阅读说明：本技术 固化性树脂组合物、固化膜、层叠体、固化膜的制造方法及半导体器件 (Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device ) 是由 井上遥菜 青岛俊荣 于 2020-03-16 设计创作，主要内容包括：本发明提供一种固化性树脂组合物、通过固化上述固化性树脂组合物而成的固化膜、包含上述固化膜的层叠体、上述固化膜的制造方法及包含上述固化膜或上述层叠体的半导体器件,上述固化性树脂组合物包含选自由聚酰亚胺前体及聚苯并噁唑前体组成的组中的至少1种聚合物前体以及具有氢键合性氮原子且具有包含2个以上烯属不饱和基的基团的聚合性化合物,相对于组合物的总固体成分的源自具有分子量2,000以下的自由基聚合性基团的化合物的自由基聚合性基团价为0.25～4.35mmol/g。(The present invention provides a curable resin composition, a cured film obtained by curing the curable resin composition, a laminate including the cured film, a method for producing the cured film, and a semiconductor device including the cured film or the laminate, wherein the curable resin composition includes at least 1 polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, and a polymerizable compound having a hydrogen-bonding nitrogen atom and having a group containing 2 or more ethylenically unsaturated groups, and the radical polymerizable group valence derived from the compound having a radical polymerizable group having a molecular weight of 2,000 or less is 0.25 to 4.35mmol/g relative to the total solid content of the composition.)

1. A curable resin composition comprising:

a polymer precursor which is at least 1 selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor; and

a polymerizable compound having a hydrogen-bonding nitrogen atom and having a group containing 2 or more ethylenically unsaturated groups,

the radical polymerizable group valence of a compound having a radical polymerizable group with a molecular weight of 2000 or less is 0.25 to 4.35mmol/g based on the total solid content of the composition.

2. The curable resin composition according to claim 1,

the polymerizable compound includes a structure a as a structure including the hydrogen-bonding nitrogen atom, the structure a being at least 1 structure selected from the group consisting of a urethane bond, a urea bond, and an amide bond.

3. The curable resin composition according to claim 2,

the polymerizable compound includes a structure B in which at least 1 bonding site in the structure a is directly bonded to an alkylene group.

4. A curable resin composition comprising:

a polymer precursor which is at least 1 selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor; and

a polymerizable compound having a urea bond or an amide bond and having a group containing 2 or more ethylenically unsaturated groups.

5. The curable resin composition according to any one of claims 1 to 4,

the polymerizable compound contains a (meth) acryloyl group as the group containing the ethylenically unsaturated group.

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

the molecular weight of the polymerizable compound is 200-1000.

7. The curable resin composition according to any one of claims 1 to 6, further comprising a photo radical polymerization initiator.

8. The curable resin composition according to any one of claims 1 to 7, further comprising an onium salt or a thermal base generator.

9. The curable resin composition according to any one of claims 1 to 8, comprising a polyimide precursor as the polymer precursor.

10. The curable resin composition according to claim 9,

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

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

11. The curable resin composition according to claim 10,

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

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

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

14. A laminate comprising 2 or more layers of the cured films of claim 13, comprising a metal layer between any of the cured films.

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

16. The method for producing a cured film according to claim 15, comprising an exposure step of exposing the film to light and a development step of developing the film.

17. The method for producing a cured film according to claim 15 or 16, which comprises a heating step of heating the film at 50 to 450 ℃.

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

Technical Field

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

Background

A resin obtained by cyclizing and curing a precursor of a polymer such as a polyimide resin or a polybenzoxazole resin (hereinafter, the precursor of a polyimide resin and the precursor of a polybenzoxazole resin are also collectively referred to as a "heterocyclic ring-containing polymer precursor") is excellent in heat resistance and insulation properties, and therefore, can be suitably used for various applications. The use is not particularly limited, but the use as a material for an insulating film or a sealing material or a protective film is exemplified by a semiconductor device for actual mounting. Further, the film is also used as a base film, a cover film, or the like of a flexible substrate.

For example, in the above-mentioned applications, the heterocyclic ring-containing polymer precursor is used in the form of a curable resin composition containing the heterocyclic ring-containing polymer precursor. The curable resin composition can be applied to a substrate by, for example, coating, and then the heterocyclic ring-containing polymer precursor is cyclized by heating or the like, whereby a cured resin can be formed on the substrate. Since the curable resin composition can be applied by a known coating method or the like, the curable resin composition to be applied has excellent manufacturing adaptability, for example, such as a degree of freedom in design as a shape, a size, an application position, and the like. From the viewpoint of excellent production adaptability in addition to high performance of polyimide resins and the like, development of industrial application of curable resin compositions containing heterocyclic ring-containing polymer precursors is increasingly expected.

For example, patent document 1 describes a photosensitive resin composition containing a polyimide precursor, at least 1 polyimide resin, and at least 1 urethane (meth) acrylate having a specific structure.

Prior art documents

Patent document

Patent document 1: international publication No. 2017/131037

Disclosure of Invention

Technical problem to be solved by the invention

In the formation of a cured film obtained by curing a curable resin composition containing a heterocyclic ring-containing polymer precursor such as a polyimide precursor, for example, when a laminate is produced by further applying and curing the curable resin composition to the cured film, the cured film may come into contact with a developer or another composition.

Therefore, among the curable resin compositions, it is desired to provide a curable resin composition having excellent chemical resistance of the obtained cured film, from the viewpoints of resistance to a developer, suppression of dissolution due to contact with another composition, and the like.

In addition, it is desired to provide a curable resin composition having excellent elongation at break in a cured film obtained by curing a curable resin composition containing a heterocyclic ring-containing polymer precursor.

An object of the present invention is to provide a curable resin composition with which an obtained cured film is excellent in chemical resistance and elongation at break, a cured film obtained by curing the curable resin composition, a laminate comprising the cured film, a method for producing the cured film, and a semiconductor device comprising the cured film or the laminate.

Means for solving the technical problem

Hereinafter, examples of representative embodiments of the present invention will be described.

< 1 > a curable resin composition comprising:

a polymer precursor which is at least 1 selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor; and

a polymerizable compound having a hydrogen-bonding nitrogen atom and having a group containing 2 or more ethylenically unsaturated groups,

the composition has a radical polymerizable group valence of 0.25 to 4.35mmol/g, relative to the total solid content of the composition, derived from a compound having a radical polymerizable group with a molecular weight of 2,000 or less.

< 2 > the curable resin composition of < 1 >, wherein the polymerizable compound comprises a structure A as a structure containing the hydrogen-bonding nitrogen atom, and the structure A is at least 1 structure selected from the group consisting of a urethane bond, a urea bond and an amide bond.

< 3 > the curable resin composition of < 2 >, wherein the polymerizable compound comprises a structure B, and the structure B is a structure in which at least 1 bonding site in the structure A is directly bonded to an alkylene group.

< 4 > a curable resin composition comprising:

a polymer precursor which is at least 1 selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor; and

a polymerizable compound having a urea bond or an amide bond and having a group containing 2 or more ethylenically unsaturated groups.

The curable resin composition according to any one of < 5 > to < 1 > - < 4 >, wherein the polymerizable compound contains a (meth) acryloyl group as the group containing the ethylenically unsaturated group.

The curable resin composition of any one of < 6 > to < 1 > -5 >, wherein the polymerizable compound has a molecular weight of 200 to 1,000.

The curable resin composition of any one of < 7 > to < 6 >, which further comprises a photo radical polymerization initiator.

The curable resin composition of any one of < 8 > to < 7 >, which further comprises an onium salt or a thermal alkali generator.

The curable resin composition of any one of < 9 > to < 1 > -to < 8 > comprising a polyimide precursor as the polymer precursor.

< 10 > and < 9 >, wherein the polyimide precursor has a repeating unit represented by the following formula (1),

[ chemical formula 1]

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

< 11 > and < 10 > of the curable resin composition, wherein R of the formula (1)¹¹³And R¹¹⁴At least 1 of them contains a radical polymerizable group.

< 12 > the curable resin composition, which is used for forming an interlayer insulating film for a rewiring layer, is as defined in any one of < 1 > to < 11 >.

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

< 14 > a laminate comprising 2 or more layers of the cured films < 13 > comprising a metal layer between any of the above cured films.

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

The method for producing a cured film described in < 16 > or < 15 > includes an exposure step of exposing the film and a development step of developing the film.

The method for producing a cured film of < 17 > such as < 15 > or < 16 > comprises a heating step of heating the film at 50 to 450 ℃.

< 18 > a semiconductor device comprising < 13 > said cured film or < 14 > said laminate.

Effects of the invention

According to the present invention, there are provided a curable resin composition with which the obtained cured film is excellent in chemical resistance and elongation at break, a cured film obtained by curing the curable resin composition, a laminate comprising the cured film, a method for producing the cured film, and a semiconductor device comprising the cured film 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 embodiments shown.

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

The term "step" in the present specification means not only an independent step but also a step which cannot be clearly distinguished from other steps as long as the required action of the step can be achieved.

With regard to the labeling of the group (atomic group) in the present specification, the label which is not labeled with substituted and unsubstituted includes both a group (atomic group) having no substituent and a group (atomic group) having a substituent. For example, "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present specification, the term "exposure" includes, unless otherwise specified, exposure using a particle beam such as an electron beam or an ion beam, in addition to exposure using light. Examples of the light used for exposure include actinic rays or radiation such as a bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer laser light, extreme ultraviolet rays (EUV light), X-rays, and electron beams.

In the present specification, "(meth) acrylate" means both or 1 of "acrylate" and "methacrylate", "meth (acrylic acid)" means both or 1 of "acrylic acid" and "methacrylic acid", and "(meth) acryl" means both or 1 of "acryl" and "methacryl".

In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

In the present specification, the total solid content means the total mass of the components excluding the solvent from the total components of the composition. In the present specification, the solid content concentration is a mass percentage of the other components except 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 based on gel permeation chromatography (GPC measurement) and defined as polystyrene equivalent values. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined by using, for example, HLC-8220GPC (TOSOH CORPORATION), and using protective columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000(TOSOH CORPORATION), as columns. Unless otherwise specified, a solution measured using THF (tetrahydrofuran) was used as an eluent. Unless otherwise specified, a 254nm wavelength detector for UV rays (ultraviolet rays) is used for detection in GPC measurement.

In the present specification, when the positional relationship of each layer constituting the laminate is described as "upper" or "lower", the other layer may be present on the upper side or the lower side of the reference layer in the concerned multilayer. That is, the 3 rd layer or the 3 rd element may be further interposed between the layer serving as the reference and the other layer, and the layer serving as the reference and the other layer do not need to be in contact. Unless otherwise specified, the direction in which the layers are stacked on the substrate is referred to as "up", or, when the photosensitive layer is present, the direction from the substrate toward the photosensitive layer is referred to as "up", and the opposite direction is referred to as "down". Note that these vertical directions are set for convenience in the present specification, and in an actual embodiment, the "up" direction in the present specification may be different from the vertical direction.

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

In the present specification, the physical property values are values under the conditions of a temperature of 23 ℃ and a gas pressure of 101,325Pa (1 gas pressure), unless otherwise specified.

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

(curable resin composition)

In a first aspect of the curable resin composition of the present invention, the curable resin composition comprises at least 1 polymer precursor (heterocyclic ring-containing polymer precursor) selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, and a polymerizable compound (hereinafter, also referred to as "specific polymerizable compound 1") having a hydrogen-bonding nitrogen atom and having a group containing 2 or more ethylenically unsaturated groups, and the radical polymerizable group valence of the compound derived from a radical polymerizable group having a molecular weight of 2,000 or less with respect to the total solid content of the composition is 0.25 to 4.35 mmol/g.

In the second embodiment of the curable resin composition of the present invention, the curable resin composition contains at least 1 polymer precursor (heterocyclic ring-containing polymer precursor) selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, and a polymerizable compound having a urea bond or an amide bond and having a group containing 2 or more ethylenically unsaturated groups (hereinafter, also referred to as "specific polymerizable compound 2").

Hereinafter, the curable resin compositions in the first and second embodiments of the curable resin composition of the present invention are also simply and collectively referred to as "curable resin compositions", and the specific polymerizable compound 1 and the specific polymerizable compound 2 are simply and collectively referred to as "specific polymerizable compounds".

The curable resin composition of the present invention preferably further contains a photo radical polymerization initiator described later.

The cured film obtained from the curable resin composition of the present invention is excellent in chemical resistance and elongation at break.

