrawing group introduced into an aromatic ring can also be used ^OX1 Is also referred to as oxime compound OX below. As the aromatic compoundRing group Ar ^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, a cyano group, preferably an acyl group and a nitro group, more preferably an acyl group, and further preferably a benzoyl group, from the viewpoint of facilitating formation of a film excellent in light resistance. The benzoyl group may have a substituent. The substituent is preferably a halogen atom, cyano group, nitro group, hydroxyl group, alkyl group, alkoxy group, aryl 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 39]

Wherein R is ^X1 Represents alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclyl, heterocyclyloxy, alkylsulfanyl, arylsulfanyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acyl, acyloxy, amino, phosphono, carbamoyl or sulfamoyl,

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

R ^X3 ～R ^X14 each independently represents a hydrogen atom or a substituent.

Wherein R is ^X10 ～R ¹¹⁴ At least 1 of which is an electron withdrawing group.

In the above formula, R is preferably ^X12 Is an electron withdrawing group and R ^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, which are incorporated herein by reference.

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.

More preferred photo radical polymerization initiator is trihalomethyltriazine compound, α -amino ketone compound, acylphosphine compound, phosphine oxide compound, metallocene compound, oxime compound, triarylimidazole dimer, onium salt compound, benzophenone compound, acetophenone compound, still more preferred is at least 1 compound selected from trihalomethyltriazine compound, α -amino ketone compound, metallocene compound, oxime compound, triarylimidazole dimer, benzophenone compound, still more preferred is metallocene compound or oxime compound.

The photo radical polymerization initiator may be a benzophenone, an aromatic ketone such as N, N ' -tetramethyl-4, 4' -diaminobenzophenone (Michler's ketone), 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, a benzoin ether compound such as alkylanthraquinone, a benzoin ether compound such as benzoin alkyl ether, a benzoin compound such as benzoin, or a benzyl derivative such as benzyl dimethyl ketal. Further, a compound represented by the following formula (I) can also be used.

[ chemical formula 40]

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, a phenyl group or a biphenyl group substituted by at least 1 of an alkyl group having 2 to 18 carbon atoms and an alkyl group having 1 to 4 carbon atoms interrupted by 1 or more oxygen atoms, R ^I01 Is a group represented by formula (II) or is associated with 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 41]

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 of those 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, since 2 or more radicals are generated from one molecule of the photo radical polymerization initiator, good sensitivity can be obtained. In addition, when a compound having an asymmetric structure is used, crystallinity is reduced, solubility in a solvent or the like is increased, and precipitation is less likely to occur with the passage of time, whereby the stability of the resin composition with time can be improved. Specific examples of the 2-functional or 3-functional or more photo-radical polymerization initiator include the photoinitiators of oxime esters described in JP-A2010-527339, JP-A2011-524436, international publication No. 2015/004565, the dimers of oxime compounds described in JP-A0407-0412, international publication No. 2017/033680 and 0039-0055, the compounds (E) and (G) described in JP-A2013-522445, cmpd 1-7 described in International publication No. 2016/034963, oxime ester photoinitiators described in JP-A2017-523465 and 0007, photoinitiators of JP-A0020-0033, photoinitiators of JP-A2017-151342 and oxime ester photoinitiators of JP-A0017-0026 and JP-A6469669, etc., which are described in the specification.

When the photo radical polymerization initiator is contained, the content thereof 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, relative to 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, the photopolymerization initiator may also function as a thermal polymerization initiator, and thus crosslinking by the photopolymerization initiator may be further promoted by heating in an oven, a hot plate, or the like.

[ sensitizer ]

The resin composition may contain 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 to cause an electron transfer, an 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, milone-based, coumarin-based, pyrazole azo-based, aniline azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, indigo-based and the like can be used.

As the sensitizer, for example, examples thereof include midone, 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 biphenyl) -benzothiazole, 2- (p-dimethylaminophenyl vinylidene) benzothiazole, and 2- (p-dimethylaminophenylvinylene) isonaphthylthiazole, 1, 3-bis (4 ' -dimethylaminobenzylidene) acetone, 1, 3-bis (4 ' -diethylaminobenzylidene) acetone, 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), and, N-phenyl-N ' -ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinylbenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyrene) benzoxazole, 2- (p-dimethylaminostyrene) benzothiazole, 2- (p-dimethylaminostyrene) naphthalene (1, 2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4' -dimethylacetanilide, and the like.

Furthermore, other sensitizing colorants can 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 are 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 2 or more.

[ chain transfer agent ]

The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in pages 683-684 of the third edition of the Polymer dictionary (university of Polymer (The Society of Polymer Science, japan) eds., 2005). As the chain transfer agent, for example, a chain transfer agent having-S-, -SO within the molecule can be used ₂ The group of compounds S-, -N-O-, SH, PH, siH and GeH, dithiobenzoate esters having thiocarbonylthio groups for RAFT (Reversible Addition Fragmentation chain Transfer: reversible addition fragmentation chain transfer) polymerization, trithiocarbonates, dithiocarbamates, xanthate compounds, etc. These supply hydrogen to the low activity radicals to generate radicals, or may generate radicals by deprotonation after oxidation. In particular, a thiol compound can be preferably used.

The chain transfer agent may be a compound 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.

< alkali Generator >

The resin composition of the present invention may contain a base generator. Here, the base generator means a compound capable of generating a base by physical action or chemical action. The alkali generator does not contain the above specific resin. 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.

When the resin composition contains a thermal base generator, for example, cyclization reaction of the precursor can be accelerated by heating, and mechanical properties and chemical resistance of the cured product are improved, for example, performance of an interlayer insulating film for a re-wiring layer included in a semiconductor package is improved.

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

The alkali generator of the present invention is not particularly limited, and a known alkali generator can be used. As the known base generating agent, for example, a carbamoyl oxime compound, a carbamoyl hydroxylamine compound, a carbamic acid compound, a carboxamide compound, an acetamide compound, a carbamic acid ester compound, a benzyl carbamic acid ester compound, a nitrobenzyl carbamic acid ester compound, a sulfonamide compound, an imidazole derivative compound, an amine imide compound, a pyridine derivative compound, an α -aminoacetophenone derivative compound, a quaternary ammonium salt derivative compound, a pyridinium salt, an α -lactone ring derivative compound, an amine imide compound, a phthalimide derivative compound, an acyloxyimide compound, or the like can be used.

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

[ chemical formula 42]

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 And (5) a seed. Wherein Rb ¹ Rb ² And not simultaneously become hydrogen atoms. Furthermore, rb ¹ 、Rb ² Rb ³ None of them has a carboxyl group. In the present specification, the tertiary amine structure means a structure in which all of 3 links of a 3-valent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, the present invention is not limited to this case, and the carbon atom to be bonded is a carbon atom forming a carbonyl group, that is, an amide group is formed together with a nitrogen atom.

In the formulae (B1) and (B2), rb is preferably ¹ 、Rb ² Rb ³ At least 1 of which comprises a cyclic structure, more preferably at least 2 of which comprises a cyclic structure. The cyclic structure may be any of a single ring and a condensed ring, and a condensed ring formed by condensing a single ring or 2 single rings is preferable. 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, the compound is a hydrogen atom, an alkyl group (having a carbon number of preferably 1 to 24, more preferably 2 to 18, still more preferably 3 to 12), an alkenyl group (having a carbon number of preferably 2 to 24, more preferably 2 to 18, still more preferably 3 to 12), an aryl group (having a carbon number of preferably 6 to 22, more preferably 6 to 18, still more preferably 6 to 10), or an aralkyl group (having a carbon number of preferably 7 to 25, more preferably 7 to 19, still more preferably 7 to 12). 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. As the ring formed, a 4-to 7-membered nitrogen-containing heterocycle is preferable. Rb (Rb) ¹ Rb ² In particular, a linear, branched or cyclic alkyl group which may have a substituent (the number of carbon atoms is preferably 1 to 24, more preferably 2 to 18, still more preferably 3 to 12), a cycloalkyl group which may have a substituent (the number of carbon atoms is preferably 3 to 24, more preferably 3 to 18, still more preferably 3 to 12), and a cyclohexyl group which may have a substituent are preferable.

As Rb ³ Examples thereof include an alkyl group (having preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms) and an aryl group (having preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 6 carbon atoms)10 Alkenyl (preferably 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 6 carbon atoms), aralkyl (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12 carbon atoms), aralkenyl (preferably 8 to 24 carbon atoms, more preferably 8 to 20 carbon atoms, still more preferably 8 to 16 carbon atoms), alkoxy (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), aryloxy (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12 carbon atoms) or aralkoxy (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12 carbon atoms). Among them, cycloalkyl groups (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 Further, the substituent may be present within a range that exerts the effects of the present invention.

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 43]

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

Rb ¹³ The alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), the alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), the aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12 carbon atoms), the aralkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12 carbon atoms) may have a substituent in a range that exerts the effect of the present invention. Wherein Rb ¹³ Aralkyl groups are preferred.

Rb ³³ Rb ³⁴ Each independently represents a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), or an alkenyl group (preferably 2 to 12 carbon atoms, more preferably2 to 8, more preferably 2 to 3), an aryl group (having preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, more preferably 6 to 10 carbon atoms), an aralkyl group (having preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, more preferably 7 to 11 carbon atoms), and preferably a hydrogen atom.

Rb ³⁵ The alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), the alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, still more preferably 3 to 8 carbon atoms), the aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12 carbon atoms), the aralkyl group (preferably 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 44]

Rb ¹¹ Rb ¹² And Rb in formula (B1-1) ¹¹ Rb ¹² The meaning is the same.

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

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

[ chemical formula 45]

In the formula (B3), L is a 2-valent hydrocarbon group having a saturated hydrocarbon group on the path of the linking chain linking the adjacent oxygen atoms and carbon atoms, and represents a hydrocarbon group having 3 or more atoms on the path of the linking chain. 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 in which the connection objects are connected at the shortest (minimum atomic number) distance among atomic chains on a path connecting 2 atoms or groups of atoms of the connection objects. For example, in a compound represented by the following formula, L is composed of styrene and has a vinyl group as a saturated hydrocarbon group, the linking chain is composed of 4 carbon atoms, and the number of atoms on the path of the linking chain (i.e., the number of atoms constituting the linking chain, hereinafter also referred to as "linking chain length" or "linking chain length") is 4.

