CN114008527A

CN114008527A - Curable resin composition, cured film, laminate, method for producing cured film, semiconductor device, and polyimide or polyimide precursor

Info

Publication number: CN114008527A
Application number: CN202080043671.XA
Authority: CN
Inventors: 野崎敦靖
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2019-06-17
Filing date: 2020-06-11
Publication date: 2022-02-01
Also published as: TW202110950A; WO2020255859A1; JP7289353B2; KR20220008885A; JPWO2020255859A1

Abstract

The present invention is a curable resin composition containing at least one resin having a polyalkyleneoxy group and a polymerizable group and selected from the group consisting of polyimide and a polyimide precursor, a polymerization initiator, a polymerizable compound, and a solvent, a cured film obtained by curing the curable resin composition, a laminate including the cured film, a method for producing the cured film, a semiconductor device including the cured film or the laminate, and polyimide or a polyimide precursor.

Description

Curable resin composition, cured film, laminate, method for producing cured film, semiconductor device, and polyimide or polyimide precursor

Technical Field

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

Background

Polyimide is excellent in heat resistance and insulation properties, and therefore is suitable for various applications. The use is not particularly limited, and when a semiconductor device for actual mounting is taken as an example, the semiconductor device is used as a material for an insulating film or a sealing material or a protective film. Also, the film is used as a base film or a cover film (COVERLAY) of a flexible substrate.

For example, in the above-mentioned applications, polyimide may be used in the form of a curable resin composition containing polyimide, and may be used in the form of a curable resin composition containing a polyimide precursor. The precursor is cyclized by heating or the like to form polyimide.

These curable resin compositions can be applied to substrates and the like by a known coating method and the like, and therefore, for example, the curable resin compositions to be applied have excellent production adaptability such as high freedom of design such as shape, size, and application position.

From the viewpoint of not only high performance possessed by polyimide but also excellent suitability for such production, development of industrial application of a curable resin composition containing at least one resin selected from the group consisting of polyimide and a polyimide precursor is increasingly desired.

For example, patent document 1 describes a curable polyimide having a structure with a specific polymerizable group.

Prior art documents

Patent document

Patent document 1: international publication No. 2018/237377

Disclosure of Invention

Technical problem to be solved by the invention

In a curable resin composition containing at least one resin selected from the group consisting of polyimide and polyimide precursor, it is desired to provide a curable resin composition having excellent coatability of the composition.

An object of one embodiment of the present invention is to provide a curable resin composition having excellent coatability, 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.

Another object of another embodiment of the present invention is to provide a novel polyimide or polyimide precursor.

Means for solving the technical problem

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

< 1 > a curable resin composition comprising:

at least one resin having a polyalkyleneoxy group and a polymerizable group and selected from the group consisting of polyimide and a polyimide precursor;

a polymerization initiator;

a polymerizable compound; and

a solvent.

< 2 > the curable resin composition of < 1 > wherein the structure having the polyalkyleneoxy group and the polymerizable group comprises a structure represented by the following formula (1-1).

[ chemical formula 1]

In the formula (1-1), R¹Each independently represents a hydrogen atom or an alkyl group, Z¹Represents a group containing a polymerizable group, n represents an integer of 2 or more, m represents an integer of 2 or more, and x represents a bonding site with another structure.

< 3 > the curable resin composition of < 2 >, wherein Z is¹At least one group selected from the group consisting of an ethylenically unsaturated group, a cyclic ether group and a methylol group is contained as the polymerizable group.

< 4 > such as < 2 > or < 3 >, wherein the resin contains a structure represented by the following formula (1-2) as a structure containing a structure represented by the following formula (1-1).

[ chemical formula 2]

In the formula (1-2), L¹Represents a b +2 valent linking group, X²Represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond, L²Represents a single bond or an a + 1-valent linking group, X¹Represents a structure represented by the formula (1-1), wherein a represents an integer of 1 or more, b represents an integer of 1 or more, and a plurality of X's are present²、L²、X¹Or a, a plurality of X²、L²、X¹Or a may be the same or different.

< 5 > the curable resin composition according to any one of < 2 > to < 4 >, wherein the repeating unit having a structure represented by the formula (1-1) includes a repeating unit represented by the formula (1-3).

[ chemical formula 3]

In the formula (1-3), L¹Represents a b +2 valent linking group, X²Represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond, L²Represents a single bond or an a + 1-valent linking group, X¹Represents a structure represented by the formula (1-1), a represents an integer of 1 or more, b represents an integer of 1 or more, L⁴Represents a structure represented by the following formula (L4-1) or formula (L4-2), wherein X is present in plural²、L²、X¹Or a, a plurality of X²、L²、X¹Or a may be the same or different.

[ chemical formula 4]

In the formula (L4-1) or the formula (L4-2), R¹¹⁵Represents a 4-valent organic group, A¹And A²Each independently represents an oxygen atom or-NH-, R¹¹³And R¹¹⁴Each independently represents a hydrogen atom or a 1-valent organic group.

The curable resin composition of < 6 > such as < 4 > or < 5 >, wherein L is¹Comprises at least one structure selected from the group consisting of structures represented by the following formulae (A-1) to (A-5).

[ chemical formula 5]

In the formulae (A-1) to (A-5), R^A11～R^A14、R^A21～R^A24、R^A31～R^A38、R^A41～R^A48And R^A51～R^A58Each independently represents a hydrogen atom, an alkyl group, a cyclic alkyl group, an alkoxy group, a hydroxyl group, a cyano group, a haloalkyl group, a halogen atom, or a group which is related to X in the above formula (1-2) or the above formula (1-3)²Bonding site of, L^A31And L^A41Each independently represents a single bond, carbonyl group, sulfonyl group, 2-valent saturated hydrocarbon group, 2-valent unsaturated hydrocarbon group, hetero atom, heterocyclic group or halogenated alkylene group, R^A11～R^A14、R^A21～R^A24、R^A31～R^A38、R^A41～R^A48And R^A51～R^A58In which b are each the same as X in the above formula (1-2) or the above formula (1-3)²The bonding sites of (a) each independently represent a bonding site with another structure.