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

For example, when a curable resin composition containing a heterocyclic ring-containing polymer precursor is heated, a cured film containing a polyimide resin or a polybenzoxazole resin can be obtained by cyclization of the precursor.

Among them, it is considered to further introduce a compound having an ethylenically unsaturated group in order to improve the chemical resistance of the cured film.

However, as a result of intensive studies, the present inventors have found that when a conventional ethylenically unsaturated compound is used, for example, in curing at a low temperature of 200 ℃ or lower, cyclization of the heterocyclic ring-containing polymer precursor is suppressed and the chemical resistance is improved in the obtained cured film, but the elongation at break is reduced, for example, when the radical polymerizable group derived from a compound having a radical polymerizable group with a molecular weight of 2,000 or less is expensive (for example, more than 4.35mmol/g) relative to the total solid content of the composition.

Thus, it is difficult to achieve both chemical resistance and elongation at break in the cured film obtained.

Accordingly, the present inventors have found that a cured film having excellent chemical resistance and elongation at break can be obtained by using a specific polymerizable compound 1 having a hydrogen-bonding nitrogen atom and a double bond in a composition and having a radical polymerizable group valence of 0.25 to 4.35mmol/g or a specific polymerizable compound 2 having a urea bond or an amide bond and having a group containing 2 or more ethylenically unsaturated groups.

This is presumably because strong films are formed by bonding the specific polymerizable compounds after crosslinking with each other or the specific polymerizable compounds after crosslinking with a polyimide resin, a polybenzoxazole resin, or the like, and hydrogen.

Further, it is considered that the curable resin composition of the present invention is easily excellent in the lithography property by using the specific polymerizable compound 2 having a radical polymerizable group valence of 0.25mol/g or more or having a urea bond or an amide bond.

Among them, patent document 1 neither describes nor suggests a curable resin composition containing a specific polymerizable compound 1 and having a radical polymerizable group valence of 0.25 to 4.35mmol/g, and a curable resin composition containing a specific polymerizable compound 2. In the curable resin composition of patent document 1, there is room for further improvement in chemical resistance of a cured film of the curable resin composition.

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

In the first and second embodiments of the curable resin composition of the present invention, the components other than the specific polymerizable compound contained in the composition and the composition or physical properties other than the radical polymerizable group valence described above are the same, and preferred embodiments thereof are the same.

< heterocyclic ring-containing Polymer precursor >

The curable resin composition of the present invention contains a heterocyclic ring-containing polymer precursor.

The curable resin composition of the present invention contains at least 1 precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors, preferably polyimide precursors, as the heterocyclic ring-containing polymer precursors.

[ polyimide precursor ]

The polyimide precursor preferably has a repeating unit represented by the following formula (1) from the viewpoint of the film strength of the obtained cured film.

[ chemical formula 2]

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

-A¹And A²-

A in the formula (1)¹And A²Each independently represents an oxygen atom or-NH-, preferably an oxygen atom.

-R¹¹¹-

R in the formula (1)¹¹¹Represents a 2-valent organic group. Examples of the 2-valent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, and a combination of 2 or more of these groups, 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, or a combination of 2 or more of these groups, and more preferably an aromatic group having 6 to 20 carbon atoms.

R in the formula (1)¹¹¹Preferably derived from a diamine. The diamine used for producing the polyimide precursor includes linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. The diamine may be used in an amount of 1 or more than 2.

Specifically, the diamine preferably contains a linear aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination of these groups in 2 or more, and more preferably contains an aromatic group having 6 to 20 carbon atoms. Examples of the aromatic group include the following aromatic groups.

[ chemical formula 3]

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

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

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

[ chemical formula 4]

[ chemical formula 5]

Further, preferred examples thereof include diamines having at least 2 alkylene glycol units in the main chain. The diamine containing 2 or more ethylene glycol chains or propylene glycol chains, or 1 or both of them, is preferably combined in one molecule, and a diamine containing no aromatic ring is more preferred. Specific examples thereof include JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (trade names shown above, manufactured by HUNTSMAN Co., Ltd.), 1- (2- (2-aminopropoxy) ethoxy) propoxy) propan-2-amine, and 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propan-2-amine, but the present invention is not limited thereto.

The following shows the structures of JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, and JEFFAMINE (registered trademark) EDR-176.

[ chemical formula 6]

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

R in the formula (1) is from the viewpoint of flexibility of the obtained cured film¹¹¹Preferably from-Ar⁰-L⁰-Ar⁰-represents. Ar (Ar)⁰Each independently an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 10 carbon atoms), preferably a phenylene group. L is⁰Represents a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C (═ O) -, -S-, -S (═ O)₂-, -NHCO-or a combination of these 2 or more groups. L is⁰The preferred ranges of (A) have the same meanings as those of (A) described above.

R in the formula (1) from the viewpoint of i-ray transmittance¹¹¹The 2-valent organic group represented by the following formula (51) or formula (61) is preferable. In particular, from the viewpoint of i-ray transmittance and ready availability, the 2-valent organic group represented by formula (61) is more preferable.

[ chemical formula 7]

In the formula (51), R⁵⁰～R⁵⁷Each independently is a hydrogen atom, a fluorine atom or a 1-valent organic group, R⁵⁰～R⁵⁷At least 1 of them is a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group, each independently represents a bonding site with another structure.

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

[ chemical formula 8]

In formula (61), R⁵⁸And R⁵⁹Each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group.

Examples of the diamine compound to which the structure of formula (51) or (61) is imparted include dimethyl-4, 4 '-diaminobiphenyl, 2' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl, 2' -bis (fluoro) -4,4 '-diaminobiphenyl, 4' -diaminooctafluorobiphenyl, and the like. One of these may be used 1 or 2 or more may be used in combination.

-R¹¹⁵-

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

[ chemical formula 9]

R¹¹²The meaning of (A) is the same as that of A, and the preferable range is the same. Each independently represents a bonding site with another structure.

With respect to R in the formula (1)¹¹⁵Specific examples of the 4-valent organic group include tetracarboxylic acid residues remaining after removal of the acid dianhydride group from the tetracarboxylic acid dianhydride. The tetracarboxylic dianhydride may be used in only 1 kind or in 2 or more kinds. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).

[ chemical formula 10]

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

Specific examples of the tetracarboxylic acid dianhydride include those selected from the group consisting of pyromellitic acid, pyromellitic acid dianhydride (PMDA), 3,3 ', 4,4 ' -biphenyltetracarboxylic acid dianhydride, 3,3 ', 4,4 ' -diphenylsulfide tetracarboxylic acid dianhydride, 3,3 ', 4,4 ' -diphenylsulfone tetracarboxylic acid dianhydride, 3,3 ', 4,4 ' -benzophenonetetracarboxylic acid dianhydride, 3,3 ', 4,4 ' -diphenylmethane tetracarboxylic acid dianhydride, 2 ', 3,3 ' -diphenylmethane tetracarboxylic acid dianhydride, 2,3,3 ', 4 ' -biphenyltetracarboxylic acid dianhydride, 2,3,3 ', 4 ' -benzophenonetetracarboxylic acid dianhydride, 4,4 ' -oxydiphthalic acid dianhydride, 2,3,6, 7-naphthalenetetracarboxylic acid dianhydride, 1,4,5, 7-naphthalenetetracarboxylic acid dianhydride, 1,4, 7-naphthalenetetracarboxylic acid dianhydride, and mixtures thereof, 2, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 1, 3-diphenylhexafluoropropane-3, 3,4, 4-tetracarboxylic dianhydride, 1,4,5, 6-naphthalenetetracarboxylic dianhydride, 2 ', 3, 3' -diphenyltetracarboxylic dianhydride, 3,4,9, 10-perylenetetracarboxylic dianhydride, 1,2,4, 5-naphthalenetetracarboxylic dianhydride, 1,4,5, 8-naphthalenetetracarboxylic dianhydride, 1,8,9, 10-phenanthrenetetracarboxylic dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 1,2,3, 4-benzenetetracarboxylic dianhydride, and at least 1 of alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

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

[ chemical formula 11]

-R¹¹³And R¹¹⁴-

R in the formula (1)¹¹³And R¹¹⁴Each independently represents a hydrogen atom or a 1-valent organic group. Preferably R¹¹³And R¹¹⁴At least 1 of them contains a radical polymerizable group, and more preferably both contain a radical polymerizable group. The radical polymerizable group is a group capable of undergoing a crosslinking reaction by the action of a radical, and preferable examples thereof include a group containing an ethylenically unsaturated bond.

Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth) acryloyl group, a group represented by the following formula (III), and the like.

[ chemical formula 12]

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

In the formula (III), R²⁰¹Represents a carbon number of 2E to EAlkylene of 12, -CH₂CH(OH)CH₂Or a (poly) oxyalkylene group having 4 to 30 carbon atoms (as an alkylene group, the number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, particularly preferably 1 to 3; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, particularly preferably 1 to 3). Further, (poly) oxyalkylene represents oxyalkylene or polyoxyalkylene.

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

Particularly preferred is R²⁰⁰Is methyl, R²⁰¹Is an ethylene group.

In formula (III), a represents a bonding site with another structure.

As a preferred embodiment of the polyimide precursor in the present invention, R is¹¹³Or R¹¹⁴Examples of the 1-valent organic group in (1) include an aliphatic group, an aromatic group, an aralkyl group and the like having 1,2 or 3 acid groups, preferably 1 acid group. Specifically, the aromatic group has 6 to 20 carbon atoms and has an acid group, and the aralkyl group has 7 to 25 carbon atoms and has an acid group. More specifically, a phenyl group having an acid group and a benzyl group having an acid group are exemplified. The acid group is preferably a hydroxyl group. Namely, R¹¹³Or R¹¹⁴Groups having a hydroxyl group are preferred.

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

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

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

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

Specific examples of the aromatic group include a substituted or unsubstituted aromatic hydrocarbon group (examples of the cyclic structure of the constituent group include a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indene ring, a perylene ring, a pentacene ring, an acenaphthylene ring, a phenanthrene ring, an anthracene ring, a tetracene ring, a,A ring, a triphenylene ring, etc.) or a substituted or unsubstituted aromatic heterocyclic group (a cyclic structure as a constituent group, a fluorene ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an indolizine ring, an indole ring, a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinazoline ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, a thianthrene ring, a benzopyran ring, a perimidine ring, a phenothiazine ring, or a phenothiazine ring).

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

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

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

[ chemical formula 13]

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

A¹¹、A¹²、R¹¹¹、R¹¹³And R¹¹⁴The meanings of the preferred ranges of (A) and (B) are respectively the same as those of A in the formula (1)¹、A²、R¹¹¹、R¹¹³And R¹¹⁴The preferred ranges of (a) and (b) are the same.

R¹¹²With R in the formula (5)¹¹²Among them, oxygen atom is more preferable.

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

In the polyimide precursor, the number of the repeating units represented by the formula (1) may be 1 or 2 or more. And may contain structural isomers of the repeating unit represented by formula (1). The polyimide precursor may contain other kinds of repeating units in addition to the repeating unit of the above formula (1).

An embodiment of the polyimide precursor of the present invention is a polyimide precursor having a repeating unit represented by formula (1) in an amount of 50 mol% or more, more preferably 70 mol% or more, and particularly 90 mol% or more of the total repeating unit. The upper limit is actually 100 mol% or less.

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

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

In the present specification, the degree of dispersion of molecular weights means a value obtained by dividing a weight average molecular weight by a number average molecular weight (weight average molecular weight/number average molecular weight).

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

In the method for producing a polyimide precursor, an organic solvent is preferably used when the reaction is carried out. The number of the organic solvents may be 1 or 2 or more.

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

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

[ polybenzoxazole precursor ]

The polybenzoxazole precursor preferably contains a repeating unit represented by the following formula (2).

[ chemical formula 14]

In the formula (2), R¹²¹Represents a 2-valent organic group, R¹²²Represents a 4-valent organic group, R¹²³And R¹²⁴Each independently represents a hydrogen atom or a 1-valent organic group.

-R¹²¹-

In the formula (2), R¹²¹Represents a 2-valent organic group. The 2-valent organic group preferably contains at least 1 of an aliphatic group (preferably 1 to 24, more preferably 1 to 12, and particularly preferably 1 to 6 carbon atoms) and an aromatic group (preferably 6 to 22, more preferably 6 to 14, and particularly preferably 6 to 12 carbon atoms). As a constituent R¹²¹Examples of the aromatic group of (3) include R of the above formula (1)¹¹¹Examples of (3). The aliphatic group is preferably a straight chain aliphatic group. R¹²¹Preferably from 4, 4' -oxodibenzoyl chloride.