[ chemical formula 46]

The number of carbon atoms in L of the formula (B3) (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 chain length 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 proceeding the intramolecular cyclization reaction. In particular, the chain length of the linkage of L is preferably 4 or 5, and most preferably 4. Specific examples of preferred compounds for the base generator include, for example, compounds described in paragraphs 0102 to 0168 of International publication No. 2020/066416 and compounds described in paragraphs 0143 to 0177 of International publication No. 2018/038002.

The base generator preferably further comprises a compound represented by the following formula (N1).

[ chemical formula 47]

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 chain length 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 chain length refers to the number of atoms present in the atomic arrangement that forms the shortest path between 2 carbonyl groups in the formula.

In the formula (N1), R ^N1 R is R ^N2 Each independently represents a 1-valent organic group (preferably 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 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 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 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 an aliphatic hydrocarbon chain, an aromatic ring, or a substituent. In particular, the manner in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain can be exemplified.

As a constituent R ^N1 R is R ^N2 Examples of the aliphatic hydrocarbon group(s) include a linear or branched alkyl group, a cyclic alkyl group, a group related to a combination of a linear alkyl group and a cyclic alkyl group, and an alkyl group having an oxygen atom in the chain. The number of carbon atoms of the linear or branched chain alkyl group is preferably 1 to 24, more preferably 2 to 18, still more preferably3 to 12. Examples of the linear or branched chain alkyl group include methyl, 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 number of carbon atoms of the cyclic alkyl group is preferably 3 to 12, more preferably 3 to 6. Examples of the cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.

The number of carbon atoms of the group involved in the combination of the chain alkyl group and the cyclic alkyl group is preferably 4 to 24, more preferably 4 to 18, and still more preferably 4 to 12. Examples of the group involved in 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 number of carbon atoms of the alkyl group having an oxygen atom in the chain is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 4. The alkyl group having an oxygen atom in the chain may be linear or cyclic, or may be linear or branched.

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 Preferably an alkyl group having 5 to 12 carbon atoms. Among them, in the formulation in which adhesion to the metal (e.g., copper) layer is important, 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, and 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 Representing hydrogen atoms or protectionA 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 a protecting group which is decomposed by an acid is preferable.

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 alkoxyalkyl group, and more specifically, a methoxymethyl group (MOM), an ethoxyethyl group (EE), and the like. Examples of the cyclic alkyl group having an oxygen atom in the chain include an epoxy group, an epoxypropyl group, an oxetanyl group, a tetrahydrofuranyl group, and a Tetrahydropyran (THP) group.

The 2-valent linking group constituting L is not particularly limited, and is preferably a hydrocarbon group, more preferably an aliphatic hydrocarbon group. The hydrocarbon group may have a substituent, and may have a kind of atom other than a carbon atom in the hydrocarbon chain. More specifically, a 2-valent hydrocarbon linking group which may have an oxygen atom in the chain is preferable, 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 is more preferable, and a 2-valent aliphatic hydrocarbon group which may have an oxygen atom in the chain is further preferable. These groups preferably do not have an oxygen atom.

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

The linking group L is 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 number of carbon atoms of the linear or branched chain alkylene group is preferably 1 to 12, more preferably 2 to 6, and still more preferably 2 to 4.

The number of carbon atoms of the cyclic alkylene group is preferably 3 to 12, more preferably 3 to 6.

The number of carbon atoms of the group involved in the combination of the chain alkylene group and the cyclic alkylene group is preferably 4 to 24, more preferably 4 to 12, and still more preferably 4 to 6.

The alkylene group having an oxygen atom in the chain may be linear or cyclic, or may be linear or branched. The number of carbon atoms of the alkylene group having an oxygen atom in the chain is preferably 1 to 12, more preferably 1 to 6, still more preferably 1 to 3.

The number of carbon atoms of the linear or branched alkenyl group is preferably 2 to 12, 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, and still more preferably 1 to 3.

The number of carbon atoms of the cyclic alkenylene group is preferably 3 to 12, more preferably 3 to 6. 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 number of carbon atoms of the arylene group is preferably 6 to 22, more preferably 6 to 18, and still more preferably 6 to 10.

The number of carbon atoms of the arylene alkylene is preferably 7 to 23, more preferably 7 to 19, and still more preferably 7 to 11.

Among them, preferred are chain alkylene groups, cyclic alkylene groups, alkylene groups having an oxygen atom in the chain, chain alkenylene groups, arylene groups, and arylene alkylene groups, and more preferred are 1, 2-vinyl groups, propane diyl groups (particularly 1, 3-propane diyl groups), cyclohexane diyl groups (particularly 1, 2-cyclohexane diyl groups), vinylidene groups (particularly cis-vinylidene groups), phenylene groups (1, 2-phenylene groups), phenylene methylene groups (particularly 1, 2-phenylene methylene groups), and ethyleneoxy vinyl groups (particularly 1, 2-ethyleneoxy-1, 2-vinyl groups).

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

[ chemical formula 48]

Further, as the nonionic base generator, a compound having a structure represented by the following formula (B-1) is also preferable.

[ chemical formula 49]

In the formula (B-1), R ^B1 R is R ^B2 Each independently represents an organic group, R ^B1 R is R ^B2 The bonds with the dotted line represent single bonds or double bonds, respectively represent bonding sites with other structures.

In the formula (B-1), R ^B1 R is R ^B2 R in the above formula (3-1) ¹ R is R ² The same is preferable.

In the formula (B-1), the bond having a dotted line portion is preferably a double bond. In the case where the bond having the dotted line is a single bond, the number of carbon atoms included in the single bond is preferably 1 ring-forming atom having a ring structure.

The molecular weight of the compound represented by the formula (B-1) is preferably 10,000 or less, more preferably 8,000 or less, and still more preferably 5,000 or less.

The molecular weight is preferably 2,000 or less, more preferably 1,000 or less.

The lower limit of the molecular weight is not particularly limited, and is preferably 100 or more, for example.

Examples of the compound represented by the formula (B-1) include, but are not limited to, the following compounds.

[ chemical formula 50]

The molecular weight of the nonionic base 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 examples of preferred compounds for the ionic base 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 51]

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

[ chemical formula 52]

When the resin composition of the present invention contains the alkali generator, the content of the alkali 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 alkali generator can 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.

In the present invention, since a base can be produced from a specific resin, the content of the base generator can be reduced as compared with a conventional resin composition containing the base generator and the cyclized resin or a precursor thereof. As a result, it is considered that residues after the alkali generation of the alkali generator, the undegraded alkali generator itself, and the like are less likely to remain in the composition, and thus the moisture resistance is improved.

In this embodiment, the content of the alkali generator is preferably 2 mass% or less based on 100 parts by mass of the resin. Further, the content of the alkali generator is preferably 1 mass% or less, and more preferably 0.5 mass% or less, based on 100 parts by mass of the resin. Further, the content of the alkali generator is preferably 1 mass% or less based on 100 parts by mass of the resin. In these modes, the lower limit of the content of the base generator may be 0 mass%.

The content of the alkali generator can be determined in consideration of the amount of alkali generated from the specific resin, heating conditions, and the like.

< 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 the 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, γ -butyrolactone, ε -caprolactone, δ -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-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-alkoxy-2-methyl propionate, and ethyl 2-alkoxypropionate, etc.), methyl 2-alkoxypropionate, 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.

As the ethers, for example, 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 can be preferably used.

Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-methylcyclohexanone, l-glucosone (levoglucosenone), and dihydro-l-glucosone.

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

As the sulfoxide, dimethyl sulfoxide is preferable, for example.

As the amides, 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 and the like can be preferably used.

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

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 monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methyl benzyl alcohol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.

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

In the present invention, it is preferable that the solvent be 1 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, levoglucosone, and dihydro-levoglucosone. Particularly preferred are dimethyl sulfoxide and gamma-butyrolactone in combination or N-methyl-2-pyrrolidone and ethyl lactate in combination.

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 is adjusted according to the thickness required by 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 thereof 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. 2014/097594, a compound described in paragraphs 2017 to 0078 of Japanese patent application laid-open No. 2018-173573, and the like. 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. Furthermore, the following compounds are also preferably used as the silane coupling agent. In the following formula, me represents methyl group, and Et represents ethyl group.

[ chemical formula 53]

/>

Examples of the other silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 3-epoxypropoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyldiethoxysilane, 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, trimethoxysilyl-3- (trimethoxy) 3-propyl-isocyanurate, 3-mercaptopropyl silane, mercapto-3-methoxypropylpropylsilane, mercapto-3-ethoxypropyl silane, mercapto-3-propylmercapto-propyl silane, mercapto-3-propyl-isocyanurate, mercapto-propyl-silane, and the like, 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 diisopropyl ester, and the like.

Further, as other metal adhesion improvers, compounds described in paragraphs 0046 to 0049 of JP-A2014-186186 and thioether compounds described in paragraphs 0032 to 0043 of JP-A2013-072935 can be used, and these are incorporated herein.

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, per 100 parts by mass of the specific resin. When the lower limit value is not less than the upper limit value, the adhesion between the pattern and the metal layer is improved, and when the upper limit value is not more than the upper limit value, the heat resistance and mechanical properties of the pattern are improved. 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, and 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), thiourea compounds, compounds having a sulfanyl group, 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 halide ions can 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 0073-0076 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 54]

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, p-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol (pyrogallol), p-t-butylcatechol, 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4 '-thiobis (3-methyl-6-t-butylphenol), 2' -methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxylamine cerium salt, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1, 2-cyclohexanediamine tetraacetic acid, glycol ether diamine tetraacetic acid, 2, 6-di-t-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthalene) hydroxylamine ammonium salt, bis (4-hydroxy-3, 5-t-butyl-4-methylphenol, 5-nitroso-5-hydroxy-3, 3-hydroxy-benzyl-4, 3H-tri-4, 3H-hydroxybenzyl ketone, 3, 5H-tri-4-hydroxy-3H-3, 5-t-butyl-4-hydroxy-methyl-4, 2, 6-tetramethylpiperidine 1-oxyl, 2, 6-tetramethylpiperidine 1-oxyl, phenothiazine, phenazine, 1-diphenyl-2-picrylhydrazine, copper (II) dibutyldithiocarbamate, nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, and the like. Further, a polymerization inhibitor described in paragraph 0060 of Japanese patent application laid-open No. 2015-127817 and a compound described in paragraphs 0031 to 0046 of International publication No. 2015/125469, which are incorporated herein by reference, can also be used.