The curable resin composition of < 7 > as described in any one of < 1 > to < 6 > for forming an interlayer insulating film for a rewiring layer.

< 8 > a cured film obtained by curing the curable resin composition described in any one of < 1 > to < 7 >.

< 9 > a laminate having 2 or more layers of < 8 > the cured films and having a metal layer between the cured films.

< 10 > 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 < 7 > to a substrate to form a film.

The method for producing a cured film described in < 11 > or < 10 > includes 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 < 12 > such as < 10 > or < 11 > comprises a step of heating the film at 50 to 450 ℃.

< 13 > a semiconductor device comprising < 8 > said cured film or < 9 > said laminate.

< 14 > a polyimide or a polyimide precursor comprising a structure represented by the following formula (1-1).

[ chemical formula 6]

Effects of the invention

According to an embodiment of the present invention, there are provided a curable resin composition having excellent coatability, 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.

Also, according to another embodiment of the present invention, a novel polyimide or polyimide precursor is provided.

Drawings

FIG. 1 is a schematic view of a step substrate used in examples.

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 denoted by a "to" 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.

In the present specification, the term "step" means not only an independent step but also a step which cannot be clearly distinguished from other steps as long as the intended function 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 this specification, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using a particle beam such as an electron beam or an ion beam. 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" represents both or either of "acrylate" and "methacrylate", "meth (acrylic acid)" represents both or either of "acrylic acid" and "methacrylic acid", and "(meth) acryloyl group" represents both or either of "acryloyl group" and "methacryloyl group".

In the present specification, 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 other than the solvent in all the 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 defined in terms of gel permeation chromatography (GPC measurement) and in terms of polystyrene. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined by using 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), for example, as the control. Unless otherwise indicated, these molecular weights were measured using THF (tetrahydrofuran) as eluent. And, unless otherwise specified, detection in GPC measurement uses a 254nm wavelength detector of UV rays (ultraviolet rays).

In the present specification, when the positional relationship of the layers constituting the laminate is described as "upper" or "lower", it is sufficient that another layer is present above or below the reference layer among the concerned plurality of layers. 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 with each other. Also, unless otherwise specified, the direction in which layers are stacked on a substrate is referred to as "up", or when a 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". The vertical direction is set for convenience of description, and in an actual embodiment, the "up" direction in the description may be different from the vertical direction.

In the present specification, unless otherwise specified, as each component contained in the composition, the composition may also contain two or more compounds that conform to the component. Also, unless otherwise indicated, the content of each ingredient in the composition means the total content of all compounds corresponding to the ingredient.

In the present specification, unless otherwise specified, the temperature is 23 ℃ and the gas pressure is 101,325Pa (1 gas pressure).

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

(curable resin composition)

The curable resin composition of the present invention (hereinafter, also simply referred to as "the composition of the present invention") contains at least one resin (hereinafter, also referred to as "specific resin") having a polyalkyleneoxy group and a polymerizable group and selected from the group consisting of polyimide and a polyimide precursor, a polymerization initiator, a polymerizable compound, and a solvent.

The curable resin composition of the present invention preferably further contains a thermal alkali generator or an onium salt described below. In particular, when the specific resin is a polyimide precursor, the curable resin composition of the present invention preferably further contains a thermal base generator or an onium salt, which will be described later.

The curable resin composition of the present invention has excellent coatability.

In the present specification, the term "excellent coatability of the composition" means that the coating film formed after coating and drying has a small thickness difference and has few defects such as coating unevenness due to bubbles and irregularities.

The mechanism by which the above-described effects can be obtained is not determined, but it is considered that the solubility of the specific resin in the solvent is excellent because the specific resin contains a polyalkyleneoxy group and a polymerizable group.

It is considered that by using such a specific resin having excellent solubility, the specific resin is less likely to precipitate even at a stage when the solvent is gradually volatilized when the composition is applied and dried, and thus a coating film formed after application is less likely to have a difference in film thickness and is less likely to have defects.

Further, for example, even when the curable resin composition of the present invention is used for a substrate having a step, a flat film can be easily obtained.

Further, it is considered that a cured film obtained by curing the coating film has a rigid polyimide structure and a flexible polyalkyleneoxy structure, and thus the strength (for example, elongation at break) of the cured film is easily improved.

Among them, patent document 1 neither describes nor suggests a resin containing a polyalkylene oxide group. The curable resin composition disclosed in patent document 1 has a problem of low coatability.

< specific resin >

The curable resin composition of the present invention contains a specific resin.

The specific resin has a polyalkyleneoxy group and a polymerizable group.

The specific resin may have a polyalkyleneoxy group in the main chain, but is preferably present in a side chain of the specific resin from the viewpoint of film strength of the obtained cured film.

In the present specification, "main chain" refers to a relatively longest bonding chain in a molecule of a polymer compound constituting a resin, and "side chain" refers to other bonding chains.

The specific resin preferably has a side chain having a polyalkyleneoxy group and a polymerizable group as a side chain.

[ Polyalkyleneoxy group ]

In the present invention, the polyalkyleneoxy group means a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the plural alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.

When the polyalkyleneoxy group includes a plurality of alkyleneoxy groups having different alkylenes, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, a block arrangement, or an alternating pattern arrangement.

The number of carbon atoms of the alkylene group (the number of carbon atoms including a substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 50, still more preferably 2 to 30, yet more preferably 2 to 10, yet more preferably 2 to 6, particularly preferably 2 to 4, and most preferably 2 or 3.

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

The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2 to 100, more preferably 2 to 50, still more preferably 2 to 30, particularly preferably 2 to 10, and most preferably 3 to 10.