-R¹²²-

In the formula (2), R¹²²Represents a 4-valent organic group. As the 4-valent organic group, the same as R in the above formula (1)¹¹⁵Similarly, the preferred ranges are also the same. R¹²²Preferably from 2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane.

-R¹²³And R¹²⁴-

R¹²³And R¹²⁴Each independently represents a hydrogen atom or a 1-valent organic group having the same meaning as R in the above formula (1)¹¹³And R¹¹⁴Similarly, the preferred ranges are also the same.

The polybenzoxazole precursor may contain other kinds of repeating units in addition to the repeating unit of the above formula (2).

From the viewpoint of being able to suppress warpage of the cured film that occurs with ring closure, the polybenzoxazole precursor preferably further contains a diamine residue represented by the following formula (SL) as another type of repeating unit.

[ chemical formula 15]

Z has a structure a and a structure b, R^1sIs a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), R^2sIs a C1-10 hydrocarbon group (preferably C1-6, more preferably C1-3), R^3s、R^4s、R^5s、R^6sAt least 1 of them is an aromatic group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, particularly preferably having 6 to 10 carbon atoms), and the remainder is a hydrogen atom or an organic group having 1 to 30 carbon atoms (preferably having 1 to 18 carbon atoms, more preferably having 1 to 12 carbon atoms, particularly preferably having 1 to 6 carbon atoms), and may be the same or different. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. In the Z portion, the a structure is preferably 5 to 95 mol%, the b structure is preferably 95 to 5 mol%, and a + b is preferably 100 mol%.

In the formula (SL), preferable Z is R in the structure of b^5sAnd R^6sIs phenyl. The molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. The molecular weight can be determined by gel permeation chromatography which is generally used. By setting the molecular weight in the above range, the effect of reducing the elastic modulus of the polybenzoxazole precursor after dehydration ring closure and suppressing warpage and the effect of improving solubility can be both achieved.

When the polybenzoxazole precursor contains a diamine residue represented by the formula (SL) as another kind of repeating unit, it is more preferable to contain a tetracarboxylic acid residue remaining after removing an acid dianhydride group from a tetracarboxylic dianhydride as a repeating unit, from the viewpoint of improving the alkali solubility of the curable resin composition. Examples of such tetracarboxylic acid residues include R in the formula (1)¹¹⁵Examples of (3).

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

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

The content of the heterocyclic ring-containing polymer precursor in the curable resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, further preferably 50% by mass or more, further preferably 60% by mass or more, and further preferably 70% by mass or more, based on the total solid content of the curable resin composition. The content of the heterocyclic ring-containing polymer precursor in the curable resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, further preferably 97% by mass or less, and further preferably 95% by mass or less, based on the total solid content of the curable resin composition.

The curable resin composition of the present invention may contain only 1 kind of the heterocycle-containing polymer precursor, or may contain 2 or more kinds. When 2 or more species are contained, the total amount is preferably within the above range.

< specific polymerizable Compound 1 >

In a first aspect of the curable resin composition of the present invention, the composition comprises a polymerizable compound (specific polymerizable compound 1) having a hydrogen-bonding nitrogen atom and having a group containing 2 or more ethylenically unsaturated groups, and the radical polymerizable group valence of the compound derived from a radical polymerizable group having a molecular weight of 2,000 or less with respect to the total solid content of the composition is 0.25 to 4.35 mmol/g.

[ radical polymerizable group valence ]

The radical polymerizable group valence derived from the compound having a radical polymerizable group with a molecular weight of 2,000 or less with respect to the total solid content of the composition means the amount (mol amount) of the ethylenically unsaturated group contained in the compound having a radical polymerizable group with a molecular weight of 2,000 or less with respect to the total solid content of the composition.

The radical polymerizable group valence can be calculated, for example, from the structure determination by separation of a compound having a radical polymerizable group with a molecular weight of 2,000 or less and the measurement of the concentration in a composition by chromatography or the like.

The radical polymerizable group valence is preferably 0.25 to 4.35mmol/g, more preferably 0.50 to 3.50 mol/g.

[ ethylenically unsaturated group ]

Examples of the ethylenically unsaturated group contained in the specific polymerizable compound 1 include a vinyl group, an allyl group, a vinylphenyl group, a (meth) acryloyl group, and the like, and a (meth) acryloyl group is preferable, and a (meth) acryloyloxy group is more preferable from the viewpoint of reactivity.

The number of ethylenic unsaturations contained in the specific polymerizable compound 1 may be 2 or more, more preferably 2 to 8, and still more preferably 2 to 6.

The molar amount (mol/g) of the ethylenically unsaturated group in 1g of the specific polymerizable compound 1 is preferably 0.004 to 0.015mol/g, and more preferably 0.005 to 0.012 mol/g.

[ hydrogen-bonded nitrogen atom ]

The hydrogen-bonding nitrogen atom contained in the specific polymerizable compound 1 is not particularly limited, and examples thereof include a urethane bond (-O-C (═ O) -NR)^N-), urea linkage (-NR)^N-C(＝O)-NR^N-), amide bond (-C (-O) -NR)^N-), amino (-NR)^N-), sulfonamide linkage (-S (═ O)₂NR^N-), nitrogen atoms contained in nitrogen-containing heterocyclic structures, etc. R^NRepresents a hydrogen atom or a hydrocarbon group, preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and still more preferably a hydrogen atom. R^NWhen there are plural in the molecule, plural R^NMay be the same or different.

The specific polymerizable compound 1 preferably contains a structure a of at least 1 structure selected from the group consisting of a urethane bond, a urea bond, and an amide bond as a structure containing a hydrogen-bonding nitrogen atom.

Further, from the viewpoint of improving the elongation at break, the specific polymerizable compound 1 preferably includes a urethane bond as a structure containing a hydrogen-bonded nitrogen atom, and from the viewpoint of improving the chemical resistance, the specific polymerizable compound 1 preferably includes at least 1 structure selected from the group consisting of a urea bond and an amide bond as a structure containing a hydrogen-bonded nitrogen atom.

The number of hydrogen-bonded nitrogen atoms in the specific polymerizable compound 1 is preferably 2 to 6, more preferably 2 to 4.

Further, the specific polymerizable compound 1 preferably contains a structure B in which at least 1 bonding site in the structure a is directly bonded to an alkylene group.

The alkylene group is preferably an alkylene group having 2 to 15 carbon atoms, and more preferably an alkylene group having 2 to 10 carbon atoms. The alkylene group may have a branched structure or a cyclic structure.

[ specific polymerizable Compound 1 having urethane bond ]

The specific polymerizable compound 1 containing a urethane bond is preferably a compound represented by the following formula (UA-1) or formula (UA-2).

[ chemical formula 16]

In formula (UA-1) or formula (UA-2), L^A1A linking group representing the valence of nA, L^A2Each independently represents a mA +1 valent linking group, R^A1Each independently represents a group containing an ethylenically unsaturated group, nA represents an integer of 2 or more, and mA represents an integer of 1 or more.

In formula (UA-1) or formula (UA-2), L^A1Preferably a nA-valent hydrocarbon group, more preferably a nA-valent aliphatic saturated hydrocarbon group, a nA-valent aromatic hydrocarbon group, or a nA-valent group represented by a combination of an aliphatic saturated hydrocarbon group and an aromatic hydrocarbon group.

In formula (UA-1) or formula (UA-2), L^A2Preferred are hydrocarbon groups, ester bonds (-C (═ O) O-), ether bonds (-O-), carbonyl groups (-C (═ O) -), and carbamate bonds (-O-C (═ O) -NR^N-), urea linkage (-NR)^N-C(＝O)-NR^N-), amide bond (-C (-O) -NR)^N-), amino (-NR)^N-) or a combination of 2 or more of these groups, more preferably an aliphatic saturated hydrocarbon group, an aromatic hydrocarbon group, an ester bond, an ether bond or a combination of 2 or more of these groups。R^NAs described above.

In the formula (UA-1) or formula (UA-2), R^A1Preferred is a vinyl group, an allyl group, a vinylphenyl group, a (meth) acrylamido group or a (meth) acryloyloxy group, and more preferred is a (meth) acryloyloxy group.

In the formula (UA-1) or (UA-2), nA represents an integer of 2 or more, preferably 2 to 10, more preferably 2 to 6, further preferably 2 to 4, and particularly preferably 2.

In the formula (UA-1) or the formula (UA-2), mA is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, particularly preferably 1 or 2, most preferably 1.

[ specific polymerizable Compound 1 having Urea bond ]

The specific polymerizable compound 1 containing a urea bond is preferably a compound represented by the following formula (UB-1).

[ chemical formula 17]

In formula (UB-1), L^B1A linking group representing a valence of nB, L^B2Each independently represents a mB +1 valent linking group, R^B1Each independently represents a group containing an ethylenically unsaturated group, nB represents an integer of 2 or more, and mB represents an integer of 1 or more.

In formula (UB-1), L^B1Preferably nB-valent hydrocarbon group, more preferably nB-valent aliphatic saturated hydrocarbon group, nB-valent aromatic hydrocarbon group or by aliphatic saturated hydrocarbon group and aromatic hydrocarbon group combination representation of nB-valent group.

In formula (UB-1), L^B2Preferred are hydrocarbon groups, ester bonds (-C (═ O) O-), ether bonds (-O-), carbonyl groups (-C (═ O) -), and carbamate bonds (-O-C (═ O) -NR^N-), urea linkage (-NR)^N-C(＝O)-NR^N-), amide bond (-C (-O) -NR)^N-), amino (-NR)^N-) or a combination of 2 or more of these groups, more preferably an aliphatic saturated hydrocarbon group, an aromatic hydrocarbon group, an ester bond, an ether bond or a combination of 2 or more of these groups. R^NAs described above.

In the formula (UB-1), R^B1Preferred is a vinyl group, an allyl group, a vinylphenyl group, a (meth) acrylamido group or a (meth) acryloyloxy group, and more preferred is a (meth) acryloyloxy group.

In the formula (UB-1), nB represents an integer of 2 or more, preferably 2 to 10, more preferably 2 to 6, further preferably 2 to 4, and particularly preferably 2.

In the formula (UB-1), mB is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, particularly preferably 1 or 2, most preferably 1.

[ specific polymerizable Compound 1 having an amide bond ]

The specific polymerizable compound 1 having an amide bond preferably contains 2 or more structures in total, i.e., a structure represented by the following formula (AM-1) and a structure represented by the following formula (AM-2).

[ chemical formula 18]

In the formulae (AM-1) and (AM-2), R^M1Represents a hydrogen atom or a methyl group, R^M2Each represents a hydrogen atom or a hydrocarbon group, and each independently represents a bonding site to another structure.

In the formulae (AM-1) and (AM-2), R^M1Preferably a hydrogen atom.

In the formula (AM-1), R^M2The hydrogen atom, the alkyl group or the aryl group is preferable, the hydrogen atom, the alkyl group having 1 to 8 carbon atoms or the phenyl group is more preferable, the hydrogen atom or the methyl group is further preferable, and the hydrogen atom is particularly preferable.

The specific polymerizable compound 1 containing an amide group is preferably a compound represented by the following formula (AM-3).

[ chemical formula 19]

In the formula (AM-3), R^M1Represents a hydrogen atom or a methyl group, R^M2Represents a hydrogen atom or a hydrocarbon group, L^M1Represents an n + 1-valent organic group, n representsDenotes an integer of 1 or more, and L is 1^M1Having a group containing an ethylenically unsaturated group.

In the formula (AM-3), R^M1Preferably a hydrogen atom.

In the formula (AM-3), R^M2The hydrogen atom, the alkyl group or the aryl group is preferable, the hydrogen atom, the alkyl group having 1 to 8 carbon atoms or the phenyl group is more preferable, the hydrogen atom or the methyl group is further preferable, and the hydrogen atom is particularly preferable.

In the formula (AM-3), L^M1Represents an n-valent organic group, preferably a hydrocarbon group, an ester bond (-C (═ O) O-), an ether bond (-O-), a carbonyl group (-C (═ O) -), and a urethane bond (-O-C (═ O) -NR)^N-), urea linkage (-NR)^N-C(＝O)-NR^N-), amide bond (-C (-O) -NR)^N-), amino (-NR)^N-) or a structure represented by the formula (AM-2) or a combination of 2 or more of these groups, and more preferably an aliphatic saturated hydrocarbon group, an aromatic hydrocarbon group, an ester bond, an ether bond, a structure represented by the formula (AM-2) or a combination of 2 or more of these groups. R^NAs described above.

n is preferably 2 to 10, more preferably 2 to 6, and further preferably 2 to 4.