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 amount thereof is preferably within the above range.

< other additives >

The resin composition of the present invention can be blended with various additives such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, anticoagulants, phenolic compounds, other high molecular compounds, plasticizers, other assistants (e.g., defoamers, flame retardants, etc.) and the like as necessary within the range to obtain the effects of the present invention. 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 of Japanese patent application laid-open No. 2012-003225 (paragraph 0237 of the specification of corresponding U.S. patent application publication No. 2013/0034812), and the descriptions of paragraphs 0101 to 0104 and 0107 to 0109 of Japanese patent application laid-open No. 2008-250074, and the like, which are incorporated herein by reference. When these additives are blended, the total blending amount is preferably 3% by 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 the surfactant to the resin composition of the present invention, the liquid properties (particularly fluidity) when the resin composition is prepared into a coating liquid can be further improved, and the uniformity of the coating thickness and the liquid saving property 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, thereby improving wettability to the surface to be coated and improving coatability to the surface to be coated. Therefore, a film having a uniform thickness with less thickness unevenness can be formed more favorably.

Examples of the fluorine-based surfactant include MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, 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 (manufactured by DIC Corporation above), fluoro FC430, fluoro FC431, fluoro FC171, novec FC4430, novec FC4432 (manufactured by 3M Japan Limited above), surflon S-382, surflon SC-101, surflon SC-103, surflon SC-104, surflon SC-105, surflon SC-1068, surflon SC-381, surflon SC-383, surflon S-40 (manufactured by DIC Corporation above), surfon FC431, fluold FC171, novelon FC4430 (manufactured by 3M Japanese Limited above), surflon SC-105, surflon SC-381, surfon SC-383, surfon S-40 (manufactured by Urfon, UF 656, PF) and PF 20, PF656 manufactured by PF 20. The fluorine-based surfactant may be any of the compounds described in paragraphs 0015 to 0158 of Japanese patent application laid-open No. 2015-117327 and the compounds described in paragraphs 0117 to 0132 of Japanese patent application laid-open No. 2011-132503, which are incorporated herein by reference. As the fluorine-based surfactant, a block polymer can be used, and specific examples thereof include compounds described in japanese patent application laid-open publication No. 2011-89090, which are incorporated herein.

The fluorine-containing polymer compound (including 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) alkyleneoxy groups (preferably ethyleneoxy group or propyleneoxy group)) can also be preferably used as the fluorine-containing surfactant used in the present invention.

[ chemical formula 55]

/>

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

As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can also be used. Specific examples thereof include compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP-A2010-164965, which are incorporated herein by reference. 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-containing surfactant having a fluorine content within this range is effective in uniformity of thickness of the coating film and liquid saving property, and 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, 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, PIONIN B-811-N, PIONIN 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).

Examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, 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, and sorbitan fatty acid esters. 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 CO., manufactured by LTD), OLFIN E1010, surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry CO., ltd.), and the like.

Specific examples of the cationic surfactant include organosiloxane polymers KP-341 (Shin-Etsu Chemical Co., ltd.), and (meth) acrylic (co) polymers POLYFLOW No.75, no.77, no.90, no.95 (Kyoeisha Chemical Co., ltd.), W001 (Yusho Co., ltd.), and the like.

Specific examples of the anionic surfactant include W004, W005, W017 (yushoco., ltd.), and saldet BL (manufactured by 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 by oxygen, a higher fatty acid derivative such as behenic acid or behenamide may be added to the resin composition of the present invention so as to be biased to 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.

When the resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass 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 thermal energy and initiates or accelerates the polymerization reaction of a compound having polymerizability. The addition of the thermal radical polymerization initiator can further progress the polymerization reaction of the resin and the polymerizable compound, and therefore can further improve the solvent resistance. The photopolymerization initiator may also 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 Japanese patent application laid-open No. 2008-063254, which are incorporated herein by reference.

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 thermal polymerization initiator is contained in an amount of 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 inorganic 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-150 (NIKKISO co., ltd.).

When 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. Further, 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, and 2- (2, 4-dihydroxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine; 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 when contained, 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 total solid content mass of the composition of the present invention.

[ organic titanium Compound ]

The resin composition of the present embodiment may contain an organic titanium compound. The resin composition can form a resin layer excellent in chemical resistance even when cured at a low temperature by containing an organic titanium compound.

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) Chelating titanium compound: among them, a chelate titanium compound having 2 or more alkoxy groups is more preferable in view of excellent storage stability of the resin composition and obtaining a good cured pattern. Specific examples are titanium bis (triethanolamine) diisopropoxide, titanium bis (n-butoxy) bis (2, 4-glutarate) diisopropoxide bis (2, 4-glutarate) titanium, titanium diisopropoxide bis (tetramethylheptanedioate) titanium, titanium diisopropoxide bis (ethylacetoacetate), and the like.

II) a titanium tetraalkoxide compound: examples of the titanium include tetra (n-butoxy) titanium, tetraethoxy titanium, tetra (2-ethylhexyl) titanium, tetraisobutoxy titanium, tetraisopropoxy titanium, tetramethoxy titanium, tetramethoxypropoxy titanium, tetramethylphenoxy titanium, tetra (n-nonoxy) titanium, tetra (n-propoxy) titanium, tetrastearoxy titanium, and tetra [ bis {2,2- (allyloxymethyl) propoxy } ] titanium.

III) titanocene compound: for example, pentamethylcyclopentadienyl trimethoxytitanium, bis (. Eta.5-2, 4-cyclopenta-1-yl) bis (2, 6-difluorophenyl) titanium, bis (. Eta.5-2, 4-cyclopenta-1-yl) bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium, and the like.

IV) monoalkoxytitanium compounds: for example, titanium isopropoxide, such as dioctyl phosphate, and titanium isopropoxide, such as dodecylbenzenesulfonate.

V) titanium oxide compound: examples of the compound include titanium oxide bis (glutarate), titanium oxide bis (tetramethylpimelate), and titanium oxide phthalocyanine.

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

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

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

When the organic titanium compound is blended, 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 blending amount is 0.05 parts by mass or more, the obtained cured pattern more effectively exhibits good heat resistance and chemical resistance, while when 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 tensile properties 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. Compounds having a substituent at a position adjacent to the phenolic hydroxyl group (ortho position) are preferred. The substituent is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms. Furthermore, the antioxidant is preferably a compound having a phenol group and a phosphite group in the same molecule. Further, the antioxidant can also preferably be a phosphorus-based antioxidant. Examples of phosphorus antioxidants include tris [2- [ [2,4,8, 10-tetrakis (1, 1-dimethylethyl) dibenzo [ d, f ] [1,3,2] dioxaphosphen-hepta-6-yl ] oxy ] ethyl ] amine, tris [2- [ (4, 6,9, 11-tetra-t-butyldibenzo [ d, f ] [1,3,2] dioxaphosphen-2-yl) oxy ] ethyl ] amine, and ethyl bis (2, 4-di-t-butyl-6-methylphenyl) phosphite. Examples of the commercially available antioxidants include ADEKA STAB AO-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB AO-50F, ADEKA STAB AO-60G, ADEKA STAB AO-80, ADEKA STAB AO-330 (manufactured by ADEKA CORPORATION). The antioxidant may be a compound described in paragraphs 0023 to 0048 of Japanese patent No. 6268967, incorporated herein by reference. Furthermore, the compositions of the present invention may contain latent antioxidants as desired. As potential antioxidants, the following compounds may be mentioned: a compound which functions as an antioxidant by protecting a site functioning as an antioxidant with a protecting group and releasing the protecting group by heating at 100 to 250 ℃ or heating at 80 to 200 ℃ in the presence of an acid/base catalyst. 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 adek acoorporation).

Examples of preferred antioxidants include 2, 2-thiobis (4-methyl-6-t-butylphenol), 2, 6-di-t-butylphenol, and compounds represented by formula (3).

[ chemical formula 56]

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 Represents a 1-to 4-valent organic group containing at least one of an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), 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 an aliphatic group and a phenolic hydroxyl group of the resin. Further, by the rust prevention effect on the metal material, oxidation of the metal can be suppressed.

In order to be able to act on both the resin and the metal material, 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 further have a substituent. Among them, alkyl ether 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 due to formation of a metal complex.

Examples of the compound represented by the general formula (3) include, but are not limited to, the following structures.

[ chemical formula 57]

[ chemical formula 58]

[ chemical formula 59]

[ chemical formula 60]

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 the adhesion to a metal material can be easily obtained by the stretching property 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 can be improved by the interaction with a sensitizer. The antioxidant may be used in an amount of 1 or 2 or more. When 2 or more kinds are used, the total amount thereof 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 anticoagulant may be used alone, or 2 or more anticoagulants may be used in combination.

The composition of the present invention may or may not contain an anticoagulant, but when contained, the content of the anticoagulant is preferably 0.01 mass% or more and 10 mass% or less, more preferably 0.02 mass% or more and 5 mass% or less, relative to the total solid content mass of the composition of the present invention.

[ phenol Compounds ]

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, methyl Tris-FR-CR, bisRS-26X (trade name, honshu Chemical Industry Co., ltd.), BIP-PC, BIR-PTBP, BIR-BIPC-F (trade name, ASAHI YUKIZAI CORPORATION).

In the present invention, 1 kind of phenol 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 when contained, 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 copolymerized with (meth) acrylic acid, a novolak resin, a resol resin, a polyhydroxystyrene resin, and a copolymer of these. The other polymer compound may be modified body 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 when contained, the content of 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. For example 1,000mm ² When it is not less than/s, it is easy to apply it with a film thickness of 12,000mm required as an insulating film for rewiring ² When the ratio is not more than/s, a coating film excellent in the coating surface shape 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%. When the content is less than 2.0%, the storage stability of the resin composition is improved.