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

[ polymerizable group ]

The polymerizable group contained in the specific resin is preferably a group containing an ethylenically unsaturated group, a cyclic ether group, or a methylol group, more preferably a vinyl group, a (meth) allyl group, a (meth) acrylamide group, a (meth) acryloyloxy group, a maleimide group, a vinylphenyl group, an epoxy group, an oxetanyl group, or a methylol group, and still more preferably a (meth) acryloyloxy group, an epoxy group, or a methylol group.

A preferable embodiment of the present invention includes an embodiment in which a polymerizable group contained in a specific resin is directly bonded to one end of the polyalkyleneoxy group. That is, the specific resin preferably has a side chain in which one terminal of the polyalkyleneoxy group is bonded to a polymerizable group.

[ Structure represented by formula (1-1) ]

The specific resin preferably contains a structure represented by the following formula (1-1) as a structure having the polyalkyleneoxy group and the polymerizable group.

The specific resin preferably contains a plurality of structures represented by the following formula (1-1). When the specific resin contains a plurality of structures represented by the formula (1-1), the structures represented by the formula (1-1) may be the same or different.

[ chemical formula 7]

-R¹-

In the formula (1-1), R¹Each of which is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and still more preferably a hydrogen atom or a methyl group.

-Z¹-

In the formula (1-1), Z¹Represents a group containing a polymerizable group.

Z¹The polymerizable group preferably includes at least one group selected from the group consisting of an ethylenically unsaturated group, a cyclic ether group, and a methylol group, more preferably includes a vinyl group, a (meth) allyl group, a (meth) acrylamide group, a (meth) acryloyloxy group, a maleimide group, a vinylphenyl group, an epoxy group, an oxetanyl group, or a methylol group, and more preferably includes a (meth) acryloyloxy group, an epoxy group, or a methylol group.

And, Z¹A group represented by the following formula (Z-1) is preferred.

[ chemical formula 8]

In the formula (Z-1), L represents a single bond or a nz + 1-valent linking group, nz represents an integer of 1 or more, Z²Represents a polymerizable group and represents a bonding site with an oxygen atom in the formula (1-1).

In the formula (Z-1), L is preferably a single bond or an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an ether bond (-O-), a carbonyl group (-C (═ O) -), a thioether bond (-O-), a sulfonyl group (-S (═ O)₂-)、-NR^NOr two or more groups bonded to each other, more preferably a single bond, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group. R is as defined above^NRepresents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, still more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

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

The aromatic hydrocarbon group is more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, still more preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms, and yet more preferably an aromatic hydrocarbon group having 6 carbon atoms.

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

In the formula (Z-1), preferably nz is 1, and L is a single bond or an alkylene group, an arylene group, an ether bond (-O-), a carbonyl group (-C (═ O) -), a thioether bond (-O-), a sulfonyl group (-S (═ O)₂-)、-NR^NOr two or more groups bonded to each other, more preferably nz is 1, and L is a single bond or an alkylene group having 1 to 10 carbon atoms, a phenylene group, an ether bond (-O-), a carbonyl group (-C (═ O) -), a thioether bond (-O-), a sulfonyl group (-S (═ O)₂-)、-NR^NOr two or more groups bonded to these.

In the formula (Z-1), Z²More preferably a vinyl group, (meth) allyl group, (meth) acrylamide group, (meth) acryloyloxy group, maleimido group, vinylphenyl group, epoxy group, oxetanyl group or hydroxymethyl group, and still more preferably a (meth) acryloyloxy group, epoxy group or hydroxymethyl group.

-n-

In the formula (1-1), n is preferably an integer of 2 to 100, more preferably an integer of 2 to 50, further preferably an integer of 2 to 30, particularly preferably an integer of 2 to 10, and most preferably an integer of 3 to 10.

-m-

In the formula (1-1), m is preferably an integer of 2 to 50, more preferably an integer of 2 to 30, further preferably an integer of 2 to 10, further preferably an integer of 2 to 6, particularly preferably an integer of 2 to 4, and most preferably 2 or 3.

The specific resin preferably contains, as the structure represented by the formula (1-1), at least one structure selected from the group consisting of a structure represented by the following formula (1-1-1), a structure represented by the following formula (1-1-2), and a structure represented by the following formula (1-1-3).

[ chemical formula 9]

In the formulae (1-1-1) to (1-1-3), n and Z¹Are as defined in formula (1-1) with n and Z, respectively¹The same and the same preferred mode.

In formulae (1-1-1) to (1-1-3), a bond to another structure is represented.

[ Structure represented by formula (1-2) ]

The specific resin preferably has a structure represented by the following formula (1-2) as a structure containing the structure represented by the above formula (1-1).

The specific resin preferably has a structure represented by the formula (1-2) in the main chain. That is, L in the formula (1-2) is preferable¹The structure represented is contained in the main chain of the specific resin.

The specific resin preferably contains a plurality of structures represented by the formula (1-2). When the specific resin contains a plurality of structures represented by the formula (1-2), the structures represented by the formula (1-2) may be the same or different.

[ chemical formula 10]

-L¹-

L¹B + 2-valent linking group, preferably aliphatic hydrocarbon group, aromatic hydrocarbon group, or a group formed by at least one of these groups and ether bond, carbonyl group, thioether bond, sulfonyl group and-NR^N-at least one bonded group of (a). R is as defined above^NRepresents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, still more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

The aliphatic hydrocarbon group is preferably an aliphatic saturated hydrocarbon group having 2 to 30 carbon atoms, and more preferably an aliphatic saturated hydrocarbon group having 2 to 10 carbon atoms.

The aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon ring group having a ring member number of 6 to 20.

The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, preferably an aliphatic hydrocarbon group having 6 to 12 carbon atoms, and more preferably an aromatic hydrocarbon group having 6 carbon atoms.