When n is 1, L^M1Has a group containing an ethylenically unsaturated group, preferably contains a structure represented by the above formula (AM-2).

Further, from the viewpoint of further improving the elongation at break of the cured film obtained, and the like, the specific polymerizable compound 1 containing an amide group is also preferably a compound represented by the following formula (AM-4) or formula (AM-5).

[ chemical formula 20]

In the formula (AM-4) or the formula (AM-5), L^B1A linking group representing a valence of nB, L^B2Each independently represents a mB +1 valent linking group, R^B1Each independently represents a group containing an ethylenically unsaturated group, nB represents an integer of 2 or more, and mB represents an integer of 1 or more.

In the formula (AM-4) or the formula (AM-5), L^B1Preferably nB-valent hydrocarbon group, more preferably nB-valent aliphatic saturated hydrocarbon group, nB-valent aromatic hydrocarbon group or by aliphatic saturated hydrocarbon group and aromatic hydrocarbon group combination representation of nB-valent group.

In the formula (AM-4) or the formula (AM-5), L^B2Preferred are hydrocarbon groups, ester bonds (-C (═ O) O-), ether bonds (-O-), carbonyl groups (-C (═ O) -), and carbamate bonds (-O-C (═ O) -NR^N-), urea linkage (-NR)^N-C(＝O)-NR^N-), amide bond (-C (-O) -NR)^N-), amino (-NR)^N-) or a combination of 2 or more of these groups, more preferably an aliphatic saturated hydrocarbon group, an aromatic hydrocarbon group, an ester bond, an ether bond or a combination of 2 or more of these groups. R^NAs described above.

In the formula (AM-4) or the formula (AM-5), R^B1Preferred is a vinyl group, an allyl group, a vinylphenyl group, a (meth) acrylamido group or a (meth) acryloyloxy group, and more preferred is a (meth) acryloyloxy group.

In the formula (AM-4) or the formula (AM-5), nB represents an integer of 2 or more, preferably 2 to 10, more preferably 2 to 6, further preferably 2 to 4, particularly preferably 2 or 3.

In the formula (AM-4) or the formula (AM-5), mB is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, particularly preferably 1 or 2, most preferably 1.

[ molecular weight ]

The molecular weight (weight average molecular weight when having a molecular weight distribution) of the specific polymerizable compound 1 is preferably 200 to 1,000, more preferably 260 to 800, and further preferably 265 to 765.

[ specific examples ]

Specific examples of the specific polymerizable compound 1 include, but are not limited to, compounds having the following structures.

[ chemical formula 21]

[ chemical formula 22]

[ Synthesis method ]

The method for synthesizing the specific polymerizable compound 1 is not particularly limited, and the compound may be synthesized by a known method.

The specific polymerizable compound 1 containing a urethane bond can be obtained by, for example, reacting a polyisocyanate compound with a compound having a hydroxyl group and an ethylenically unsaturated group. Further, another synthesis method can be obtained by, for example, reacting a polyol compound with a compound having an isocyanate group and an ethylenically unsaturated group.

The specific polymerizable compound 1 having a urea bond can be obtained by, for example, reacting a polyisocyanate compound with a compound having an amino group and an ethylenically unsaturated group.

The specific polymerizable compound 1 having an amide bond can be obtained by, for example, reacting a polyamine compound with an unsaturated carboxylic acid compound. Further, another synthesis method can be obtained by reacting a compound having an amino group and an ethylenically unsaturated group with a polycarboxylic acid halide compound, for example.

Further, as the specific polymerizable compound 1, a commercially available compound may be used.

[ content ]

The content of the specific polymerizable compound 1 is preferably more than 0 mass% and 60 mass% or less with respect to the total solid content of the composition in the first embodiment of the curable resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and still more preferably 30% by mass or less.

The specific polymerizable compound 1 may be used alone in 1 kind, or may be used in combination with 2 or more kinds. When 2 or more kinds are used simultaneously, the total amount is preferably in the above range.

< specific polymerizable Compound 2 >

In the second embodiment of the curable resin composition of the present invention, the composition includes a polymerizable compound (specific polymerizable compound 2) having a urea bond or an amide bond and having a group containing 2 or more ethylenically unsaturated groups.

[ ethylenically unsaturated group ]

Examples of the ethylenically unsaturated group contained in the specific polymerizable compound 2 include a vinyl group, an allyl group, a vinylphenyl group, a (meth) acryloyl group, and the like, and a (meth) acryloyl group is preferable, and a (meth) acryloyloxy group is more preferable from the viewpoint of reactivity.

The number of ethylenic unsaturations contained in the specific polymerizable compound 2 may be 2 or more, more preferably 2 to 8, and still more preferably 2 to 6.

The molar amount (mol/g) of the ethylenically unsaturated group in 1g of the specific polymerizable compound 2 is preferably 0.004 to 0.015mol/g, and more preferably 0.005 to 0.012 mol/g.

[ Urea bond or amide bond ]

The specific polymerizable compound 2 contains a urea bond (-NR)^N-C(＝O)-NR^N-) in the case of the specific polymerizable compound 2, the number of urea bonds is preferably 1 to 10, more preferably 2 to 6, and still more preferably 2 to 4. R^NAs described above.

The specific polymerizable compound 2 contains an amide bond (-NR)^NIn the case of — C (═ O) -), the number of amide bonds in the specific polymerizable compound 2 is preferably 1 to 10, more preferably 2 to 6, and still more preferably 2 to 4. R^NAs described above.

The specific polymerizable compound 2 having a urea bond includes the same compounds as those of the specific polymerizable compound 1 having a urea bond, and preferred embodiments and specific examples thereof are also the same.

The specific polymerizable compound 2 having an amide bond includes the same compounds as the specific polymerizable compound 1 having an amide bond, and preferred embodiments and specific examples thereof are also the same.

[ molecular weight ]

The molecular weight (weight average molecular weight when having a molecular weight distribution) of the specific polymerizable compound 2 is preferably 200 to 1,000, more preferably 200 to 800, and further preferably 260 to 600.

[ content ]

The content of the specific polymerizable compound 2 is preferably more than 0 mass% and 60 mass% or less with respect to the total solid content of the composition in the second embodiment of the curable resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and still more preferably 30% by mass or less.

The specific polymerizable compound 2 may be used alone in 1 kind, or may be used in combination of 2 or more kinds. When 2 or more kinds are used simultaneously, the total amount is preferably in the above range.

[ radical polymerizable group valence ]

When the composition contains the specific polymerizable compound 2, the radical polymerizable group valence of the compound derived from the radical polymerizable group having a molecular weight of 2,000 or less with respect to the total solid content of the composition is preferably 0.25mmol/g or more, more preferably 0.50mmol/g or more.

< onium salt >

The curable resin composition of the present invention preferably contains an onium salt.

The kind of onium salt is not particularly limited, and preferable examples thereof include ammonium salts, imine salts, sulfonium salts, iodine salts, and phosphonium salts.

Among them, ammonium salts and imine salts are preferable from the viewpoint of high thermal stability, and sulfonium salts, iodonium salts, and phosphonium salts are preferable from the viewpoint of compatibility with the polymer.

The onium salt is a salt of a cation having an onium structure and an anion, and the cation and the anion may be bonded to each other through a covalent bond or may not be bonded to each other through a covalent bond.

That is, the onium salt may be an intramolecular salt having a cation portion and an anion portion in the same molecular structure, or may be an intermolecular salt in which cation molecules and anion molecules of different molecules are ionically bonded, and an intermolecular salt is preferable. In the curable resin composition of the present invention, the cation portion or the cation molecule and the anion portion or the anion molecule may be bonded to each other by an ionic bond or may be dissociated from each other.

As the cation in the onium salt, an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation is preferable, and at least 1 kind of cation selected from the group consisting of a tetraalkylammonium cation, a sulfonium cation and an iodonium cation is more preferable.

The onium salt used in the present invention may also be a thermal alkali generator.

The thermal alkali generator is a compound which generates an alkali by heating, and examples thereof include an acidic compound which generates an alkali when heated to 40 ℃ or higher.

[ ammonium salt ]

In the present invention, the ammonium salt means a salt of an ammonium cation with an anion.

Ammonium cation-

As ammonium cation, quaternary ammonium cations are preferred.

Further, as the ammonium cation, a cation represented by the following formula (101) is preferable.

[ chemical formula 23]

In the formula (101), R¹～R⁴Each independently represents a hydrogen atom or a hydrocarbon group, R¹～R⁴At least 2 of which may be bonded to form a ring.

In the formula (101), R¹～R⁴Each independently is preferably a hydrocarbon group, more preferably an alkyl group or an aryl group, and still more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms. R¹～R⁴The substituent may be a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, or the like.

R¹～R⁴When at least 2 of the groups are bonded to form a ring, the ring may contain a hetero atom. Examples of the hetero atom include a nitrogen atom.

The ammonium cation is preferably represented by any 1 of the following formulae (Y1-1) to (Y1-2).

[ chemical formula 24]

In the formulae (Y1-1) and (Y1-2), R¹⁰¹Represents an n-valent organic group, R¹With R in the formula (101)¹Same as Ar¹⁰¹And Ar¹⁰²Each independently represents an aryl group, and n represents an integer of 1 or more.

In the formula (Y1-1), R¹⁰¹The aliphatic hydrocarbon, the aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from the bonded structure is preferable, and a saturated aliphatic hydrocarbon having 2 to 30 carbon atoms, or a group obtained by removing n hydrogen atoms from benzene or naphthalene is more preferable.

In the formula (Y1-1), n is preferably 1 to 4, more preferably 1 or 2, and further preferably 1.

In formula (Y1-2), Ar¹⁰¹And Ar¹⁰²Each independently is preferably phenyl or naphthyl, more preferably phenyl.

Anions-

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

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

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

[ chemical formula 25]

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

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

Examples of the substituent having a positive σ m include CF₃Base (. sigma.m.0.43), CF₃C (═ O) group (σ m ═ 0.63), HC ≡ C group (σ m ═ 0.21), CH ≡ C group₂CH (σ m) group (0.06), Ac (σ m) group (0.38), MeOC (O) group (σ m) 0.37), MeC (O) CH (CH) group (σ m) 0.21), PhC (O) group (σ m) 0.34), H₂NC(＝O)CH₂And a group (σ m ═ 0.06). In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (hereinafter, the same applies).

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

[ chemical formula 26]

In the formulae (EWG-1) to (EWG-6), R^x1～R^x3Each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group or a carboxyl group, and Ar represents an aromatic group.

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

[ chemical formula 27]

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

Specific examples of the carboxylate anion include maleate anion, phthalate anion, N-phenyliminodiacetate anion, and oxalate anion.

From the viewpoint that cyclization of the specific precursor is easily performed at a low temperature and storage stability of the curable resin composition is easily improved, the onium salt in the present invention preferably contains an ammonium cation as a cation and the onium salt contains an anion having a conjugate acid pka (pkah) of 2.5 or less as an anion, and more preferably contains an anion of 1.8 or less.

The lower limit of the pKa is not particularly limited, but is preferably-3 or more, more preferably-2 or more, from the viewpoint that the generated base is not easily neutralized and the cyclization efficiency of a specific precursor or the like is improved.

As the pKa, there can be referred to values described in the Determination of Organic Structures by Physical Methods (authors: Brown, H.C., McDaniel, D.H., Hafliger, O.A., Nachod, F.C.; authors: Braude, E.A., Nachod, F.C.; Academic Press, New York,1955) or Data for Biochemical Research (authors: Dawson, R.M.C. et; Oxford, Clarendon Press, 1959). As for the compounds not described in these documents, values calculated from the structural formulae using software using ACD/pKa (manufactured by ACD/Labs) were used.

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

[ chemical formula 28]

[ Iminium salt ]

In the present invention, an imide salt means a salt of an imide cation with an anion. Examples of the anion include the same anions as those in the ammonium salt, and preferred embodiments are also the same.

Imide cation-

As the imine cation, a pyridinium cation is preferable.

Further, as the imide cation, a cation represented by the following formula (102) is also preferable.