Examples of the method for maintaining the water content include adjusting the humidity under the storage conditions and reducing the porosity 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 a complex 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: the raw material having a small metal content is selected as the raw material for forming the resin composition of the present invention, the raw material for forming the resin composition of the present invention is filtered by a filter, the inside of the apparatus is lined with polytetrafluoroethylene or the like, and distillation or the like is performed under a condition that contamination is suppressed as much as possible.

In the resin composition of the present invention, when the use 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. Wherein the amount present in the state of halide ion is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, further preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. The total of the chlorine atom and the bromine atom or the chlorine ion and the bromine ion is preferably 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 kinds of 6 layers of resins constituting the inner wall of the container and a bottle having 6 kinds of resins and 7 layers of resins are preferably used for the purpose of suppressing the mixing of impurities 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 >

By curing the resin composition of the present invention, a cured product of the resin composition can be obtained,

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, more preferably at a heating temperature 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. The shape of the cured product can be selected by patterning the resin composition according to the use of the resin composition, such as forming a protective film on a wall surface, forming a through hole for conduction, adjusting impedance, electrostatic capacitance, 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 of the resin composition of the present invention upon curing is preferably 50% or less, more preferably 45% or less, and still more preferably 40% or less. The shrinkage ratio herein refers to the percentage of the volume change of the resin composition before and after curing, and can be calculated from 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. At 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.

The mixing may be performed by stirring the mixture with stirring blades, mixing by a ball mill, or mixing by rotating the tank itself.

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, it is preferable to filter the resin composition by using a filter. 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. When a plurality of filters are used, filters having different pore diameters or different materials may be used in combination. Examples of the connection method include the following: HDPE filters with a pore size of 1 μm were used as the first stage, HDPE filters with a pore size of 0.2 μm were used as the second stage, and the two were connected in series. Moreover, various materials may be filtered multiple times. When the filtration is performed a plurality of times, the filtration may be a cyclic filtration. Moreover, pressure filtration may be performed. When the pressure filtration is performed, for example, the pressure applied is 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 may be performed using an adsorbent. It is also possible to combine filter filtration and impurity removal treatment using an adsorbent material. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

After filtration with the filter, the resin composition filled in the bottle may be further subjected to a step of deaeration by placing the resin composition under reduced pressure.

(method for producing cured product)

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

[ substrate ]

The type of the substrate may be appropriately determined according to the application, and examples thereof include substrates for semiconductor production such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, metal substrates such as quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflective films, ni, cu, cr, fe (for example, any of substrates formed of metal and substrates formed with a metal layer by plating, vapor deposition, and the like), papers, SOG (Spin On Glass), TFT (thin film transistor) array substrates, mold substrates, electrode plates of Plasma Display Panels (PDP), and the like, without particular limitation. In the present invention, a substrate for semiconductor production 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, an oxide layer, or the like formed of Hexamethyldisilazane (HMDS), 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 in the case of a circular shape. In the case of rectangular shapes, the length of the short side is, for example, 100 to 1000mm, preferably 200 to 700mm.

As the base material, for example, a plate-like base material (substrate) is preferably used.

When a resin composition is applied to the surface of a resin layer (for example, a layer formed of a cured product) or the surface of a metal layer to form a film, the resin layer and the metal layer serve 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 application method include dip coating, air knife coating, curtain coating, bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. The spin coating method, the slit coating method, the spray coating method, or the inkjet method is more preferable from the viewpoint of film thickness uniformity, and the spin coating method and the slit coating method are preferable from the viewpoint of film thickness uniformity and productivity. By adjusting the solid content concentration and the coating conditions of the resin composition according to the method, a film having a desired thickness can be obtained.

In addition, a coating method can be appropriately selected according to the shape of the substrate, and spin coating, spray coating, ink jet method, or the like is preferable in the case of a round substrate such as a wafer, and slit coating, spray coating, ink jet method, or the like is preferable in the case of a rectangular substrate. In the case of spin coating, for example, a spin speed of 500 to 3,500rpm can be applied for about 10 seconds to 3 minutes.

Further, a method of transferring a coating film formed by previously applying the above-described applying method to a temporary support onto a substrate can also be applied.

As the transfer method, the production method described in paragraphs 0023, 0036 to 0051 of japanese patent application laid-open publication No. 2006-023696 or 0096 to 0108 of japanese patent application laid-open publication No. 2006-047592 can be preferably used in the present invention.

Further, a step of removing an excess film on the end portion of the base material may be performed. Examples of such a process include Edge Bead Rinse (EBR) and back surface rinse.

Furthermore, the following pre-wetting process may be employed: before the resin composition is applied to the substrate, various solvents are applied to the substrate to improve wettability of the substrate, and then the resin composition is applied.

< drying Process >

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

That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed in 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 ℃. Further, drying may be performed by decompression. 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 subjected to 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 in the film forming step.

Selective exposure refers to exposing a portion of the film. By performing selective exposure, 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 determined in the range of 190 to 1,000 nm, preferably 240 to 550nm.

As the exposure wavelength, there may be mentioned (1) a semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) a metal halide lamp, (3) a high-pressure mercury lamp, g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), i-rays (wavelength 365 nm), broadband (g, h, 3 wavelengths of i-rays), (4) an excimer laser, a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), 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, particularly, high-pressure mercury lamp exposure is preferable, and among them, i-ray exposure 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, and examples thereof include exposure using a photomask, exposure by a laser direct imaging method, and the like.

< post-exposure heating Process >

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

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 appropriately changed during the heating process.

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

In addition, the heating is preferably performed in an atmosphere having a low oxygen concentration by passing an inert gas such as nitrogen, helium, or argon.

< developing Process >

The exposed film may be subjected to 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.

By performing development, one of the exposed portion and the non-exposed portion of the film is removed to form a pattern.

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

[ developer solution ]

As the developer used in the developing step, an aqueous alkali solution or a developer containing an organic solvent is exemplified.

When the developer is an aqueous alkali solution, examples of the basic compound that can be contained in the aqueous alkali solution include inorganic bases, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts, preferably TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltrimethylammonium 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, when TMAH is used, the content of the alkaline compound in the developer is preferably 0.01 to 10 mass%, more preferably 0.1 to 5 mass%, and even more preferably 0.3 to 3 mass% based on the total amount of the developer.

When the developer contains an organic solvent, examples of the esters 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, epsilon-caprolactone, delta-valerolactone, and alkyl alkoxyacetate (for example: 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-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate, and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), 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, and as sulfoxides, dimethyl sulfoxide, and as alcohols, methanol, ethanol, isopropanol, diethylene glycol, methyl butanol, N-butyl glycol, methyl pyrrolidone, N-methyl pyrrolidone, and the like, and as methyl-pyrrolidone, and the like, and as alcohols, and as methyl-N-butyl amide, and the like, are preferable.

When 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 cyclopentanone, γ -butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is preferable, a developer containing at least 1 selected from cyclopentanone, γ -butyrolactone, and dimethyl sulfoxide is more preferable, and a developer containing cyclopentanone is most preferable.

When the developing solution contains an organic solvent, the content of the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more, relative to the total mass of the developing solution. 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 the desired pattern can be formed, and there are the following methods: a method of immersing a substrate on which a film is formed in a developer, a spin-on immersion developing method of supplying a developer to a film formed on a substrate by a nozzle, or a method of continuously supplying a developer. The type of the nozzle is not particularly limited, and examples thereof include a direct current nozzle, a shower nozzle, a spray nozzle, and the like.

The method of supplying the developer with the direct current nozzle or the method of continuously supplying the developer with the 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 with the spray nozzle is more preferable from the viewpoints of the permeability of the developer to the image portion.

The process of continuously supplying the developer to the substrate by the dc nozzle, then rotating the substrate to remove the developer from the substrate, after spin-drying, and then continuously supplying the developer again by the dc nozzle, and then rotating the substrate to remove the developer from the substrate may be employed, or the process 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 on the substrate in a substantially stationary state, 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 used.

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 may be preferably 10 to 45 ℃, more preferably 18 to 30 ℃.

In the developing step, after the treatment with the developer, the pattern may be further washed (rinsed) with a 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 ]

When the developer is an aqueous alkali solution, water can be used as the rinse liquid, for example. When 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.

When the rinse liquid contains an organic solvent, examples of the organic solvent include ethyl acetate, n-butyl acetate, pentyl formate, isopentyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ -butyrolactone, ε -caprolactone, δ -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.), alkyl 2-alkoxypropionate (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, methyl 2-ethoxypropionate, methyl 2-alkoxymethyl 2-alkoxypropionate, methyl 2-alkoxymethyl 2-ethoxypropionate, methyl 2-ethoxymethyl 2-alkoxymethyl 2-ethoxypropionate, etc.), and the like (e.g., methyl 2-ethoxypropionate, methyl 2-ethoxymethyl 2-alkoxypropionate, etc.), and the like, 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, and as sulfoxides, dimethyl sulfoxide, and as alcohols, methanol, ethanol, isopropanol, diethylene glycol, methyl butanol, N-butyl glycol, methyl pyrrolidone, N-methyl pyrrolidone, and the like, and as methyl amides, and the like, and as ketones, and as preferred examples.

When the rinse liquid contains an organic solvent, the organic solvent may be used in an amount of 1 or 2 or more kinds thereof may be used in combination. In the present invention, particularly preferred are cyclopentanone, γ -butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME, more preferred are cyclopentanone, γ -butyrolactone, dimethyl sulfoxide, PGMEA, and PGME, and still more preferred are cyclohexanone and PGMEA.

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, the rinse solution may be 100 mass% organic solvent.

The rinse solution may also contain other ingredients.

[ method for supplying rinse solution ]

The method of supplying the rinse liquid is not particularly limited as long as the desired pattern can be formed, and there are the following methods: a method of immersing a substrate in a rinse solution, a method of supplying the rinse solution onto the substrate by spin-coating immersion, a method of supplying the rinse solution onto the substrate by a shower head, a method of continuously supplying the rinse solution onto the substrate by a direct-current nozzle or the like.

From the viewpoints of the permeability of the rinse liquid, the removability of the non-image portion, and the efficiency in production, a method of supplying the rinse liquid by using a spray nozzle, a direct-current nozzle, a spray nozzle, or the like is preferable, and a method of continuously supplying the rinse liquid by using a spray nozzle is more preferable from the viewpoint of the permeability of the rinse liquid to the image portion. The type of the nozzle is not particularly limited, and examples thereof include a direct current 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 by a direct-current nozzle, and more preferably a step of supplying a rinsing liquid by 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 on the substrate in a substantially stationary state, 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 used.