Among these, L is L from the viewpoint of solvent solubility¹The group containing an aliphatic hydrocarbon ring group or an aromatic hydrocarbon ring group is preferable, and the group containing an aromatic hydrocarbon ring group is more preferable.

And, L¹The resin composition preferably contains at least one structure selected from the group consisting of structures represented by any one of the following formulae (A-1) to (A-5), and more preferably any one of the following formulae (A-1) to (A-5).

[ chemical formula 11]

In the formulae (A-1) to (A-5), R^A11～R^A14、R^A21～R^A24、R^A31～R^A38、R^A41～R^A48And R^A51～R^A58Each independently represents a hydrogen atom, an alkyl group, a cyclic alkyl group, an alkoxy group, a hydroxyl group, a cyano group, a haloalkyl group, a halogen atom or X in the above formula (1-2) or the above formula (1-3)²Bonding site of, L^A31And L^A41Each independently represents a single bond, carbonyl group, sulfonyl group, 2-valent saturated hydrocarbon group, 2-valent unsaturated hydrocarbon group, hetero atom, heterocyclic group or halogenated alkylene group, R^A11～R^A14、R^A21～R^A24、R^A31～R^A38、R^A41～R^A48And R^A51～R^A58In the formula (1), b are independently X in the formula (1-2) or the formula (1-3)²The bonding sites of (a) each independently represent a bonding site with another structure.

Among these, L is¹Preferably a structure represented by the formula (A-1), the formula (A-2), the formula (A-3) or the formula (A-4).

In the formula (A-1), R^A11～R^A14Preferably independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a cyano group, a haloalkyl group having 1 to 3 carbon atoms or a halogen atom, more preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a haloalkyl group having 1 to 3 carbon atoms, and still more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, from the viewpoint of solvent solubility.

And, R^A11～R^A14Wherein b are the same as X in the formula (1-2) or the formula (1-3) described later²The bonding site of (3), preferably R^A13And X²Or R is a bonding site of^A12And R^A14And X²The bonding site of (3).

As the above-mentioned R^A11～R^A14The halogen atom in the above-mentioned haloalkyl group or the above-mentioned halogen atom in the above-mentioned haloalkyl group may be a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like, and is preferably a chlorine atom or a bromine atom.

In the formula (A-2), R^A21～R^A24Are each as defined for R in the formula (A-1)^A11～R^A14The same and the same preferred mode.

And, R^A21～R^A24Wherein b are the same as X in the formula (1-2) or the formula (1-3) described later²The bonding site of (3).

In the formula (A-3), R^A31～R^A38Preferably independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a cyano group, a haloalkyl group having 1 to 3 carbon atoms or a halogen atom, from the viewpoint of solvent solubilityMore preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a haloalkyl group having 1 to 3 carbon atoms, and still more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

As the above-mentioned R^A31～R^A38The halogen atom in the above-mentioned haloalkyl group or the above-mentioned halogen atom in the above-mentioned haloalkyl group may be a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like, and is preferably a chlorine atom or a bromine atom.

And, R^A31～R^A38Wherein b are the same as X in the formula (1-2) or the formula (1-3) described later²The bonding site of (3), preferably R^A31And R^A36And X²The bonding site of (3).

In the formula (A-3), L^A31Preferably represents a single bond, a C1-6 saturated C2-valent hydrocarbon group, a C5-24 unsaturated C2-valent hydrocarbon group, -O-, -S-, -NR-^NThe-heterocyclic group or the C1-6 haloalkylene group is preferably a single bond, a C1-6 saturated hydrocarbon group, -O-or a heterocyclic group, and more preferably a single bond or-O-.

R is as defined above^NRepresents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, still more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

The above-mentioned 2-valent unsaturated hydrocarbon group may be a 2-valent aliphatic unsaturated hydrocarbon group, may be a 2-valent aromatic hydrocarbon group, and is preferably a 2-valent aromatic hydrocarbon group.

The heterocyclic group is preferably a group obtained by removing two hydrogen atoms from an aliphatic or aromatic heterocyclic ring, and more preferably a group obtained by removing two hydrogen atoms from a ring structure such as a pyrrolidine ring, tetrahydrofuran ring, tetrahydrothiophene ring, pyrrole ring, furan ring, thiophene ring, piperidine ring, tetrahydropyran ring, pyridine ring, or morpholine ring. These heterocyclic rings may further have a condensed ring with other heterocyclic rings or hydrocarbon rings.

The number of ring members of the heterocycle is preferably 5 to 10, more preferably 5 or 6.

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

Examples of the halogen atom in the above-mentioned haloalkylene group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a chlorine atom or a bromine atom is preferable.

In the formula (A-4), R^A41～R^A48Are each as defined for R in the formula (A-3)^A31～R^A38The same and the same preferred mode.

And, R^A41～R^A48Wherein b are the same as X in the formula (1-2) or the formula (1-3) described later²The bonding site of (3), preferably R^A41And R^A48And X²The bonding site of (3).

In the formula (A-4), L^A41With L in the formula (A-3)^A31The same and the same preferred mode.

In the formula (A-5), R^A51～R^A58Are each as defined for R in the formula (A-1)^A11～R^A14The same and the same preferred mode.

In the formulae (a-1) to (a-5), each is preferably independently a bonding site to the main chain in the resin.

-X²-

In the formula (1-2), X²Represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond, and is preferably an ester bond or an ether bond.

And, X²The method may be determined in consideration of the synthesis method and the like.

X²In the case of an ester bond, the carbon atom which may be an ester bond may be bonded to L¹Bonded, also being an oxygen atom and L¹And (4) bonding.

X²In the case of a urethane bond, it is preferable that the oxygen atom of the urethane bond is bonded to L¹And (4) bonding.

X²When the group is an amide bond, the carbon atom of the amide bond is preferably bonded to L¹And (4) bonding.