[ chemical formula 29]

In the formula (102), R⁵And R⁶Each independently represents a hydrogen atom or a hydrocarbon group, R⁷Represents a hydrocarbon group, R⁵～R⁷At least 2 of which may be bonded to form a ring.

In the formula (102), R⁵And R⁶Has the same meaning as R in the above formula (101)¹～R⁴Likewise, the preferred mode is the same.

In the formula (102), R⁷Preferably with R⁵And R⁶At least 1 of which is bonded to form a ring. The above rings may contain heteroatoms. Examples of the hetero atom include a nitrogen atom. The ring is preferably a pyridine ring.

The imide cation is preferably represented by any 1 of the following formulae (Y1-3) to (Y1-5).

[ chemical formula 30]

In the formulae (Y1-3) to (Y1-5), R¹⁰¹Represents an n-valent organic group, R⁵With R in the formula (102)⁵Same as R⁷With R in the formula (102)⁷Similarly, n and m represent an integer of 1 or more.

In the formula (Y1-3), R¹⁰¹The aliphatic hydrocarbon, the aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from the bonded structure is preferable, and a saturated aliphatic hydrocarbon having 2 to 30 carbon atoms, or a group obtained by removing n hydrogen atoms from benzene or naphthalene is more preferable.

In the formula (Y1-3), n is preferably 1 to 4, more preferably 1 or 2, and further preferably 1.

In the formula (Y1-5), m is preferably 1 to 4, more preferably 1 or 2, and further preferably 1.

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

[ chemical formula 31]

[ sulfonium salt ]

In the present invention, sulfonium salt means a salt of a sulfonium cation with an anion. Examples of the anion include the same anions as those in the ammonium salt, and preferred embodiments are also the same.

Sulfonium cation-

As the sulfonium cation, a tertiary sulfonium cation is preferable, and a triarylsulfonium cation is more preferable.

The sulfonium cation is preferably a cation represented by the following formula (103).

[ chemical formula 32]

In formula (103), R⁸～R¹⁰Each independently represents a hydrocarbon group.

R⁸～R¹⁰Each independently preferably represents an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, still more preferably an aryl group having 6 to 12 carbon atoms, and yet still more preferably a phenyl group.

R⁸～R¹⁰Examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, and the like. Among these, the substituent is preferably an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and still more preferably a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

R⁸～R¹⁰The groups may be the same or different, and from the viewpoint of synthetic compatibility, the same group is preferable.

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

[ chemical formula 33]

[ iodine salt ]

In the present invention, an iodonium salt means a salt of an iodonium cation with an anion. Examples of the anion include the same anions as those in the ammonium salt, and preferred embodiments are also the same.

Iodine cation-

As the iodonium cation, a diaryliodonium cation is preferable.

Further, as the iodonium cation, a cation represented by the following formula (104) is preferable.

[ chemical formula 34]

In the formula (104), R¹¹And R¹²Each independently represents a hydrocarbon group.

R¹¹And R¹²Each independently preferably represents an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, still more preferably an aryl group having 6 to 12 carbon atoms, and yet still more preferably a phenyl group.

R¹¹And R¹²The substituent may be a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, or the like. Among these, the substituent is preferably an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and still more preferably a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

R¹¹And R¹²The groups may be the same or different, and from the viewpoint of synthetic compatibility, the same group is preferable.

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

[ chemical formula 35]

[ phosphonium salt ]

In the present invention, phosphonium salts mean salts of phosphonium cations with anions. Examples of the anion include the same anions as those in the ammonium salt, and preferred embodiments are also the same.

Phosphonium cation-

The phosphonium cation is preferably a quaternary phosphonium cation, and examples thereof include a tetraalkylphosphonium cation, a triarylmonoalkylphosphonium cation and the like.

Further, as the phosphonium cation, a cation represented by the following formula (105) is preferable.

[ chemical formula 36]

In the formula (105), R¹³～R¹⁶Each independently represents a hydrogen atom or a hydrocarbon group.

R¹³～R¹⁶Each independently preferably represents an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, still more preferably an aryl group having 6 to 12 carbon atoms, and yet still more preferably a phenyl group.

R¹³～R¹⁶The substituent may be a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, or the like. Among these, the substituent is preferably an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and still more preferably a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

R¹³～R¹⁶The groups may be the same or different, and from the viewpoint of synthetic compatibility, the same group is preferable.

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

[ chemical formula 37]

When the curable resin composition of the present invention contains an onium salt, the content of the onium salt is preferably 0.1 to 50% by mass based on the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, still more preferably 0.85% by mass or more, and still more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, still more preferably 20% by mass or less, still more preferably 10% by mass or less, and may be 5% by mass or less, or may be 4% by mass or less.

The onium salt may be used in 1 species or 2 or more species. When 2 or more species are used, the total amount is preferably within the above range.

< thermal alkali production agent >

The curable resin composition of the present invention may contain a thermal alkali generator.

The thermal alkali-producing agent may be a compound corresponding to the onium salt, or may be a thermal alkali-producing agent other than the onium salt.

Examples of the other thermal alkali-producing agent include nonionic thermal alkali-producing agents.

Examples of the nonionic thermoalcogenating agent include compounds represented by the formula (B1) or the formula (B2).

[ chemical formula 38]

In the formulae (B1) and (B2), Rb¹、Rb²And Rb³Each independently represents an organic group having no tertiary amine structure, a halogen atom or a hydrogen atom. Wherein, Rb is¹And Rb²Not both as hydrogen atoms. And, Rb¹、Rb²And Rb³None have a carboxyl group. In the present specification, the tertiary amine structure means a structure of a nitrogen atom having a valence of 3And 3 bonding bonds each covalently bonded to a carbon atom of the hydrocarbon system. Therefore, when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when an amide group is formed together with a nitrogen atom, the carbon atom is not limited thereto.

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

More specifically, Rb¹And Rb²Preferably a hydrogen atom, an alkyl group (preferably 1 to 24, more preferably 2 to 18, further preferably 3 to 12, carbon atoms), an alkenyl group (preferably 2 to 24, more preferably 2 to 18, further preferably 3 to 12, carbon atoms), an aryl group (preferably 6 to 22, more preferably 6 to 18, further preferably 6 to 10, carbon atoms) or an aralkyl group (preferably 7 to 25, more preferably 7 to 19, further preferably 7 to 12 carbon atoms). These groups may have a substituent in a range in which the effect of the present invention is exerted. Rb¹And Rb²May be bonded to each other to form a ring. As the ring to be formed, a 4 to 7-membered nitrogen-containing heterocyclic ring is preferable. In particular, Rb¹And Rb²The alkyl group is preferably 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, further preferably 3 to 12), more preferably a cycloalkyl group which may have a substituent (the number of carbon atoms is preferably 3 to 24, more preferably 3 to 18, further preferably 3 to 12), and still more preferably a cyclohexyl group which may have a substituent.

As Rb³Examples thereof include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, further preferably 2 to 6 carbon atoms), an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 12 carbon atoms), an aralkenyl group (preferably having 8 to 24 carbon atoms, more preferably 8 to 20 carbon atoms, further preferably 8 to 16 carbon atoms), an alkoxy group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 8 to 16 carbon atoms), and the likeMore preferably 3 to 12), an aryloxy group (preferably 6 to 22, more preferably 6 to 18, still more preferably 6 to 12 carbon atoms), or an aralkyloxy group (preferably 7 to 23, more preferably 7 to 19, still more preferably 7 to 12 carbon atoms). Among them, preferred cycloalkyl groups are (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms), aralkenyl groups, and aralkyloxy groups. Rb is in the range of exerting the effect of the present invention³May further have a substituent.

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 39]

In the formula, Rb¹¹And Rb¹²And Rb³¹And Rb³²Are each as defined for Rb in the formula (B1)¹And Rb²The same is true.

Rb¹³The alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 12 carbon atoms) may have a substituent within a range in which the effects of the present invention are exerted. Wherein, Rb is¹³Aralkyl groups are preferred.

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

Rb³⁵Is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, further preferably 3 to 8 carbon atoms), an aryl group(preferably 6 to 22, more preferably 6 to 18, further preferably 6 to 12 carbon atoms), an aralkyl group (preferably 7 to 23, more preferably 7 to 19, further preferably 7 to 12 carbon atoms), preferably an aryl group.

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

[ chemical formula 40]

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

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

Rb¹⁷The alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 12 carbon atoms), and among them, an aryl group is preferable.

The molecular weight of the nonionic thermal alkali-producing agent is preferably 800 or less, more preferably 600 or less, and still more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and still more preferably 300 or more.

Among the onium salts, specific examples of the compound as the thermal alkali-producing agent and specific examples of other thermal alkali-producing agents include the following compounds.

[ chemical formula 41]

[ chemical formula 42]

[ chemical formula 43]

The content of the thermal alkali generator is preferably 0.1 to 50% by mass based on the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less. The thermal alkali generator can be used in 1 or more than 2 kinds. When 2 or more species are used, the total amount is preferably within the above range.

< photopolymerization initiator >

The curable resin composition of the present invention preferably contains a photopolymerization initiator.

The photopolymerization initiator is preferably a photo radical polymerization initiator. The photo radical polymerization initiator is not particularly limited, and can be appropriately selected from known photo radical polymerization initiators. For example, a photo radical polymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferable. Also, it may be an active agent that produces some action with a photo-excited sensitizer and generates active radicals.

The photo radical polymerization initiator preferably contains at least 1 type of initiator having at least about 50L-mol in the range of about 300 to 800nm (preferably 330 to 500nm)^-1·cm^-1A compound having a molar absorptivity. The molar absorption coefficient of a compound can be measured by a known method. For example, it is preferable to perform measurement by an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer, manufactured by Varian corporation) at a concentration of 0.01g/L using an ethyl acetate solvent.

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

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

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

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

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

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

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

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

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

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

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

[ chemical formula 44]

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

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

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

From the viewpoint of exposure sensitivity, the photo radical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyldimethylketal 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, and 3-aryl-substituted coumarin compounds.

More preferred photo radical polymerization initiators are trihalomethyl oxazine compounds, α -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, acetophenone compounds, further preferably at least 1 compound selected from the group consisting of trihalomethyl triazine compounds, α -aminoketone compounds, oxime compounds, triarylimidazole dimers, benzophenone compounds, still further preferably metallocene compounds or oxime compounds are used, still further preferably oxime compounds are used.

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

[ chemical formula 45]

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

[ chemical formula 46]

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

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

When the photopolymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass, based on the total solid content of the curable resin composition of the present invention. The photopolymerization initiator may contain only 1 kind or 2 or more kinds. When 2 or more photopolymerization initiators are contained, the total amount thereof is preferably within the above range.

< thermal polymerization initiator >

As the polymerization initiator, the curable resin composition of the present invention may contain a thermal polymerization initiator, and particularly 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 a polymerization reaction of a compound having polymerizability. By adding the thermal radical polymerization initiator, the heterocyclic ring-containing polymer precursor can be cyclized, and the polymerization reaction of the heterocyclic ring-containing polymer precursor can be performed, so that a higher heat resistance can be achieved.

Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of Japanese patent application laid-open No. 2008-063554.

When the thermal radical polymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 5 to 15% by mass, based on the total solid content of the curable resin composition of the present invention. The thermal radical polymerization initiator may contain only 1 species or 2 or more species. When 2 or more thermal radical polymerization initiators are contained, the total amount thereof is preferably within the above range.

< other polymerizable Compound >

[ other radically polymerizable Compounds ]

The curable resin composition of the present invention preferably contains another polymerizable compound different from the specific polymerizable compound.

The compound contained in the specific polymerizable compound is not contained in the other polymerizable compound.

As the other polymerizable compound, a radical polymerizable compound can be used. The radical polymerizable compound is a compound having a radical polymerizable group. Examples of the radical polymerizable group include groups having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth) acryloyl group. The radical polymerizable group is preferably a (meth) acryloyl group, and more preferably a (meth) acryloyloxy group from the viewpoint of reactivity.

The number of radical polymerizable groups of the radical polymerizable compound may be 1 or 2 or more, and the radical polymerizable compound preferably has 2 or more radical polymerizable groups, and more preferably 3 or more radical polymerizable groups. The upper limit is preferably 15 or less, more preferably 10 or less, and further preferably 8 or less.

The molecular weight of the radical polymerizable compound 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 polymerizable compound is preferably 100 or more.