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

< heating Process >

The pattern obtained by the development step (the pattern after the rinsing step in the case of performing the rinsing step) may be subjected to a heating step of 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 include a heating step of heating a pattern obtained by another method without performing the development step or a film obtained by the film forming step.

In the heating step, the specific resin is cyclized to be a resin such as 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 ℃.

Further, since the resin composition of the present invention can give a cured film excellent in elongation at break even at low temperature, a preferable embodiment is also one in which the heating temperature is set to 200 ℃ or less, and further 180 ℃ or less.

The heating step is preferably the following step: the cyclization reaction of the specific resin is promoted in the pattern by the action of a base or the like generated from the base generator by heating.

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 temperature rise rate is set to 1 ℃/min or more, whereby excessive volatilization of the acid or solvent can be prevented while ensuring productivity, and the residual stress of the cured product can be relaxed by setting the temperature rise rate to 12 ℃/min or less.

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

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 means the temperature at the start of the step of heating to the highest heating temperature. For example, when 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 interlayer adhesiveness.

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

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

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

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

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

< post-development exposure Process >

The pattern obtained by the development 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 development step instead of or in addition to the heating 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, cyclization reaction of a specific resin by light-receiving of a photo-alkali generator, release reaction of an acid-decomposable group by light-receiving of a photo-acid generator, and the like can be promoted.

In the post-development exposure step, at least a part of the pattern obtained in the development step may be exposed, and preferably all of the pattern is exposed.

The exposure amount in the post-development exposure step is preferably 50 to 20,000mJ/cm as calculated by the exposure energy conversion at a wavelength at which the photosensitive compound has sensitivity 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, at least one of the heating step and the post-development exposure step) may be subjected 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 the pattern obtained by the developing step (preferably, at least one of a heating step and a post-developing exposure step is performed).

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 (lift off), electroplating, electroless plating, etching, printing, a method of combining these, and the like can be considered. More specifically, a patterning method in which sputtering, photolithography, and etching are combined, and a patterning method in which photolithography and electroplating are combined can be cited. A preferred embodiment of plating includes plating using a copper sulfate plating solution or a copper cyanide plating solution.

The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm, in terms of the thickest part.

< 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 pattern formed on an insulating film for mounting such as the above by etching, or 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", release of polyimide material base and development "11 th 2011", release of polyimide material base and application "NTS, 8 th 2010, etc., of the kaki ben yan min/prison, CMC technical library.

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, use of a molded part in etching, production of a protective paint and a dielectric layer in electronics, particularly microelectronics, and the like.

(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 comprising 2 or more layers of cured products, and may be a laminate comprising 3 or more layers.

Of the layers of the cured product of 2 or more layers contained in the laminate, at least 1 layer is a layer of the cured product of the present invention, and from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product accompanying the shrinkage, it is also preferable that all of the layers of the cured product contained 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 a 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 carried out a plurality of times. The preferable mode of the metal layer forming step is as described above.

As the laminate, for example, a laminate having a layer structure in which at least 3 layers of 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 is preferable.

The layer formed of the first cured product and the layer formed of the second cured product are each preferably a layer formed of the cured product of the present invention. The resin composition of the present invention for forming a layer formed of the first cured product and the resin composition of the present invention for forming a layer formed of the second cured product may have the same composition or may have a composition different from each other. 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. The film formation step (a) and at least one of the heating step and the post-development exposure step (d) may be repeated. Further, the method may include (e) a metal layer forming step after at least one of the heating step and the post-development exposure step. The lamination step may obviously further include the above-described drying step or the like as appropriate.

When the lamination step is further performed after the lamination step, a surface activation treatment step may be further performed after the exposure step, after the heating step, or after the metal layer formation step. As the surface activation treatment, a plasma treatment is 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, the resin layer is preferably a structure of 2 or more and 20 or less layers, more preferably a structure of 2 or more and 9 or less layers, such as a resin layer/metal layer/resin layer/metal layer.

The composition, shape, film thickness, etc. of the layers may be the same or different.

The following is particularly preferred in the present invention: after the metal layer is provided, a cured product (resin layer) of the resin composition of the present invention is further formed to cover the metal layer. Specifically, the method includes a method in which (a) the film forming step, (b) the exposure step, (c) the developing step, (d) at least one of the heating step and the post-developing exposure step, and (e) the metal layer forming step are repeated in this order, or a method in which (a) the film forming step, (d) at least one of the heating step and the post-developing exposure step, and (e) the metal layer forming step are repeated in this order. 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 activation treatment Process)

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. The surface activation treatment is preferably performed on at least a part of the metal layer, and preferably, a part or the whole of the region of the metal layer where the resin composition layer is formed is surface-activated. In this way, by performing the surface activation treatment on the surface of the metal layer, the adhesion to the resin composition layer (film) provided on the surface thereof can be improved.

Further, it is also preferable to perform a surface activation treatment on a part or the whole of the resin composition layer (resin layer) after exposure. In this way, by performing the surface activation treatment on the surface of the resin composition layer, the adhesion to the metal layer or the resin layer provided on the surface subjected to the surface activation treatment can be improved. In particular, in the case of performing negative development or the like, when the resin composition layer is cured, the resin composition layer is less likely to be damaged by the surface treatment, and adhesion is easily improved.

The surface activation treatment may be specifically performed from various source gases (oxygen, hydrogen, argonNitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, CF-based ₄ /O ₂ 、NF ₃ /O ₂ 、SF ₆ 、NF ₃ 、NF ₃ /O ₂ The etching treatment, the surface treatment by Ultraviolet (UV) ozone method, the treatment of immersing in an aqueous hydrochloric acid solution to remove an oxide film and then immersing in an organic surface treating agent containing a compound having at least 1 of an amino group and a thiol group, and the mechanical roughening treatment using a brush are selected, and plasma treatment is preferable, and oxygen plasma treatment using oxygen as a source gas is particularly preferable. In the case of corona discharge treatment, the energy is preferably 500 to 200,000J/m ² More preferably 1000 to 100,000J/m ² Most preferably from 10,000 to 50,000J/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 forming 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, which are incorporated herein by reference.

(resin)

The resin of the present invention has at least one of a repeating unit represented by the following formula (1-1) and a repeating unit represented by the following formula (1-2).

[ chemical formula 61]

In the formula (1-1) or the formula (1-2), W ¹ Represents a 2-valent organic group, X ¹ Represents a 4-valent organic group, R ¹ ～R ³ Each independently represents a group represented by the following formula (3-1) or a group represented by the formula (3-2)Group W ² Represents a 2-valent organic group, X ² Represents a 3-valent organic group, the resin comprising a compound selected from the group consisting of those represented by the formula (1-1) and R ¹ R is R ² At least one of them is a repeating unit of a group represented by the formula (3-1), and R is represented by the formula (1-2) ³ At least 1 kind of repeating units among repeating units of the group represented by the formula (3-1).

[ chemical formula 62]

The preferred mode of the resin of the present invention is the same as the preferred mode of the specific resin contained in the above-described resin composition of the present invention.

Examples

The present invention will be described in further detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment order, 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 polyimide precursor resin (SA-1)

19.1g (61.2 mmol) of 4,4' -oxydiphthalic dianhydride, 12.3g (94 mmol) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 21.5g (272 mmol) of pyridine, 80g of diglyme are mixed and stirred at 25 ℃. Next, 2.18g (30.6 mmol) of pyrrolidine was dissolved in 10g of diglyme and added dropwise over 30 minutes, followed by stirring at 60 ℃ for 4 hours and cooling to 25 ℃. Then, after the reaction solution was cooled to-10 ℃, 15.3g (127 mmol) of thionyl chloride was added dropwise over 90 minutes, and stirred for 2 hours. Then, a solution of 18.8g (51 mmol) of 4,4' -bis (4-aminophenoxy) biphenyl dissolved in 100mL of NMP was added dropwise via 1, and the mixture was stirred for 2 hours. Next, 9.0g (195 mmol) of ethanol was added, the mixture was stirred for 2 hours, 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 ℃ under reduced pressure for 2 days to obtain a polyimide precursor (SA-1). The polyimide precursor SA-1 obtained had a weight average molecular weight (Mw) of 23, 100 and a number average molecular weight (Mn) of 8,900.

The structure of SA-1 is assumed to be represented by the following formula (SA-1).

[ chemical formula 63]

(SA-1)

< Synthesis of polyimide precursor resins (SA-2 to SA-5) ]

SA-2 to SA-5 were synthesized in the same manner as SA-1 except that the types and molar ratios of the amine (pyrrolidine in SA-1 synthesis) and the alcohol (2-hydroxyethyl methacrylate in SA-1 synthesis) were changed as described in the following table, and the carboxylic anhydride (4, 4 '-oxydiphthalic dianhydride in SA-1 synthesis) and the diamine (4, 4' -bis (4-aminophenoxy) biphenyl in SA-1 synthesis) were appropriately changed.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of these resins are shown in the columns of Mw and Mn, respectively, of the following tables.

The structures of SA-2 to SA-5 are assumed to be represented by the following formulas (SA-2) to (SA-5), respectively. In the following formula, the subscript of brackets indicating the repeating units indicates the molar ratio of each repeating unit.

TABLE 1

[ chemical formula 64]

(SA-2)

(SA-3)

(SA-4)

[ chemical formula 65]

(SA-5)

/>

< Synthesis of CSAH-1 >

In a flask equipped with a stirrer and a condenser, 22.1g (105 mmol) of trimellitic anhydride chloride (Tokyo Chemical Industry co., ltd.) and 8.70g of pyridine (Tokyo Chemical Industry co., ltd.) were dissolved in 150mL of tetrahydrofuran, and cooled to 0 to 10 ℃. Then, 13.0g (100 mmol) of 2-hydroxyethyl methacrylate (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 3 hours. Subsequently, the reaction solution was diluted with 700mL of ethyl acetate, and transferred to a separating funnel. Next, the organic layer was washed with 200mL of water, 300mL of saturated sodium bicarbonate (sodium bicarbonate), 300mL of diluted hydrochloric acid, and 300mL of saturated brine, dried over magnesium sulfate, filtered, and then washed with water The organic solvent was removed by distillation to obtain 25g of CSAH-1. According to ¹ The H-NMR spectrum was found to be CSAH-1.