-L²-

In the formula (1-2), L²Preferably represents a single bond or a + 1-valent linking group, a single bond or aliphatic hydrocarbon group, aromatic hydrocarbon group, ether bond, carbonyl group, thioetherBond, sulfonyl, -NR^NOr two or more groups bonded to each other, more preferably a single bond, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group. R is as defined above^NRepresents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, still more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

-X¹-

In the formula (1-2), X¹The structure represented by the above formula (1-1) is shown, and a preferable embodiment is described in the description of the formula (1-1).

-a-

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

-b-

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

[ repeating units represented by the formula (1-3) ]

The specific resin preferably contains a repeating unit represented by the following formula (1-3) as a repeating unit containing a structure represented by the formula (1-1).

The specific resin preferably has a repeating unit represented by the formula (1-3) in the main chain.

[ chemical formula 12]

In the formula (1-3), L¹Represents a b +2 valent linking group, X²Represents an ester bond or a urethane bondUrea bond, amide bond or ether bond, L²Represents a single bond or an a + 1-valent linking group, X¹Represents a structure represented by the formula (1-1), a represents an integer of 1 or more, b represents an integer of 1 or more, L⁴Represents a structure represented by the following formula (L4-1) or formula (L4-2), wherein X is present in plural²、L²、X¹Or a, a plurality of X²、L²、X¹Or a may be the same or different.

[ chemical formula 13]

-L¹、X²、L²、X¹A and b-

In the formula (1-3), L¹、X²、L²、X¹A and b are as defined for L in formula (1-2)¹、X²、L²、X¹A and b are the same, and the preferred embodiment is the same.

-L⁴-

< (L4-1) >)

In the formula (L4-1), R¹¹⁵The organic group having a valence of 4 and containing an aromatic ring is preferable, and the group represented by the following formula (5) or (6) is more preferable.

[ chemical formula 14]

R¹¹²Preferably a 2-valent linking group, 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 two or more of these, more preferably a single bondSelected from the group consisting of C1-3 alkylene 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. Each independently represents a bonding site with another structure.

With respect to R in the formula (L4-1)¹¹⁵Specific examples of the 4-valent organic group include tetracarboxylic acid residues remaining after removal of the acid dianhydride group from the tetracarboxylic acid dianhydride. The tetracarboxylic dianhydride may be used alone or in combination of two or more. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).

[ chemical formula 15]

R¹¹⁵Represents a 4-valent organic group. R¹¹⁵With R of the formula (L4-1)¹¹⁵The same is true.

Specific examples of the tetracarboxylic acid dianhydride include tetracarboxylic acid dianhydrides selected from the group consisting of pyromellitic acid, pyromellitic acid dianhydride (PMDA), 3,3 ', 4, 4' -biphenyltetracarboxylic acid dianhydride, 3,3 ', 4, 4' -diphenyl sulfide 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, 4, 4' - (hexafluoroisopropylidene) diphthalic acid dianhydride, 2,3,6, 7-naphthalenetetracarboxylic acid dianhydride, 1,4,5, 7-naphthalenetetracarboxylic dianhydride, 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' -biphenyltetracarboxylic dianhydride, 3,4, 9, 10-perylenetetracarboxylic dianhydride, 1,2,4, 5-naphthalenetetracarboxylic dianhydride, 1,4,5, 8-naphthalenetetracarboxylic dianhydride, 1, 8, 9, 10-phenanthrenecarboxylic dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 1, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 1,2, 3, 4-benzenetetracarboxylic acid dianhydride, and at least one of C1-6 alkyl derivatives and C1-6 alkoxy derivatives thereof.

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

[ chemical formula 16]

< formula (L4-2) >)

In the formula (L4-2), A¹And A²Each independently represents an oxygen atom or-NH-, preferably an oxygen atom.

In the formula (L4-2), R¹¹³And R¹¹⁴Each independently represents a hydrogen atom or a 1-valent organic group, preferably R¹¹³And R¹¹⁴At least one of them contains a polymerizable group, and more preferably both contain a polymerizable group.

As R¹¹³Or R¹¹⁴The polymerizable group in (2) includes the same groups as those mentioned for Z in the above formula (1-1)¹The same polymerizable group as in (1).

R¹¹³Or R¹¹⁴Also preferred is a vinyl group, an allyl group, a (meth) acryloyl group, or a group represented by the following formula (III).

[ chemical formula 17]

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

In the formula (III), R²⁰¹An alkylene group having 2 to 12 carbon atoms, -CH₂CH(OH)CH₂Or a (poly) alkyleneoxy group having 4 to 30 carbon atoms (the alkylene group preferably has 1 to 12 carbon atoms, more preferably has 1 to 12 carbon atoms)1 to 6, especially 1 to 3; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3). The (poly) alkyleneoxy group represents an alkyleneoxy group or a polyalkyleneoxy group.

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 preferably R²⁰⁰Is methyl, R²⁰¹Is an ethylene group.

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

As a preferred embodiment, R in the formula (L4-2) is mentioned¹¹³Or R¹¹⁴The 1-valent organic group(s) of (a) has one, two or three (preferably one) acid groups, an aliphatic group, an aromatic group, an aralkyl group, etc. Specifically, the aromatic group has 6 to 20 carbon atoms and an aralkyl group has 7 to 25 carbon atoms. 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 R¹¹⁴Preferred is a group having a hydroxyl group.

As 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 more preferably an alkyl group substituted with an aromatic group.

The number of carbon atoms of the alkyl group is preferably 1 to 30 (3 or more in the case of a cyclic group). The alkyl group may be linear, branched, or cyclic. Examples of the straight-chain or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, an octadecyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 1-ethylpentyl group, and a 2-ethylhexyl group. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of monocyclic cyclic alkyl groups 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 perylene 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).

Also, the polyimide precursor preferably has a fluorine atom in the repeating unit. 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 a specific resin for the purpose of improving adhesion to a base material. Specifically, examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane.

In the formula (L4-2), R¹¹⁵With R in the formula (L4-1)¹¹⁵The same and the same preferred mode.