From the viewpoint of developability, the curable resin composition of the present invention preferably contains at least 12 or more functional radically polymerizable compounds containing 2 or more radically polymerizable groups, and more preferably contains at least 13 or more functional radically polymerizable compounds. Further, a mixture of a 2-functional radical polymerizable compound and a 3-or more-functional radical polymerizable compound may be used. For example, the number of functional groups of the polymerizable monomer having 2 or more functions means that the number of radical polymerizable groups in 1 molecule is 2 or more.

Specific examples of the radical polymerizable compound include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters and amides thereof, and esters of unsaturated carboxylic acids and polyhydric alcohol compounds are preferable. Further, addition reaction products of unsaturated carboxylic acid esters having an affinity substituent such as a hydroxyl group, an amino group, or a mercapto group with monofunctional epoxies, dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, and the like can also be preferably used. Also, addition reaction products of unsaturated carboxylic acid esters having electrophilic substituent groups such as isocyanate group or epoxy group with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters having dissociative substituent groups such as halogen group or tosyloxy group with monofunctional or polyfunctional alcohols, amines, or thiols are preferable. As another example, instead of the unsaturated carboxylic acid, 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 can be used. As a specific example, reference can be made to the descriptions in paragraphs 0113 to 0122 of Japanese patent laid-open No. 2016-027357, which are incorporated herein by reference.

The radical polymerizable compound is also preferably a compound having a boiling point of 100 ℃ or higher under normal pressure. Examples thereof include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloxypropyl) ether, tris (acryloxyethyl) isocyanurate, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylating them, polyester acrylates described in Japanese unexamined patent publication No. Sho 48-064183, Japanese examined patent publication No. Sho 49-043191 and Japanese examined patent publication No. Sho 52-030490, polyfunctional acrylates such as epoxy acrylates as reaction products of epoxy resins and (meth) acrylic acid, and the like A methacrylate ester; and mixtures of these. Further, the compounds described in paragraphs 0254 to 0257 of Japanese patent laid-open No. 2008-292970 are also preferable. Further, there can be mentioned a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth) acrylate.

Further, as a preferable radical polymerizable compound other than the above, compounds having a fluorene ring and having 2 or more groups containing an ethylenically unsaturated bond or cardo (cardo) resins described in japanese patent application laid-open nos. 2010-160418, 2010-129825, 4364216, and the like can be used.

Further, as other examples, specific unsaturated compounds described in Japanese patent publication No. 46-043946, Japanese patent publication No. 01-040337, and Japanese patent publication No. 01-040336, vinylphosphonic acid-based compounds described in Japanese patent publication No. 02-025493, and the like can be cited. Furthermore, a compound containing a perfluoroalkyl group as described in Japanese patent application laid-open No. 61-022048 can also be used. Further, compounds described as photopolymerizable monomers and oligomers in Journal of the administration Society of Japan, pages 20 to 308 (1984), and No.7, can also be used.

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

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

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

As the radical polymerizable compound, dipentaerythritol triacrylate (KaYARAD-330; Nippon Kayaku Co., manufactured by Ltd., as a commercial product), dipentaerythritol tetraacrylate (KaYARAD-320; Nippon Kayaku Co., manufactured by Ltd., as a commercial product), dipentaerythritol penta (meth) acrylate (KAYARAD-310; Nippon Kayaku Co., manufactured by Ltd., as a commercial product), dipentaerythritol hexa (meth) acrylate (KAYARAD DPHA; Nippon Kayaku Co., manufactured by Ltd., as a commercial product, manufactured by Ltd., A-DPH; Shin-Nakamura Co., manufactured by Ltd., as a commercial product), and a structure in which these (meth) acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues are preferable. Oligomer types of these can also be used.

Commercially available products of the radical polymerizable compound include, for example, SR-494 (manufactured by Sartomer Company, Inc.) which is a 4-functional acrylate having 4 vinylene chains, SR-209, 231, 239 (manufactured by Sartomer Company, Inc.) which is a 2-functional acrylate having 4 vinyloxy chains, SR-209, 231, 239 (manufactured by Inc.), Nippon Kayaku Co., manufactured by Ltd., DPCA-60 (manufactured by Ltd.) which is a 6-functional acrylate having 6 pentylene oxy chains, TPA-330 (manufactured by Ltd.) which is a 3-functional acrylate having 3 isobutoxy chains, urethane oligomer UAS-10, UAB-140(NIPPON PAPER INDUSTRIES CO., manufactured by LTD.), NK ester M-40G, NK, ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (n-Nakamura Co., Ltd.), DPHA-40K CO., manufactured by Chemical Co., Kappan CO., manufactured by Ltd.), Niyaku Co., Ltd UA-306T, UA-306I, AH-600, T-600, AI-600(Kyoeisha chemical Co., Ltd.), BLEMMER PME400(NOF corporation.) and the like.

Further, as the radical polymerizable compound, compounds having an amino structure or a sulfide structure in the molecule as described in Japanese patent application laid-open Nos. 63-277653, 63-260909 and 01-105238 can be used.

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

The acid value of the radical polymerizable compound having an acid group is preferably 0.1 to 40mgKOH/g, and particularly preferably 5 to 30 mgKOH/g. If the acid value of the radical polymerizable compound is within the above range, the production workability is excellent, and the developability is further excellent. Further, the polymerizability is good. The acid value is in accordance with JIS K0070: 1992.

The curable resin composition of the present invention can preferably use a monofunctional radical polymerizable compound as a radical polymerizable compound from the viewpoint of suppressing warpage accompanying control of the elastic modulus of a cured film. As the monofunctional radical polymerizable compound, 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, (meth) acrylic acid derivatives such as glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allyl glycidyl ether, diallyl phthalate and triallyl trimellitate. The monofunctional radical polymerizable compound is preferably a compound having a boiling point of 100 ℃ or higher under normal pressure in order to suppress volatilization before exposure.

[ polymerizable Compound other than the above-mentioned radical polymerizable Compound ]

The curable resin composition of the present invention may further contain, as the other polymerizable compound, a polymerizable compound other than the radical polymerizable compound. Examples of the polymerizable compound other than the radical polymerizable compound include compounds having a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group; an epoxy compound; an oxetane compound; a benzoxazine compound.

Compounds having hydroxymethyl, alkoxymethyl or acyloxymethyl groups

As the compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, a compound represented by the following formula (AM1), (AM4) or (AM5) is preferable.

[ chemical formula 47]

(wherein t represents an integer of 1 to 20, R¹⁰⁴Represents a t-valent organic group having 1 to 200 carbon atoms, R¹⁰⁵Is represented by-OR¹⁰⁶or-OCO-R¹⁰⁷A group represented by R¹⁰⁶R represents a hydrogen atom or an organic group having 1 to 10 carbon atoms¹⁰⁷Represents an organic group having 1 to 10 carbon atoms. )

[ chemical formula 48]

(in the formula, R⁴⁰⁴Represents a 2-valent organic group having 1 to 200 carbon atoms, R⁴⁰⁵Is represented by-OR⁴⁰⁶or-OCO-R⁴⁰⁷A group represented by R⁴⁰⁶R represents a hydrogen atom or an organic group having 1 to 10 carbon atoms⁴⁰⁷Represents an organic group having 1 to 10 carbon atoms. )

[ chemical formula 49]

(wherein u represents an integer of 3 to 8, R⁵⁰⁴Represents a u-valent organic group having 1 to 200 carbon atoms, R⁵⁰⁵Is represented by-OR⁵⁰⁶or-OCO-R⁵⁰⁷A group represented by R⁵⁰⁶R represents a hydrogen atom or an organic group having 1 to 10 carbon atoms⁵⁰⁷Represents an organic group having 1 to 10 carbon atoms. )

Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (trade name, manufactured by ASAHI YUKIZAI CORPORATION), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylBISOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (trade name, manufactured by Honshu Chemical Industry Co., manufactured by Ltd.), NIKALAC MX-290 (trade name, manufactured by Sanwa Chemical Co., manufactured by Ltd.), 2, 6-dimethylymethyl-4-t-butylphenol (2, 6-dimethoxymethyl-4-t-butylphenol), 2, 6-dimethylymethyl-cresol (2, 6-dimethoxymethyl-4-cresol), 6-diacetoxymethyl-p-cresol), and the like.

Specific examples of the compound represented by the formulｃA (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., manufactured by Ltd.), TM-BIP-A (trade name, manufactured by ASAHI YUKIZAI CORATION), NIKALAMX-280, NIKALAMX-270, and NIKALAC MW-100LM (trade name, manufactured by SanwｃA Chemical Co., manufactured by Ltd.).

Epoxy compound (compound having epoxy group) -

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 easily cause shrinkage of the film since a dehydration reaction derived from crosslinking is not caused. Therefore, the epoxy compound is contained, whereby the low-temperature curing and warpage of the curable resin composition can be effectively suppressed.

The epoxy compound preferably contains a polyethylene oxide group. This further reduces the elastic modulus and suppresses warpage. The polyethylene oxide group represents an ethylene oxide having a repeating unit number of 2 or more, and the repeating unit number is preferably 2 to 15.

Examples of the epoxy compound include bisphenol a type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; epoxy group-containing silicones such as polymethyl (glycidoxypropyl) siloxane, but the epoxy group-containing silicones are not limited to these. Specifically, EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4850-. Among them, an epoxy resin containing a polyethylene oxide group is preferable in terms of suppressing warpage and excellent heat resistance. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, and RIKARESIN (registered trademark) BEO-60E contain a polyethylene oxide group, and are therefore preferable.

Oxetane compound (compound having oxetanyl group) -

Examples of the oxetane compound include a compound having 2 or more oxetane rings in one molecule, 3-ethyl-3-hydroxyoxetane, 1, 4-bis { [ (3-ethyl-3-oxetanyl) methoxy ] methyl } benzene, 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1, 4-benzenedicarboxylic acid-bis [ (3-ethyl-3-oxetanyl) methyl ] ester, and the like. As a specific example, TOAGOSEI co, a series of ARON oxoetane (e.g., OXT-121, OXT-221, OXT-191, and OXT-223) made by ltd can be preferably used, and these may be used alone or 2 or more kinds may be mixed.

Benzoxazine compound (compound having polybenzoxazole group)

The benzoxazine compound is preferable because the crosslinking reaction due to the ring-opening addition reaction does not generate degassing during curing, and further reduces thermal shrinkage to suppress generation of warpage.

Preferable examples of the benzoxazine compound include B-a type benzoxazine, B-m type benzoxazine (trade name, manufactured by Shikoku Chemicals Corporation), benzoxazine adduct of polyhydroxystyrene resin, and novolak type dihydrobenzoxazine compound. These may be used alone, or 2 or more kinds may be mixed.

When other polymerizable compounds are contained, the content thereof is preferably more than 0 mass% and 60 mass% or less with respect to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and still more preferably 30% by mass or less.

The other polymerizable compounds may be used alone in 1 kind or in combination of 2 or more kinds. When 2 or more kinds are used simultaneously, the total amount is preferably in the above range.

< solvent >

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

As the esters, preferable esters include, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ -butyrolactone, ε -caprolactone, δ -valerolactone, alkyl alkoxyacetates (for example, methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (for example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, etc.), Ethyl 3-ethoxypropionate, etc.)), alkyl esters of 2-alkoxypropionic acid (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl 2-oxobutyrate, etc, Ethyl 2-oxobutyrate, and the like.

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

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

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

The sulfoxide is preferably a sulfoxide such as dimethyl sulfoxide.

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

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

In the present invention, it is preferable that 1 kind of solvent or a mixed solvent of 2 or more kinds 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 and propylene glycol methyl ether acetate be used. Particularly preferably, dimethyl sulfoxide and gamma-butyrolactone are used simultaneously.

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

The solvent may contain only 1 species or 2 or more species. When 2 or more solvents are contained, the total amount thereof is preferably within the above range.

< migration inhibitor >

The curable resin composition of the present invention preferably further contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively inhibit the metal ions originating from the metal layer (metal wiring) from migrating into the curable resin composition layer.

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, and triazine ring), compounds having a thiourea and a mercapto group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole-based compounds such as 1,2, 4-triazole and benzotriazole, and tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

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

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

Specific examples of the migration inhibitor include the following compounds.

[ chemical formula 50]

When the curable resin composition contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and still more preferably 0.1 to 1.0% by mass, based on the total solid content of the curable resin composition.

The migration inhibitor may be only 1 species or 2 or more species. When the number of migration inhibitors is 2 or more, the total amount thereof is preferably within the above range.