[ chemical formula 66]

< Synthesis of CSA-1 >

In a flask equipped with a stirrer and a condenser, 20.0g (135 mmol) of phthalic anhydride (Tokyo Chemical Industry co., ltd.) was dissolved in 200mL of ethyl acetate, and cooled to 0 to 10 ℃. Then, 8.64g (122 mmol) of pyrrolidine (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 3 hours. Then, the precipitated crystals were filtered, washed with 100mL of ethyl acetate, and filtered. It was dried at 25℃for 24 hours, thereby obtaining 19g of CSA-1. According to ¹ The H-NMR spectrum confirmed CSA-1.

[ chemical formula 67]

< Synthesis of CSA-2 to CSA-8 >

CSA-2 to CSA-8 were synthesized in the same manner as in the synthesis of CSA-1 described above, except that the starting materials were appropriately changed.

[ chemical formula 68]

< Synthesis of CS-1 >

To a flask equipped with a stirrer and a condenser, 11.0g (50 mmol) of the CSA-1, 4-methoxyaniline synthesized in the above (Tokyo Chemical Industry co., ltd.) 6.16g (50 mmol), 4-methylaminopyridine (Tokyo Chemical Industry co., ltd.) 7 were added. 41g (60 mmol) and 100g of tetrahydrofuran, and cooling to 0 to 10 ℃. Subsequently, 11.5g (60 mmol) of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (Tokyo Chemical Industry co., ltd.) was added, and after stirring at 0 to 10℃for 1 hour, the temperature was raised to 25℃and stirred for 3 hours. Then, the reaction solution was poured into 500mL of ethyl acetate, transferred to a separating funnel, washed with 300mL of water, 300mL of saturated sodium bicarbonate (sodium bicarbonate) and 300mL of 1N hydrochloric acid water, dried over magnesium sulfate, and then ethyl acetate was removed by a distiller. After 70g of tetrahydrofuran was added thereto and dissolved, 700g of hexane was crystallized, stirred for 30 minutes and filtered. It was dried at 25℃for 24 hours, thereby obtaining 19g of CS-1. According to ¹ The H-NMR spectrum confirmed CS-1.

[ chemical formula 69]

< Synthesis of BS-1 >

In a flask equipped with a stirrer and a condenser, 27.44g (200 mmol) of 2- (4-aminophenyl) ethyl alcohol (TokyoChemical 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 from a solution of ethyl acetate (800 mL/200 mL in hexane) and filtered. Subsequently, the filtrate was stirred in 500mL of ethyl acetate for 1 hour, and filtered. It was dried at 45℃for 24 hours, whereby 45g of BS-1 was obtained. According to ¹ The H-NMR spectrum confirmed to be BS-1.

[ chemical formula 70]

< Synthesis of BS-2 >

In a flask equipped with a stirrer and a condenser, 13.0g (100 mmol) of 2-hydroxyethyl methacrylate (Tokyo Chemical Industry CO., ltd.), 0.001g of p-methoxyphenol (Tokyo Chemical Industry CO., ltd.), and 0.01g of Neostan U-600 (NITTO KASEI CO.,. Ltd.) were dissolved in 60mL of tetrahydrofuran, and stirred at 25 ℃. Subsequently, 11.9g (100 mmol) of phenyl isocyanate (Tokyo Chemical Industry co., ltd.) was added dropwise over 1 hour, and then the mixture was heated to 50 ℃ and stirred for 4 hours. Then, it was dissolved in 800mL of ethyl acetate and transferred to a separating funnel. Then, the mixture was washed with dilute hydrochloric acid, sodium hydrogencarbonate and saturated brine in this order, and the solvent was removed by a distiller, whereby 18g of BS-2 was obtained. According to ¹ The H-NMR spectrum confirmed to be BS-2.

[ chemical formula 71]

< Synthesis of SA-6 >

19.1g (61.2 mmol) of 4,4' -oxydiphthalic dianhydride, 13.9g (105 mmol) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 21.5g (272 mmol) of pyridine, 80g of diglyme are mixed and stirred at 25 ℃. Next, 1.31g (18.4 mmol) of pyrrolidine was dissolved in 10g of diglyme and added dropwise over 30 minutes, followed by stirring at 60℃for 4 hours and cooling to 25 ℃. Then, 2.42g of CSA-1 was added, the reaction mixture was cooled to-10℃and 18.1g (150 mmol) of thionyl chloride was added dropwise over 90 minutes, followed by stirring for 2 hours. Then, a solution of 22.4g (60.6 mmol) of 4,4' -bis (4-aminophenoxy) biphenyl dissolved in 100mL of NMP was added dropwise over 1 hour, followed by stirring for 3 hours. Next, 100mL of tetrahydrofuran was added, 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 again in 4 liters of water for 30 minutes and filtered again, and the obtained polyimide precursor resin was dried at 45 ℃ under reduced pressure for 24 hours. Next, the dried polyimide precursor resin was dissolved in 300mL of tetrahydrofuran, 50g of ion exchange resin was added and stirred for 6 hours, and then 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. Filtration was performed to obtain a polyimide precursor resin, which was dried at 45 ℃ for 2 days, thereby obtaining a polyimide precursor (SA-6). The polyimide precursor SA-6 thus obtained had a weight average molecular weight of 19700 and a number average molecular weight of 7,900.

The structure of SA-6 is assumed to be represented by the following formula (SA-6).

[ chemical formula 72]

(SA-6)

< Synthesis of polyimide precursor resins (SA-7 to SA-12) ]

SA-7 to SA-12 were synthesized in the same manner as SA-6 except that the types of amine (pyrrolidine in the synthesis of SA-6) and alcohol (2-hydroxyethyl methacrylate in the synthesis of SA-6), the molar ratios thereof, and the capping agent (CSA-1 in the synthesis of SA-6) were changed as described in the following tables, and carboxylic anhydride (4, 4 '-oxydiphthalic dianhydride in the synthesis of SA-6) and diamine (4, 4' -bis (4-aminophenoxy) biphenyl) were appropriately changed.

The structures of SA-7 to SA-12 are assumed to be those represented by the following formulas (SA-7) to (SA-12), respectively.

TABLE 2

Resin name

The amine used

The alcohol used

Amine/alcohol molar ratio

End capping agent

Mw

Mn

SA-7

Pyrrolidine compounds

Methacrylic acid 2-hydroxyethyl ester

10/90

CSA-7

16900

6500

SA-8

Pyrrolidine compounds

Methacrylic acid 2-hydroxyethyl ester

0.5/99.5

CSA-5

18900

7200

SA-9

3, 5-dimethylpiperidine

Methacrylic acid 2-hydroxyethyl ester

30/70

CSA-1

21800

8600

SA-10

Morpholine (III)

Methacrylic acid 2-hydroxyethyl ester

25/75

CSA-1

20000

8100

SA-11

Pyrrolidine compounds

Glycerol dimethacrylate

25/75

CSA-2

26400

9800

SA-12

Pyrrolidine compounds

BS-1

25/75

CSA-6

35200

12600

[ chemical formula 73]

(SA-7)

(SA-8)

(SA-9)

(SA-10)

[ chemical formula 74]

(SA-11)

(SA-12)

< Synthesis of SA-13 >

155.1g of 4,4' -oxydiphthalic dianhydride (0 DPA) was placed in a separate flask, and 97.6g of 2-hydroxyethyl methacrylate (HEMA), 17.8g of pyrrolidine and 400ml of gamma-butyrolactone were added. 79.1g of pyridine was added while stirring at room temperature, whereby a reaction mixture was obtained. After the completion of the heat generation by the reaction, the reaction mixture was cooled to room temperature and allowed to stand for 16 hours.

Then, after adding CSA-3 to 15.2g of the reaction solution under ice-cooling, 243g of Dicyclohexylcarbodiimide (DCC) was added to the reaction mixture over 40 minutes while stirring a solution of 180ml of gamma-butyrolactone. Subsequently, a suspension of 99.1g of 4,4' -diaminodiphenyl ether in 350ml of gamma-butyrolactone was added over 60 minutes while stirring. After stirring at room temperature for 2 hours, 30ml of ethanol was added thereto and stirred for 1 hour. Thereafter, 400ml of gamma-butyrolactone was added. The precipitate formed in the reaction mixture was obtained by filtration, and a reaction solution was obtained.

The obtained reaction solution was added to 3 liters of ethanol, and a precipitate composed of a crude polymer was formed. The crude polymer thus obtained was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. 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 SA-13 was obtained in the form of powder. As a result of measuring the weight average molecular weight (Mw) of this polymer SA-13, it was 20,100, and the number average molecular weight (Mn) was 8,000.

The structure of SA-13 is assumed to be represented by the following formula (SA-13).

[ chemical formula 75]

(SA-13)

< Synthesis of SA-14 >

19.1g (61.2 mmol) of 4,4' -oxydiphthalic dianhydride, 0.05g of hydroquinone, 21.5g (272 mmol) of pyridine, 80g of diglyme are mixed and stirred at 25 ℃. Then, 2.45g (40 mmol) of pyrrolidine, 5.01g (40 mmol) of cis-octahydroisoindole, 7.97 g (43 mmol) of 2- (tert-butylamino) ethyl methacrylate were dissolved in 20g of diglyme, and after dropwise addition over 1 hour, they were stirred at 60℃for 4 hours and cooled to 25 ℃. Then, 2.52g of CSA-7 was added, the reaction mixture was cooled to-10℃and 15.5g (129 mmol) of thionyl chloride was added dropwise over 90 minutes, followed by stirring for 2 hours. Then, a solution of 12.1g (60.6 mmol) of 4,4' -diaminodiphenyl ether dissolved in 100mL of NMP was added dropwise over 1 hour, and the mixture was stirred for 3 hours. Next, 100mL of tetrahydrofuran was added, 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 again in 4 liters of water for 30 minutes and filtered again, and the obtained polyimide precursor resin was dried at 45 ℃ under reduced pressure for 24 hours. Next, the dried polyimide precursor resin was dissolved in 300mL of tetrahydrofuran, 50g of ion exchange resin was added and stirred for 6 hours, and then 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. Filtration was performed to obtain a polyimide precursor resin, which was dried at 45℃for 2 days, thereby obtaining a polyimide precursor (SA-14). The polyimide precursor SA-14 thus obtained had a weight average molecular weight of 22000 and a number average molecular weight of 8600.