Resin species-

In the formula (1-3), L⁴In the case of the structure represented by the group represented by the formula (L4-1), the specific resin is preferably polyimide.

In the formula (1-3), L⁴In the case of the structure represented by the group represented by the formula (L4-2), the specific resin is preferably a polyimide precursor.

Content-

When the specific resin contains the repeating unit represented by the formula (1-3), the content of the repeating unit represented by the formula (1-3) is preferably 0.1 to 80% by mass, more preferably 0.5 to 70% by mass, and still more preferably 1 to 60% by mass, based on the total mass of the specific resin.

The specific resin may contain only one kind of repeating unit represented by the formula (1-3), or may contain two or more kinds.

[ Structure represented by formula (1-1B) ]

The specific resin may have a structure represented by the following formula (1-1B) and may have a polymerizable group at another site of the specific resin.

The specific resin may have a structure represented by the following formula (1-1B) in the main chain or may have a structure in the side chain, and is preferably in the main chain from the viewpoint of film strength. In addition, it preferably has a side chain in view of coatability.

[ chemical formula 18]

In the formula (1-1B), R^B1Are respectively independentEach independently represents a hydrogen atom or an alkyl group, nB represents an integer of 2 or more, mB represents an integer of 2 or more, and each independently represents a bonding site to another structure.

-R^B1-

In the formula (1-1B), R^B1Each of which is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and still more preferably a hydrogen atom or a methyl group.

-nB-

In the formula (1-1B), nB is preferably an integer of 2 to 100, more preferably an integer of 2 to 50, further preferably an integer of 2 to 30, particularly preferably an integer of 2 to 10, and most preferably an integer of 3 to 10.

-mB-

In the formula (1-1B), m is preferably an integer of 2 to 50, more preferably an integer of 2 to 30, further preferably an integer of 2 to 10, further preferably an integer of 2 to 6, particularly preferably an integer of 2 to 4, and most preferably 2 or 3.

The specific resin preferably contains, as the structure represented by the formula (1-1B), at least one structure selected from the group consisting of a structure represented by the following formula (1-1B-1), a structure represented by the following formula (1-1B-2), and a structure represented by the following formula (1-1B-3).

[ chemical formula 19]

In the formulae (1-1B-1) to (1-1B-3), nB is the same as nB in the formula (1-1B), and the preferable mode is the same.

In the formulae (1-1B-1) to (1-1B-3), the bond sites to other structures are each independently represented.

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

The specific resin preferably contains a structure represented by the following formula (1-2B) or a structure represented by the following formula (1-2C) as the structure containing the formula (1-1B).

When the specific resin contains a structure represented by the following formula (1-2B), the specific resin preferably contains a structure represented by the following formula (1-2B) in the main chain.

When the specific resin contains a structure represented by the following formula (1-2C), the specific resin preferably contains a structure represented by the following formula (1-2C) at a terminal of a main chain or a side chain, and more preferably contains a structure in a side chain.

The specific resin preferably contains a plurality of structures represented by the formula (1-2B) or the formula (1-2C). When the specific resin contains a plurality of structures represented by the formula (1-2B) or a plurality of structures represented by the formula (1-2C), the plurality of structures represented by the formula (1-2B) or the plurality of structures represented by the formula (1-2C) may be the same or different.

[ chemical formula 20]

*-L^B1-L^X-L^B2-* (1-2B) *-L^B3-L^X-R^B2 (1-2C)

In the formula (1-2B), L^B1And L^B2Each independently represents a single bond or a 2-valent linking group, L^XThe structure represented by the above formula (1-1B) is shown.

In the formula (1-2C), L^B3Represents a single bond or a 2-valent linking group, L^XRepresents a structure represented by the formula (1-1B) above, R^B2Represents a hydrogen atom or a substituent having no polymerizable group.

In the formula (1-2B), L^B1And L^B2Preferably independently of one another, a single bond or alkylene, arylene, ether linkage, carbonyl, thioether linkage, -NR^NOr two or more groups bonded to each other, more preferably a single bond, an alkylene group or an arylene group, and still more preferably a single bond or an alkylene group. R is as defined above^NRepresents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, still more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

The alkylene group is preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, and still more preferably an ethylene group or a propylene group.

In the formula (1-2B), L^XThe structure represented by the above formula (1-1B) is shown, and preferred embodiments are as described in the above formula (1-1B).

In the formula (1-2C), L^B3Means ofAnd L in the above formula (1-2B)^B1Or L^B2The same and the same preferred mode.

In the formula (1-2C), L^XThe structure represented by the above formula (1-1B) is shown, and preferred embodiments are as described in the above formula (1-1B).

In the formula (1-2C), R^B2The substituent is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and still more preferably an alkyl group, as long as it is a known substituent such as a hydrogen atom, an alkyl group, an aryl group, or a halogen atom.

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

The aryl group is preferably an alkyl group having 6 to 20 carbon atoms, more preferably an alkyl group having 6 to 12 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms.

[ repeating units represented by the formula (1-3B) ]

When the specific resin contains a structure represented by the formula (1-2B), the specific resin preferably contains a repeating unit represented by the following formula (1-3B).

[ chemical formula 21]

In the formula (1-3B), L^B1And L^B2Each independently represents a single bond or a 2-valent linking group, L^XRepresents a structure represented by the above formula (1-1B), L^B4The structure represented by the formula (L4-1) or the formula (L4-2) in the formula (1-3) is shown.

In the formula (1-3B), L^B1、L^B2And L^XAre each as defined for L in the formula (1-2B)^B1、L^B2And L^XThe same and the same preferred mode.

In the formula (1-3B), L^B4Has the same meaning as that of L in the above formula (1-3)⁴The same and the same preferred mode.

Resin species-

In the formula (1-3B)，L^B4In the case of the structure represented by the group represented by the formula (L4-1), the specific resin is preferably polyimide.