< polymerization inhibitor >

The curable resin composition of the present invention preferably contains a polymerization inhibitor.

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

Further, the following compound (Me is methyl) can also be used.

[ chemical formula 51]

When the curable resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, and still more preferably 0.05 to 2.5% by mass, based on the total solid content of the curable resin composition of the present invention.

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

< modifier for improving adhesion of Metal >

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

Examples of the silane coupling agent include a compound described in paragraph 0167 of International publication No. 2015/199219, a compound described in paragraphs 0062 to 0073 of Japanese patent application laid-open No. 2014-191002, a compound described in paragraphs 0063 to 0071 of International publication No. 2011/080992, a compound described in paragraphs 0060 to 0061 of Japanese patent application laid-open No. 2014-191252, a compound described in paragraphs 0045 to 0052 of Japanese patent application laid-open No. 2014-041264, and a compound described in paragraph 0055 of International publication No. 2014/097594. Further, it is also preferable to use 2 or more different silane coupling agents as described in paragraphs 0050 to 0058 of Japanese patent application laid-open No. 2011-128358. Further, the following compounds are also preferably used as the silane coupling agent. In the following formula, Et represents an ethyl group.

[ chemical formula 52]

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

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and still more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the heterocycle-containing polymer precursor. When the lower limit value is set to the upper limit value or more, the adhesion between the cured film and the metal layer after the curing step is good, and when the upper limit value is set to the lower limit value or less, the heat resistance and the mechanical properties of the cured film after the curing step are good. The number of the metal adhesion improvers may be 1 or 2 or more. When 2 or more kinds are used, the total amount is preferably within the above range.

< other additives >

The curable resin composition of the present invention may contain, as necessary, various additives, for example, a thermal acid generator, a sensitizer such as N-phenyldiethanolamine, a chain transfer agent, a surfactant, a higher fatty acid derivative, inorganic particles, a curing agent, a curing catalyst, a filler, an antioxidant, an ultraviolet absorber, an agglomeration inhibitor, and the like, within a range not impairing the effects of the present invention. When these additives are blended, the total blending amount thereof is preferably 3% by mass or less of the solid content of the curable resin composition.

[ sensitizer ]

The curable resin composition of the present invention may contain a sensitizer. The sensitizer absorbs a specific active radiation to become an electron excited state. The sensitizer in an electron excited state is brought into contact with a thermosetting accelerator, a thermal radical polymerization initiator, a photo radical polymerization initiator, or the like to produce effects such as electron transfer, energy transfer, heat generation, and the like. Thereby, the thermal curing accelerator, the thermal radical polymerization initiator, and the photo radical polymerization initiator are chemically changed and decomposed to generate radicals, acids, or bases.

Examples of the sensitizer include N-phenyldiethanolamine and the like.

As the sensitizer, a sensitizing dye may be used.

The details of the sensitizing dye can be found in paragraphs 0161 to 0163 of Japanese patent application laid-open No. 2016-027357, which is incorporated herein by reference.

When the curable resin composition of the present invention 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 still more preferably 0.5 to 10% by mass, based on the total solid content of the curable resin composition of the present invention. The sensitizer may be used singly or in combination of 1 or more.

[ chain transfer agent ]

The curable resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in page 683-684 of The third edition of The Polymer dictionary (The Society of Polymer Science, Japan, 2005). As the chain transfer agent, for example, a compound group having SH, PH, SiH, and GeH in a molecule is used. These radicals can be generated by supplying hydrogen to a low-activity radical to generate a radical, or by deprotonation after oxidation. In particular, a thiol compound can be preferably used.

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

When the curable resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, and still more preferably 1 to 5 parts by mass, based on 100 parts by mass of the total solid content of the curable resin composition of the present invention. The chain transfer agent may be only 1 type or 2 or more types. When the number of the chain transfer agents is 2 or more, the total amount thereof is preferably within the above range.

[ surfactant ]

In view of further improving coatability, various surfactants may be added to the curable resin composition of the present invention. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. Also, the following surfactants are also preferable. In the following formulae, the parentheses indicating the structural unit of the main chain indicate the content (mol%) of each structural unit, and the parentheses indicating the structural unit of the side chain indicate the number of repetitions of each structural unit.

[ chemical formula 53]

Further, as the surfactant, the compounds described in paragraphs 0159 to 0165 of International publication No. 2015/199219 can be used.

When the curable resin composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the curable resin composition of the present invention. The number of the surfactants may be only 1 or 2 or more. When the number of the surfactants is 2 or more, the total amount thereof is preferably within the above range.

[ higher fatty acid derivatives ]

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

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

When the curable resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass based on the total solid content of the curable resin composition of the present invention. The number of the higher fatty acid derivatives may be only 1 or 2 or more. When the number of the higher fatty acid derivatives is 2 or more, the total amount thereof is preferably within the above range.

< restrictions on other contained substances >

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

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

Further, as a method for reducing metal impurities unexpectedly contained in the curable resin composition of the present invention, there can be mentioned the following methods: a method in which a raw material having a small metal content is selected as a raw material constituting the curable resin composition of the present invention, the raw material constituting the curable resin composition of the present invention is filtered through a filter, and the inside of the apparatus is lined with polytetrafluoroethylene or the like, and distillation is performed under conditions that minimize contamination.

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

As the container for the curable resin composition of the present invention, a conventionally known container can be used. Further, for the purpose of suppressing the mixing of impurities into the raw material or the curable resin composition, a multilayer bottle having an inner wall of the container made of 6 kinds of 6-layer resins, or a bottle having a 7-layer structure made of 6 kinds of resins is also preferably used as the storage container. Examples of such a container include those disclosed in Japanese patent laid-open publication No. 2015-123351.

< preparation of curable resin composition >

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

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

In addition to filtration using a filter, an impurity removal treatment using an adsorbent may be performed. It is also possible to combine filter filtration and impurity removal treatment using an adsorption 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.

< use of curable resin composition >

The curable resin composition of the present invention is preferably used for forming an interlayer insulating film for a rewiring layer.

Further, the present invention can also be used for formation of an insulating film of a semiconductor device, formation of a stress buffer film, or the like.

(cured film, laminate, semiconductor device, and methods for producing these)

Next, the cured film, the laminate, the semiconductor device, and the methods for producing these will be described.

The cured film of the present invention is obtained by curing the curable resin composition of the present invention. The thickness of the cured film of the present invention can be set to, for example, 0.5 μm or more and 1 μm or more. The upper limit value may be 100 μm or less, and may be 30 μm or less.

The cured film of the present invention may be laminated with 2 or more layers, and further laminated with 3 to 7 layers to form a laminate. The laminate of the present invention preferably includes 2 or more cured films, and a metal layer is preferably included between any of the cured films. Such a metal layer can be preferably used as a metal wiring such as a rewiring layer.

Examples of the field to which the cured film of the present invention can be applied include an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like. In addition, there are cases where a sealing film, a substrate material (a base film, a cover film, or an interlayer insulating film of a flexible printed circuit board), or an insulating film for practical mounting as described above is etched to form a pattern, and the like. For these uses, for example, reference can be made to Science & Technology co, ltd, "high functionalization and application Technology of polyimide" 4 months 2008, kaki benayu mingming/prison, CMC technical library "foundation and development of polyimide material" 11 months 2011 issue, japan polyimide aromatic system polymer research institute/compilation "latest polyimide foundation and application" NTS, 8 months 2010, and the like.

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

The method for producing a cured film of the present invention (hereinafter, also simply referred to as "the method for producing the present invention") preferably includes a film-forming step of applying the curable resin composition of the present invention to a substrate to form a film.

The method for producing a cured film of the present invention preferably includes the film forming step, an exposure step of exposing the film to light, and a development step of developing the film.

The method for producing a cured film of the present invention preferably further comprises the film forming step and, if necessary, the developing step, and further comprises a heating step of heating the film at 50 to 450 ℃.

Specifically, the method preferably includes the following steps (a) to (d).

(a) Film formation step for forming a film (curable resin composition layer) by applying the curable resin composition to a substrate

(b) An exposure step of exposing the film after the film formation step

(c) A developing step of developing the exposed film

(d) A heating step of heating the developed film at 50 to 450 DEG C

By heating in the heating step, the resin layer cured by exposure can be further cured. In this heating step, for example, the thermal alkali generator is decomposed, and sufficient curability can be obtained.

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

< film formation step (layer formation step) >

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

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

As the substrate, for example, a plate-shaped substrate (substrate) is used.

When the curable resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer serves as a substrate.

The curable resin composition is preferably applied to a substrate by coating.

Specifically, examples of suitable methods include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, a slit coating method, and an ink jet method. From the viewpoint of the thickness uniformity of the curable resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an ink jet method are more preferable. By adjusting the solid content concentration and the coating conditions appropriately according to the method, a resin layer having a desired thickness can be obtained. The coating method can be appropriately selected according to the shape of the substrate, and a spin coating method, a spray coating method, an ink jet method, and the like are preferable if the substrate is a circular substrate such as a wafer, and a slit coating method, a spray coating method, an ink jet method, and the like are preferable if the substrate is a rectangular substrate. In the case of spin coating, the coating can be applied, for example, at a rotation speed of 500 to 2,000rpm for about 10 seconds to 1 minute.

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

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

< drying Process >

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

< Exposure Process >

The production method of the present invention may include an exposure step of exposing the film (curable resin composition layer) to light. The exposure amount is not particularly limited as long as the curable resin composition can be cured, and for example, it is preferably 100 to 10,000mJ/cm in terms of exposure energy at a wavelength of 365nm²More preferably 200 to 8,000mJ/cm²。

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

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

< development processing step >

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

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

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

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

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

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

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

< heating Process >

The production method of the present invention preferably includes a heating step (heating step) of heating the developed film at 50 to 450 ℃.

It is preferable to include a heating step after the film formation step (layer formation step), the drying step, and the development step. In the heating step, for example, the thermal alkali generator is decomposed to generate an alkali, and a cyclization reaction of the heterocyclic ring-containing polymer precursor is performed. In addition, curing of the specific polymerizable compound and other polymerizable compounds added as needed can be performed in this step. The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50 ℃ or higher, more preferably 80 ℃ or higher, further preferably 140 ℃ or higher, further preferably 150 ℃ or higher, further preferably 160 ℃ or higher, and further preferably 170 ℃ or higher. The upper limit is preferably 500 ℃ or lower, more preferably 450 ℃ or lower, further preferably 350 ℃ or lower, further preferably 250 ℃ or lower, and further preferably 220 ℃ or lower.

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

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

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

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

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

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

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

< Process for Forming Metal layer >

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

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

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

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

< laminating Process >

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

The laminating step is a series of steps including (a) a film forming step (layer forming step), (b) an exposure step, (c) a development treatment step, and (d) a heating step, which are sequentially performed again on the surface of the cured film (resin layer) or the metal layer. However, the film forming step (a) may be repeated. The heating step (d) may be performed at the end or in the middle of the lamination. That is, the following method may be adopted: repeating the steps (a) to (c) a predetermined number of times, and then heating the laminate (d), thereby collectively curing the laminated curable resin composition layers. In addition, the developing step (c) may be followed by the metal layer forming step (e), and in this case, the heating of (d) may be performed every time or may be performed collectively after the lamination is performed a predetermined number of times. It is needless to say that the lamination step may appropriately include the drying step, the heating step, and the like.

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

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

For example, the resin layer such as resin layer/metal layer/resin layer/metal layer preferably has a structure of 3 layers or more and 7 layers or less, and more preferably 3 layers or more and 5 layers or less.

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

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

Examples

The present invention will be described in further detail below with reference to examples. The materials, the amounts used, the ratios, the contents of the processes, the processing steps, and the like described in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.

< Synthesis example 1 >

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

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

[ chemical formula 54]

< Synthesis example 2 >

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

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

[ chemical formula 55]

< Synthesis example 3 >

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

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

[ chemical formula 56]

< Synthesis example 4 >

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

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

[ chemical formula 57]

< Synthesis example 5 >

[ Synthesis of polyimide precursor derived from 4,4 '-oxydiphthalic anhydride, 4' -diaminodiphenyl ether, and 2-hydroxyethyl methacrylate (A-5: polyimide precursor having radical polymerizable group) ]

155.1g of 4, 4' -oxydiphthalic anhydride (ODPA) was placed in a 2-liter separable flask, and 134.0g of 2-hydroxyethyl methacrylate (HEMA) and 400ml of γ -butyrolactone were added thereto. While stirring at room temperature, 79.1g of pyridine was added to obtain a reaction mixture. After completion of the heat generation by the reaction, the reaction mixture was cooled to room temperature and allowed to stand for a further 16 hours.