The structure of SA-14 is assumed to be represented by the following formula (SA-14).

[ chemical formula 76]

(SA-14)

< Synthesis of SA-15 to SA-18 >

SA-15 to SA-18 were synthesized in the same manner as SA-14 except that the types of the pyrrolidine, cis-octahydroisoindole, 2- (tert-butylamino) ethyl methacrylate and alcohol, the molar ratios thereof, and the capping agent (CSA-7 in the synthesis of SA-6) were changed as described in the following tables, and the carboxylic anhydride (4, 4 '-oxydiphthalic dianhydride in the synthesis of SA-14) and the diamine (4, 4' -diaminodiphenyl ether) were appropriately changed.

The structures of SA-15 to SA-18 are assumed to be those represented by the following formulas (SA-15) to (SA-18), respectively.

TABLE 3

[ chemical formula 77]

(SA-15)

(SA-16)

(SA-17)

(SA-18)

Here, the ratio (%) of the total molar amount of the groups represented by the formula (3-1) and the ratio (%) of the total molar amount of the groups represented by the formula (3-2) in each resin are shown in the following table.

In the following table, the column "ratio 1" indicates the ratio (%) of the total molar amount of the groups represented by the formula (3-1) to the total molar amount of the groups represented by the formula (3-1) and the groups represented by the formula (3-2) contained in the resin.

TABLE 4

Resin name	The ratio of the total molar amount of the groups represented by the formula (3-1)	The ratio of the total molar amount of the groups represented by the formula (3-2)	Proportion 1
				SA-1	15	85	15
SA-2	10	90	10
				SA-3	50	50	50
SA-4	30	70	30
				SA-5	25	75	25
SA-6	15	85	15
				SA-7	10	90	10
SA-8	0.5	99.5	0.5
				SA-9	30	70	30
SA-10	25	75	25
				SA-11	25	75	25
SA-12	25	75	25
				SA-13	25	75	25
SA-14	100	0	100
				SA-15	100	0	100
SA-16	100	0	100
				SA-17	100	0	100
SA-18	45	55	45

< Synthesis of C-1 >

In a flask equipped with a stirrer and a condenser, 27.44g (200 mmol) of 2- (4-aminophenyl) ethyl alcohol (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 from a solution of ethyl acetate (800 mL/200 mL in hexane) and filtered. Subsequently, the filtrate was stirred in 500mL of ethyl acetate for 1 hour, and filtered. It was dried at 45℃for 24 hours, whereby 45g of C-1 was obtained. According to ¹ The H-NMR spectrum confirmed C-1.

[ chemical formula 78]

< Synthesis of BMB-1 >

In a flask equipped with a stirrer and a condenser, 8.88g (52.5 mmol) of the CSA-3, 2-bis [4- (4-aminophenoxy) phenyl ] synthesized in the above was charged]Propane 10.26g (25 milliMoles), 1.22g (10 mmoles) of 4-methylaminopyridine, 10.54g (55 mmoles) of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 60g of tetrahydrofuran, and stirred at 25℃for 6 hours. Subsequently, the reaction solution was transferred to a separating funnel while being diluted with 500mL of ethyl acetate, washed with 300mL of water, 300mL of diluted hydrochloric acid, 300mL of saturated sodium bicarbonate (sodium bicarbonate) and 300mL of saturated brine, and dried over 50g of magnesium sulfate. After it was filtered with filter paper, the solvent was removed in a distiller, thereby obtaining 11g of BMB-1. According to ¹ The H-NMR spectrum confirmed to be BMB-1.

[ chemical formula 79]

< Synthesis of BMB-2 >

The synthesis was performed in the same manner as BMB-1 except that CSA-1 of BMB-1 was changed to CSA-8.

[ chemical formula 80]

< Synthesis of comparative example Cmp-1 >

[ Cmp-1: synthesis of polyimide precursor (Cmp-1: polyimide precursor having radical polymerizable group) from 4,4 '-oxydiphthalic dianhydride, 4' -diaminodiphenyl ether and 2-hydroxyethyl methacrylate

155.1g of 4,4' -oxybisphthalic anhydride (ODPA) was placed in a separate flask, and 134.0g of 2-hydroxyethyl methacrylate (HEMA) and 400ml of gamma-butyrolactone were added. 79.1g of pyridine was added while stirring at room temperature, whereby a reaction mixture was obtained. After the completion of the heat generation by the reaction, the reaction mixture was cooled to room temperature and allowed to stand for 16 hours.

Then, a solution of 206.3g of Dicyclohexylcarbodiimide (DCC) dissolved in 180ml of γ -butyrolactone was added to the reaction mixture over 40 minutes while stirring under ice-cooling. Subsequently, 93.0g of 4,4' -diaminodiphenyl ether was added to a suspension of 350ml of gamma-butyrolactone with stirring over a period of 60 minutes. After stirring at room temperature for 2 hours, 30ml of ethanol was added thereto and stirred for 1 hour. Thereafter, 400ml of gamma-butyrolactone was added. The precipitate formed in the reaction mixture was obtained by filtration, and a reaction solution was obtained.

The obtained reaction solution was added to 3 liters of ethanol, and a precipitate composed of a crude polymer was formed. The crude polymer thus obtained was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. 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 Cmp-1 was obtained in the form of powder. The weight average molecular weight (Mw) of this polymer Cmp-1 was measured and found to be 24,000.

< examples and comparative examples >

In each example, the components described in the following table were mixed, respectively, to thereby obtain each resin composition. In each comparative example, the ingredients 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 in the table.

The obtained resin composition and 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 any corresponding components.

TABLE 5

TABLE 6

TABLE 7

TABLE 8

The details of the components described in the table are as follows.

[ resin ]

SA-1 to SA-18: SA-1 to SA-18 synthesized in the above

Cmp-1: above synthetic product (comparative example)

[ Compound B ]

BM-1: n, N' -ethylene bismaleimide (Tokyo Chemical Industry Co., ltd.)

BM-2:1, 8-bis (maleimide) diethylene glycol (Tokyo Chemical Industry co., ltd.)

BM-3:2, 2-bis [4- (4-maleimidophenoxy) phenyl ] propane (Tokyo Chemical Industry Co., ltd.)

BMB-1 to BMB-2: the above-mentioned synthetic product

[ polymerizable Compound (trade name in each case) ]

SR-209: SR-209 (manufactured by Sartomer Company, tnc)

SR-231: SR-231 (Sartomer Company, manufactured by Inc)

a-DPH: A-DPH (Shin-Nakamura Chemical Co., ltd., dipivalol hexaacrylate)

BS-1 to BS-2: the above-mentioned synthetic product

C-1: the above-mentioned synthetic product

C-2:2, 2-bis (4-hydroxyphenyl) propane diglycidyl ether (Tokyo Chemical Industry co., ltd., manufactured)

C-3: diepoxypropyl 4-cyclohexene-1, 2-dicarboxylate (Tokyo Chemical Industry Co., ltd.)

·C-4：Karenz BEI(SHOWA DENKO K.K.)

[ polymerization initiators (all trade names) ]

OXE-01: IRGACURE OXE 01 (manufactured by BASF corporation)

OXE-02: IRGACURE OXE 02 (manufactured by BASF corporation)

[ alkali-generating agent ]

D-1 to D-2: compounds of the structure

·D-3：WPBG-027(FUJIFILM Wako Pure Chemical Corporation)

CS-1: the above-mentioned synthetic product

[ chemical formula 81]

[ migration inhibitor ]

E-1 to E-6: compounds of the structure

[ chemical formula 82]

[ Metal adhesion improver ]

F-1 to F-3: compounds of the structure

[ chemical formula 83]

[ polymerization inhibition System ]

G-1:1, 4-benzoquinone

G-2: 4-methoxyphenol

G-3:1, 4-dihydroxybenzene

G-4: compounds of the structure

[ chemical formula 84]

[ other additives ]

H-1: n-phenyl diethanolamine (Tokyo Chemical Industry Co., ltd.)

BS-1 to BS-3: the compounds BS-1 to BS-3 having the following structures correspond to the above-mentioned compound D.

[ chemical formula 85]

[ solvent ]

DMSO: dimethyl sulfoxide

GBL: gamma-butyrolactone

NMP: n-methylpyrrolidone

In the table, "DMSO/GBL" means that a solvent in which DMSO and GBL are mixed at a mixing ratio (mass ratio) of DMSO to gbl=80:20 was used.

< evaluation >

[ evaluation of elongation at Break ]

In each of examples and comparative examples, a resin composition layer was formed by applying a resin composition or a composition for comparison to a silicon wafer by spin coating. The silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100℃for 5 minutes, and a uniform resin composition layer of about 15 μm thickness was obtained on the silicon wafer.

Using a stepper (Nikon NSR 2005 i9C) at 500mJ/cm ² The entire surface of the obtained resin composition layer was subjected to i-ray exposure.

The resin composition layer (resin layer) after the exposure was heated at a temperature rise rate of 10 ℃/min under a nitrogen atmosphere to a temperature described in the column "temperature" of "curing conditions" in the table, and then 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 out by a punching machine to prepare a test piece having a sample width of 3mm and a sample length of 30 mm. The elongation at break of the obtained test piece in the longitudinal direction was measured in accordance with JIS-K6251 in an environment of 25℃and 65% RH (relative humidity) at a crosshead speed of 300 mm/min by a tensile tester (TEN SILON). Each of the evaluations was performed 5 times, and the arithmetic average value 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 70% or more.

B: the index value is 60% or more and less than 70%.

C: the index value is 50% or more and less than 60%.

D: the index value is less than 50%.