In the formula (1-3B), L^B4In the case of the structure represented by the group represented by the formula (L4-2), the specific resin is preferably a polyimide precursor.

Content-

When the specific resin contains the repeating unit represented by the formula (1-3B), the content of the repeating unit represented by the formula (1-3B) is preferably 0.1 to 80% by mass, more preferably 10 to 70% by mass, and still more preferably 20 to 60% by mass, based on the total mass of the specific resin.

The specific resin may contain only one kind of repeating unit represented by the formula (1-3B), or may contain two or more kinds.

[ Structure represented by formula (1-3C) ]

When the specific resin contains a structure represented by the formula (1-2C), the specific resin preferably contains a structure represented by the following formula (1-3C) as a structure containing a structure represented by the formula (1-2C).

The specific resin preferably has a structure represented by the formula (1-3C) in the main chain. Namely, L in the formula (1-3C)^B5The structure represented is preferably contained in the main chain of the specific resin.

The specific resin preferably contains a plurality of structures represented by the formulae (1 to 3C). When the specific resin contains a plurality of structures represented by the formulae (1 to 3C), the structures represented by the formulae (1 to 3C) may be the same or different.

[ chemical formula 22]

In the formula (1-3C), L^B5Represents nB2+ 2-valent linking group, X^B2Represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond, X^B1Represents a structure represented by the above formula (1-2C), nB2 represents an integer of 1 or more, and a plurality of X's are present^B1Or X^B2When a plurality of X^B1Or X^B2May be the same or different.

In the formula (1-3C), L^B5The meaning of (1) and the above formula2) L in (1)¹The same and the same preferred mode.

Formula L^B5When any of the structures represented by the formulae (A-1) to (A-5) is included, "R" in the description of the formulae (A-1) to (A-5)^A11～R^A14、R^A21～R^A24、R^A31～R^A38、R^A41～R^A48And R^A51～R^A58Wherein b are independently X in the formula (1-2) or the formula (1-3)²The bonding site of (1), "replaceable with" R^A11～R^A14、R^A21～R^A24、R^A31～R^A38、R^A41～R^A48And R^A51～R^A58Wherein nB2 are respectively X in the formula (2-1)^B2The bonding site of (a) ".

In the formula (1-3C), X^B2Has the same meaning as X in the above formula (1-2)²The same and the same preferred mode.

In the formula (1-3C), X^B1The structure represented by the above formula (1-2C) is shown, and preferred embodiments are as described in the above formula (1-2C).

In the formula (1-3C), nB2 has the same meaning as b in the formula (1-2) described above, and the preferable embodiment is also the same.

[ repeating units represented by the formula (1-4C) ]

When the specific resin contains a structure represented by the formula (1-2C) or a structure represented by the formula (1-3C), the specific resin preferably contains a repeating unit represented by the following formula (1-4C).

[ chemical formula 23]

In the formula (1-4C), L^B5Represents nB2+ 2-valent linking group, X^B2Represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond, X^B1Represents a structure represented by the above formula (1-2C), nB2 represents an integer of 1 or more, L^B4Represents a structure represented by the formula (L4-1) or the formula (L4-2) in the formula (1-3), wherein a plurality of X's are present^B1Or X^B2When a plurality of X^B1Or X^B2May be the same or different.

In the formula (1-4C), L^B5、X^B2、X^B1And nB2 are as defined above for L in the formula (1-3C)^B5、X^B2、X^B1And nB2, and the preferred mode is the same.

In the formula (1-4C), L^B4Has the same meaning as that of L in the above formula (1-3)⁴The same and the same preferred mode.

Resin species-

In the formula (1-4C), L^B4In the case of the structure represented by the group represented by the formula (L4-1), the specific resin is preferably polyimide.

In the formula (1-4C), L^B4In the case of the structure represented by the group represented by the formula (L4-2), the specific resin is preferably a polyimide precursor.

Content-

When the specific resin contains the repeating unit represented by the formula (1-4C), the content of the repeating unit represented by the formula (1-4C) is preferably 0.1 to 80% by mass, more preferably 10 to 80% by mass, and still more preferably 20 to 75% by mass, based on the total mass of the specific resin.

The specific resin may contain only one kind of repeating unit represented by the formula (1-4C), or may contain two or more kinds.

[ repeating Unit represented by the formula (2-1) ]

The specific resin may further contain a repeating unit represented by the following formula (2-1).

When the specific resin contains a structure represented by the formula (1-2B) or the formula (1-2C), the specific resin contains a polymerizable group in a structure other than the structure represented by the formula (1-2B) or the formula (1-2C).

When the specific resin is a polyimide, the specific resin preferably further contains L represented by the following formula (2-1) as a repeating unit having a polymerizable group²¹Is a repeating unit of formula (L4-1).

When the specific resin is a polyimide precursor, the specific resin is preferably L in the repeating unit represented by the formula (1-3B)^B4Or L in the repeating unit represented by the formula (1-4C)^B4Contains a polymerizable group, orFurther comprises a compound represented by the following formula (2-1) and L²¹Is a repeating unit of formula (L4-2). L in the repeating unit represented by the formula (1-3B)^B4Or L in the repeating unit represented by the formula (1-4C)^B4When the polymerizable group is contained, L is preferably the above-mentioned^B4Is represented by formula (L4-2) and R in formula (L4-2)¹¹³And R¹¹⁴At least one of which comprises a polymerizable group.

[ chemical formula 24]

In the formula (2-1), L²¹Represents a b2+2 valent linking group, X²²Represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond, X²¹Represents a group containing a polymerizable group, X²¹And X²²Is a group not containing a polyoxyalkylene group, b2 represents an integer of 1 or more, L⁴Represents a structure represented by the formula (L4-1) or the formula (L4-2) in the formula (1-3), wherein a plurality of X's are present²²Or X²¹When a plurality of X²²Or X²¹May be the same or different.