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

The obtained reaction solution was added to 3 liters of ethanol, and a precipitate composed of a crude polymer was generated. The resulting crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran, thereby obtaining a crude polymer solution. The obtained crude polymer solution was dropwise added to 28 liters of water to precipitate a polymer, and the obtained precipitate was collected by filtration and then vacuum-dried, whereby a polymer A-5 was obtained in the form of a powder. The weight average molecular weight (Mw) of the polymer A-5 was measured and found to be 20,000.

< Synthesis example 6 >

[ Synthesis of polyimide precursor derived from 3,3 ', 4 ' -Biphenyltetracarboxylic dianhydride, 4 ' -diaminodiphenyl ether, and 2-hydroxyethyl methacrylate (A-7: polyimide precursor having radical polymerizable group) ]

A reaction was carried out in the same manner as in Synthesis example 5 except that 147.1g of 3,3 ', 4 ' -biphenyltetracarboxylic dianhydride was used in place of 155.1g of 4,4 ' -oxydiphthalic anhydride in Synthesis example 5, thereby obtaining Polymer A-6. The weight average molecular weight (Mw) of the polymer A-6 was determined to be 22,000.

< Synthesis example 7 >

[ Synthesis of Compound C-1 ]

A mixture of hexamethylene diisocyanate heated to 30-90 ℃ and a catalyst such as dibutyltin dilaurate is added dropwise with light acrylate PE-3A (KYOEISHA CHEMICAL Co., LTD.) and reacted for 6-12 hours, thereby synthesizing a compound C-1.

< Synthesis example 8 >

[ Synthesis of Compound C-2 ]

Compound C-2 was synthesized in the same manner as in the synthesis of compound C-1, except that hexamethylene diisocyanate was changed to isophorone diisocyanate in the synthesis of compound C-1.

< synthetic example 9 >

[ Synthesis of Compound C-3 ]

P-xylylenediamine was added dropwise to Karenz BEI (manufactured by SHOWA DENKO K.K.) under ice-cooling, and the mixture was reacted at room temperature for 6 to 12 hours, whereby a compound C-3 was synthesized.

< synthetic example 10 >

[ Synthesis of Compound C-4 ]

Compound C-4 was synthesized by the synthesis method described in Japanese patent laid-open No. 2012-206992.

< Synthesis example 11 >

[ Synthesis of Compound C-5 ]

1,2, 4-butanetriol is added dropwise to a mixture of Karenz MOI heated to 30 to 90 ℃ and a catalyst such as dibutyltin dilaurate, and the mixture is reacted for 6 to 12 hours, whereby a compound C-5 is synthesized.

< Synthesis example 12 >

[ Synthesis of Compound C-6 ]

Under ice-cooling, 2-aminoethyl methacrylate hydrochloride was added dropwise to 1,3, 5-benzenetricarboxylic acid, and the mixture was reacted at room temperature for 6 to 12 hours, whereby a compound C-6 was synthesized.

The structures of the compounds C-1 to C-6 are represented by the following formulae (C-1) to (C-6), respectively.

[ chemical formula 58]

[ chemical formula 59]

< examples and comparative examples >

In each example, the components shown in table 1 below were mixed to obtain each curable resin composition. In each comparative example, the components shown in table 1 below were mixed to obtain each comparative composition.

Specifically, the contents of the components described in the column of table 1 except for "solvent" are the amounts described in "parts by mass" of table 1, and the contents of the components described in the column of "solvent" of table 1 are the amounts at which the solid content concentration of the composition becomes the value described in table 1.

The "I-1/I-2" and "80/20" of the "solvent" in table 1 indicate that the content ratio of I-1 to I-2 is 80:20 in terms of mass ratio.

The obtained curable resin composition and comparative composition were passed through a polytetrafluoroethylene filter having a pore width of 0.8 μm and subjected to pressure filtration.

In table 1, the column "C ═ C valency" indicates the valency (mmol/g) of the radical polymerizable group derived from the compound having a radical polymerizable group having a molecular weight of 2,000 or less, contained in the composition.

In table 1, the expression "-" indicates that the component is not contained.

The details of each component shown in table 1 are as follows.

[ Polymer precursor ]

A-1 to A-6: a-1 to A-6 synthesized in the above

[ other polymerizable Compound ]

B-1 and B-2: a compound of the structure

[ chemical formula 60]

[ specific polymerizable Compound ]

C-1 to C-6: the compounds obtained in the above synthesis examples

[ photopolymerization initiator ]

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

[ chemical formula 61]

[ onium salts or other thermoalkaligenic agents ]

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

[ chemical formula 62]

[ polymerization inhibitor ]

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

F-3: 2-nitroso-1-naphthol (Tokyo Chemical Industry Co., Ltd.; manufactured by Ltd.) [ Chemical formula 63]

[ migration inhibitor ]

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

[ chemical formula 64]

[ Metal adhesion improver ]

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

[ chemical formula 65]

[ solvent ]

I-1: gamma-butyrolactone (manufactured by SANWAYUKA INDUSTRY CORPORATION)

I-2: dimethyl sulfoxide (manufactured by FUJIFILM Wako Pure Chemical Corporation)

I-3: n-methyl-2-pyrrolidone (manufactured by Ashland Co., Ltd.)

I-4: ethyl lactate (Tokyo Chemical Industry Co., Ltd.; manufactured by Ltd.)

[ other additives ]

J-1: n-phenyldiethanolamine (Tokyo Chemical Industry Co., Ltd.)

< production of cured film >

In each of examples and comparative examples, a curable resin composition or a comparative composition was applied to a silicon wafer by a spin coating method to form a resin layer. The silicon wafer having the above resin layer formed thereon was dried on a hot plate at 100 ℃ for 4 minutes to obtain a resin composition layer having a uniform thickness of 20 μm on the silicon wafer.

Using a broadband exposure machine (manufactured by USHIO INC., UX-1000SN-EH01) at 400mJ/cm²The exposure of (2) can be carried out by exposing the resin composition layer on the silicon wafer, heating the exposed resin composition layer to 180 ℃ for 2 hours at a heating rate of 5 ℃/min under a nitrogen atmosphere. The heated resin composition layer and the silicon wafer were immersed in a 3 mass% hydrofluoric acid aqueous solution, and the heated resin composition layer was peeled from the silicon wafer. The resin composition layer after heating peeled off as described above was used as a cured film.

< evaluation >

In each of examples and comparative examples, the obtained cured films were evaluated for chemical resistance, elongation at break, and resolution.

The details of the evaluation method in each evaluation are described below.

[ drug resistance ]

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

Liquid medicine: 90:10 (mass ratio) mixture of dimethyl sulfoxide (DMSO) and 25 mass% aqueous tetramethylammonium hydroxide (TMAH) solution

Evaluation conditions were as follows: the cured film was immersed in the chemical solution at 75 ℃ for 15 minutes, and the film thickness before and after immersion was compared to calculate the dissolution rate (nm/min). The film thickness was measured by an optical film thickness meter (KT-22, manufactured by Footfill Co.).

The evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in table 2. It can be said that the smaller the dissolution rate value, the more excellent the chemical resistance of the cured film.

Evaluation criteria-

A: the dissolution rate was less than 250 nm/min.

B: the dissolution rate is 250 nm/min or more and less than 350 nm/min.

C: the dissolution rate is 350 nm/min or more and less than 450 nm/min.

D: the dissolution rate is 450 nm/min or more.

[ elongation at break ]

The elongation at break of the obtained cured film was measured. The elongation at break of the cured film was measured in accordance with JIS-K6251 (Japanese Industrial Standard) under an environment of 25 ℃ and 65% RH (relative humidity) in the longitudinal direction and the width direction of the film using a tensile Tester (TENSILON) with a crosshead speed of 300 mm/min, a sample width of 10mm, and a sample length of 50 mm. The elongation at break was calculated from Eb (%) (Lb-L0)/L0 (Eb: elongation at break, L0: length of the test piece before the test, Lb: length of the test piece when the test piece was cut). The elongation at break was measured 10 times each, and the average value (the arithmetic average of the measured values of 10 elongation at break values measured 10 times in total based on the longitudinal direction) was used for the evaluation.

The evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in table 2. It can be said that the larger the value of elongation at break, the more excellent the elongation at break of the cured film.

Evaluation criteria-

A: the average value is 60% or more

B: the average value is more than 50% and less than 60%

C: the average value is more than 45% and less than 50%

D: the average value is less than 45 percent

[ evaluation of lithography (resolution) ]

In each of examples and comparative examples, a curable resin composition or a comparative composition was spin-coated on a silicon wafer to form a resin layer. Drying the silicon wafer with the resin layer on a hot plate at 100 deg.C for 4 min to obtain a 20 μm layer on the silicon waferm is a resin composition layer having a uniform film thickness. The resin composition layer on the silicon wafer was exposed by a stepper (Nikon NSR 2005i9C), and the exposed resin composition layer was obtained. The exposure was carried out by i-ray, and the exposure dose at 365nm wavelength was 400mJ/cm². Further, exposure was performed using a photomask in which lines and space patterns with 1 μm scale were formed at 5 μm to 25 μm. The above-exposed resin composition layer was developed with cyclopentanone for 60 seconds.

The resin composition layer (line pattern) after the above development was observed with a Scanning Electron Microscope (SEM), and the minimum line width was determined.

The evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in table 2. The smaller the minimum line width, the more excellent the photolithography (resolution).

Evaluation criteria-

A: minimum line width less than 10 μm

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

C: the minimum line width is 20 μm or more or a pattern having edge acuity cannot be obtained.

[ Table 2]

	Resistance to chemicals	Elongation at break	Litho-etch property
				Example 1	B	B	A
Example 2	B	A	A
				Example 3	A	B	B
Example 4	A	B	A
				Example 5	A	A	A
Example 6	A	B	A
				Example 7	B	A	A
Example 8	B	B	A
				Example 9	A	B	A
Example 10	B	B	A
				Example 11	A	B	A
Example 12	A	B	B
				Example 13	A	A	B
Example 14	A	A	B
				Example 15	A	A	A
Example 16	A	A	A
				Example 17	A	A	A
Example 18	A	A	A
				Example 19	A	A	A
Comparative example 1	D	C	C
				Comparative example 2	D	C	A
Comparative example 3	C	C	A
				Comparative example 4	D	D	A
Comparative example 5	C	D	C

From the above results, it is understood that a cured film obtained from the curable resin composition of the present invention containing the heterocyclic ring-containing polymer precursor and the specific polymerizable compound 1 and having a radical polymerizable group valence of 0.25 to 4.35mmol/g derived from a compound having a radical polymerizable group having a molecular weight of 2,000 or less or the curable resin composition containing the specific polymerizable compound 2 is excellent in chemical resistance and elongation at break.

The curable resin compositions of comparative examples 1 to 4 do not contain any of the specific polymerizable compound 1 and the specific polymerizable compound 2. It is found that the cured films obtained from the curable resin compositions of comparative examples 1 to 4 have poor chemical resistance.

The curable resin composition of comparative example 5 contains the specific polymerizable compound 1, but the radical polymerizable group valence of the compound derived from a radical polymerizable group having a molecular weight of 2,000 or less exceeds 4.35 mol/g. It is found that the cured film obtained from the curable resin composition of comparative example 5 has a low elongation at break.

< example 101 >

The curable resin composition described in example 1 was applied in a layer form to the surface of a resin substrate having a copper thin layer formed thereon by spin coating, dried at 100 ℃ for 5 minutes to form a curable resin composition layer having a film thickness of 20 μm, and then exposed to light using a stepper (manufactured by Nikon Corporation, NSR1505 i 6). The exposure was carried out at a wavelength of 365nm via a mask (binary mask with pattern 1:1 line and space and line width of 10 μm). After exposure, development was performed with cyclopentanone for 30 seconds, and rinsing was performed with PGMEA for 20 seconds, whereby a pattern was obtained.

Subsequently, the substrate was heated at 230 ℃ for 3 hours to form an interlayer insulating film for a rewiring layer. The interlayer insulating film for a rewiring layer has excellent insulating properties.

Then, it was confirmed that the semiconductor device was normally operated as a result of manufacturing the semiconductor device using the interlayer insulating film for the rewiring layer.