[ evaluation of drug resistance ]

The resin compositions prepared in each of the examples and comparative examples or the comparative composition was applied to a silicon wafer by spin coating, respectively, to thereby 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, and a uniform resin composition layer of about 15 μm in thickness was formed on the silicon wafer. Using a stepper (Nikon NSR 2005 i9C) at 500mJ/cm ² The entire surface of the resin composition layer on the silicon wafer was exposed to light, the exposed resin composition layer (resin layer) was heated at a temperature rise rate of 10 ℃/min under a nitrogen atmosphere, and the resin composition layer was heated at a temperature described in the column "temperature" of "curing conditions" in the table for 180 minutes, 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: mixture of dimethyl sulfoxide (DMSO) and 25% by mass of tetramethylammonium hydroxide (TMAH) in water at a ratio of 90:10 (mass ratio)

Evaluation conditions: the resin layer was immersed in the chemical solution at 75℃for 15 minutes, and the film thicknesses before and after immersion were compared to calculate the dissolution rate (nm/min). Film thickness was measured on the coated surface 10 by ellipsometry (KT-22, manufactured by Foothill Co., ltd.) and the arithmetic average value was obtained as the film thickness.

The evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in the column "chemical resistance" in the table. It can be said that the slower the dissolution rate, the more excellent the chemical resistance.

In the examples described as "-" in the column of "chemical resistance" of the table, no evaluation of chemical resistance was performed.

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 moisture resistance ]

The obtained cured layer was put into a high-temperature and high-humidity tank having a temperature of 121 ℃ and a humidity of 100% for 250 hours, and the cured layer before and after the putting was immersed in the following chemical solution under the following conditions, whereby the film thickness reduction was measured.

Evaluation conditions: the film thickness of the resin layer before and after immersing the resin layer in the chemical solution at 75℃for 15 minutes was compared with the film thickness before and after immersing, and the film thickness reduction (%) was calculated. Film thickness was measured on the coated surface 10 by ellipsometry (KT-22, manufactured by Foothill Co., ltd.) and the arithmetic average value was obtained as the film thickness.

The evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in the column "moisture resistance" of the table. The smaller the difference (%) between the film thickness reduction before and after the high-temperature and high-humidity tank is put in, the more excellent the moisture resistance is.

Film thickness reduction before and after high temperature and high humidity input =a-B

A: the film thickness after immersing in the chemical solution under the above conditions in the cured layer before being put into the high-temperature and high-humidity tank/the film thickness before immersing is multiplied by 100

B: the film thickness after immersing in the chemical solution under the above conditions in the cured layer after being put into the high-temperature and high-humidity tank/the film thickness before immersing is multiplied by 100

Evaluation criterion-

A: the difference between the thickness reduction amounts before and after the high-temperature high-humidity input is less than 5%.

B: the difference between the thickness reduction amounts before and after the high-temperature high-humidity input is 5% or more and less than 10%.

C: the difference between the thickness reduction amounts before and after the high-temperature high-humidity input is 10% or more and less than 20%.

D: the difference between the thickness reduction amounts before and after the high-temperature high-humidity input is 20% or more.

[ evaluation of curing shrinkage ]

In each of examples and comparative examples, a resin composition layer was formed by applying a resin composition or a composition for comparison to a silicon wafer by spin coating. The silicon wafer to which the obtained resin composition layer was applied was dried on a heating plate at 100℃for 5 minutes, and a uniform curable resin composition layer having a thickness of about 15 μm was obtained on the silicon wafer. The film thickness of the curable resin composition layer was measured by a reflection spectroscopic film thickness meter (FE-3000 OTSUKA ELECTRONICS CO, LTD), and this value was designated as "film thickness A".

Next, the entire surface of the obtained curable resin composition layer was subjected to 500mJ/cm by a stepper (Nikon NSR 2005 i9C) ² I-ray exposure is performed at the exposure energy of (a).

The curable resin composition layer (resin layer) after the exposure was heated at a heating rate of 10 ℃/min under 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 and cooled to 25 ℃.

The film thickness of the cured product was measured by a reflection spectroscopic film thickness meter (FE-3000 OTSUKA ELECTRONICS CO, LTD), and this value was designated as "film thickness B".

Film shrinkage was calculated by the following calculation formula.

The calculation formula: shrinkage (%) =100- (film thickness B ≡film thickness a×100)

The evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in the column of "cure shrinkage" in the table. The smaller the above-mentioned shrinkage value, the more excellent the curing shrinkage of the obtained composition layer. In the examples and comparative examples in which the column of "cure shrinkage" is not shown in the table, no evaluation of cure shrinkage was performed.

Evaluation criterion-

A: the film shrinkage was less than 20%.

B: the film shrinkage is 20% or more and less than 25%.

C: the film shrinkage is 25% or more and less than 30%.

D: the film shrinkage is 30% or more.

From the above results, it was found that the cured film formed from the resin composition of the present invention was excellent in elongation at break.

The resin contained in the comparative composition of comparative examples 1 to 2 does not contain the resin represented by the formula (1-1) and R ¹ R is R ² At least one of them is a repeating unit of a group represented by the formula (3-1), and R is represented by the formula (1-2) ³ Any one of the repeating units of the group represented by the formula (3-1). It was found that the elongation at break of the cured films formed from these comparative compositions was poor.

< example 101>

The resin composition used in example 1 was applied to the copper thin layer surface of the resin substrate having a copper thin layer formed thereon in a layer form by spin coating, dried at 100℃for 4 minutes to form a resin composition layer having a film thickness of 20. Mu.m, and then exposed to light by a stepper (manufactured by Nikon Corporation, NSR1505 i 6). Exposure was performed at 365nm wavelength through a mask (binary mask with a pattern of 1:1 lines and spaces, line width of 10 μm). After exposure, the layer was developed with cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds, thereby obtaining a pattern of the layer.

Then, the temperature was raised at a temperature raising rate of 10 ℃/min under a nitrogen atmosphere, and after reaching 230 ℃, the temperature was maintained at 230 ℃ for 3 hours, thereby forming an interlayer insulating film for a rewiring layer. The interlayer insulating film for a rewiring layer is excellent in insulation properties.

Further, 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:

The solvent is used for the preparation of the aqueous solution,

in the formula (1-1) or the formula (1-2), W ¹ Represents a 2-valent organic group, X ¹ Represents a 4-valent organic group, R ¹ ～R ³ Each independently represents a group represented by the following formula (3-1) or a group represented by the formula (3-2), W ² Represents a 2-valent organic group, X ² Represents an organic group having a valence of 3,

the resin comprises a resin selected from the group represented by the formula (1-1) and R ¹ R is R ² At least one of them is a repeating unit of a group represented by the formula (3-1), and R is represented by the formula (1-2) ³ At least 1 kind of repeating units among repeating units of the group represented by the formula (3-1),

in the formula (3-1) and the formula (3-2), Z ¹ Z is as follows ² Each independently represents an organic group, Z ¹ And Z ² Optionally bonded to form a ring structure, A ² Represents an oxygen atom or-NH-, R ¹¹³ Represents a hydrogen atom or a monovalent organic group, and represents a bonding site to other structures.

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

the group represented by the formula (3-1) is a group represented by the formula (3-1-1) or the formula (3-1-2),

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

the ratio of the molar amount of the group represented by formula (3-1) to the total molar amount of the group represented by formula (3-1) and the group represented by formula (3-2) contained in the resin is 0.1 mol% or more.

4. The resin composition according to any one of claim 1 to 3, wherein,

5. The resin composition according to any one of claim 1 to 4, wherein,

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

r in formula (3-2) ¹¹³ Is a group having a polymerizable group.

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

w in formula (1-1) ¹ Or W in formula (1-2) ² Comprising a group represented by any one of the following formulas (5) to (7),

in the formula (5), Y ¹ Represents a single bond or a 2-valent linking group, each represents a bonding site to another structure,

in the formula (6), Y ² Represents a single bond or a 2-valent linking group, each represents a bonding site to another structure,

in formula (7), each represents a bonding site to another structure.

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

the weight average molecular weight of the resin is 10000 or more.

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

the acid value of the resin is 0 mmol/g-1 mmol/g.

10. The resin composition according to any one of claims 1 to 9, further comprising a polymerization initiator.

11. The resin composition according to any one of claims 1 to 10, further comprising a polymerizable compound.

12. The resin composition according to claim 11, wherein,

the polymerizable compound has at least 1 group selected from the group consisting of an imide group, an urea group and a urethane group.

13. The resin composition according to any one of claims 1 to 12, further comprising a compound B which is at least 1 compound selected from the group consisting of a compound having a maleimide structure and a precursor of a compound having a maleimide structure.

14. The resin composition according to claim 13, further comprising a compound C which is a compound having a group capable of reacting with a maleimide structure.

15. The resin composition according to claim 14, wherein,

the group capable of reacting with maleimide structure in the compound C is at least 1 group selected from ethylenically unsaturated group, hydroxyl group, epoxy group and amino group.

16. The resin composition according to any one of claims 1 to 15, which is used for forming an interlayer insulating film for a rewiring layer.

17. A cured product obtained by curing the resin composition according to any one of claims 1 to 16.

18. A laminate comprising 2 or more layers formed from the cured product of claim 17, wherein at least 1 metal layer is included between the layers formed from the cured product.

19. 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 16 to a substrate to form a film.

20. The method for producing a cured product according to claim 19, comprising an exposure step of exposing the film and a development step of developing the film.

21. The method for producing a cured product according to claim 19 or 20, comprising a heating step of heating the film at 50 to 450 ℃.

22. A semiconductor device comprising the cured product of claim 17 or the laminate of claim 18.

23. A resin having at least one of a repeating unit represented by the formula (1-1) and a repeating unit represented by the formula (1-2),

in the formula (1-1) or the formula (1-2), W ¹ Represents a 2-valent organic group, X ¹ Represents a 4-valent organic group, R ¹ ～R ³ Each independently represents a group represented by the following formula (3-1) or a group represented by the formula (3-2), W ² Represents a 2-valent organic group, X ² Represents a 3-valent organic group, the resin comprising a compound selected from the group consisting of those represented by the formula (1-1) and R ¹ R is R ² At least one of them is a repeating unit of a group represented by the formula (3-1), and R is represented by the formula (1-2) ³ The weight of the group represented by the formula (3-1)At least 1 kind of repeating units in the complex unit,

24. The resin according to claim 23, wherein,

r in formula (3-2) ¹¹³ Is a group having a polymerizable group.

25. The resin according to any one of claims 23 or 24, wherein,

w in formula (1-1) ¹ And W in formula (1-2) ² Comprising a group represented by the following formula (4),

in formula (4), each represents a bonding site to another structure.