In the formula (2-1), L²¹、X²²B2 and L⁴Are as defined above for L in the formula (1-3)¹、X²B and L⁴The same and the same preferred mode.

Formula L²¹When any of the structures represented by the formulae (A-1) to (A-5) is included, "R" in the description of the formulae (A-1) to (A-5)^A11～R^A14、R^A21～R^A24、R^A31～R^A38、R^A41～R^A48And R^A51～R^A58Wherein b are independently X in the formula (1-2) or the formula (1-3)²The bonding site of (1), "replaceable with" R^A11～R^A14、R^A21～R^A24、R^A31～R^A38、R^A41～R^A48And R^A51～R^A58Wherein b2 are respectively X in the formula (2-1)²²The bonding site of (a) ".

In the formula (2-1),X²¹the group is preferably a group represented by the formula (Z-1).

Resin species-

In the formula (2-1), L⁴In the case of the structure represented by the group represented by the formula (L4-1), the specific resin is preferably polyimide.

In the formula (2-1), L⁴In the case of the structure represented by the group represented by the formula (L4-2), the specific resin is preferably a polyimide precursor.

Content-

When the specific resin contains the repeating unit represented by the formula (2-1), the content of the repeating unit represented by the formula (1-4C) is preferably 0.1 to 80% by mass, more preferably 10 to 80% by mass, and still more preferably 20 to 75% by mass, based on the total mass of the specific resin.

The specific resin may contain only one kind of repeating unit represented by the formula (2-1), or may contain two or more kinds.

[ other repeating units ]

A repeating unit represented by the formula (4)

The specific resin may further contain a repeating unit represented by the following formula (4).

When the specific resin contains a repeating unit represented by the following formula (4), the specific resin is preferably polyimide.

When the specific resin contains a repeating unit represented by the following formula (4), the specific resin preferably contains a repeating unit represented by the following formula (4) in the main chain.

[ chemical formula 25]

In the formula (4), R¹³¹Represents a 2-valent organic group, R¹³²Represents a 4-valent organic group.

As R¹³¹Examples of the 2-valent organic group represented by the formula (1) include R¹¹¹The same groups, and the preferred ranges are also the same. As R¹³²Examples of the 4-valent organic group represented by the formula (L4-1) include R¹¹⁵The same groups, and the preferred ranges are also the same.

R in the structure represented by the formula (1-1) in the specific resin¹When the substituent does not contain a polymerizable group, R¹³¹And R¹³²At least one of the polyimide resins may contain a polymerizable group, or may have a structure containing a polymerizable group at the end of the polyimide.

When the specific resin contains the repeating unit represented by the formula (4) (for example, when the specific resin is a polyimide), the specific resin preferably contains the repeating unit represented by the formula (4) in an amount of 1 to 80% by mass, more preferably 10 to 70% by mass, and still more preferably 20 to 60% by mass, based on the total mass of the specific resin.

When the specific resin is a polyimide, the specific resin may be a resin in which the repeating unit represented by formula (4) is not substantially contained, and in such a resin, the content of the repeating unit represented by formula (4) is preferably 5% by mass or less, and more preferably 1% by mass or less, based on the total mass of the specific resin.

When the specific resin is a polyimide, the total content of the repeating unit represented by the formula (1-3), the repeating unit represented by the formula (1-3B), the repeating unit represented by the formula (1-4C), the repeating unit represented by the formula (2-1), and the repeating unit represented by the formula (4) contained in the specific resin (in the repeating units, the repeating unit not contained may be present) is preferably 50 to 100% by mass, more preferably 60 to 99% by mass, and still more preferably 70 to 95% by mass, based on the total mass of the specific resin.

A repeating unit represented by the formula (1) -

The specific resin may further contain a repeating unit represented by the following formula (1).

When the specific resin contains a repeating unit represented by the following formula (1), the specific resin is preferably a polyimide precursor.

When the specific resin contains a repeating unit represented by the following formula (1), the specific resin preferably has a repeating unit represented by the following formula (1) in the main chain.

[ chemical formula 26]

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.

In the formula (1), A¹、A²、R¹¹³、R¹¹⁴And R¹¹⁵Are each independently of A in the above formula (L4-2)¹、A²、R¹¹³、R¹¹⁴And R¹¹⁵The same and the same preferred mode.

In the formula (1), R¹¹¹Represents a 2-valent organic group. Examples of the 2-valent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, and a combination of two or more thereof, and 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 two or more thereof, 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, and the like. One diamine may be used alone, or two or more diamines may be used.

Specifically, the diamine preferably contains a linear aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination of two or more of these groups, 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 27]

Wherein A is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, and is preferably-O-, -C (═ O) -, -S-, -S (═ O)₂-, -NHC (═ O) -, or a combination of two or more of these, 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 ' -or 3,3 ' -diaminobiphenyl, 4 ' -diaminodiphenyl ether, 3-diphenyl ether, 4 ' -or 3,3 ' -diaminodiphenylmethane, 4 ' -or 3,3 ' -diaminodiphenylsulfone, 4 ' -or 3,3 ' -diaminodiphenylsulfide, 4 ' -or 3,3 ' -diaminobenzophenone, 3 ' -dimethyl-4, 4 ' -diaminobiphenyl, 2 ' -dimethyl-4, 4 ' -diaminobiphenyl (4,4 ' -diamino-2, 2 ' -dimethylbiphenyl), mixtures thereof, 3,3 '-dimethoxy-4, 4' -diaminobiphenyl, bis (4-amino-3-carboxyphenyl) methane, 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, 4,4 '-diaminop-triphenyl, 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, 3,3 '-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, 4, 4' -diaminodiphenylsulfone, 3,3 ', 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, 4, 6-dihydroxy-1, 3-phenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, 2, 7-diaminofluorene, 2, 5-diaminopyridine, 1, 2-bis (4-aminophenyl) ethane, diaminobenzanilide, diaminobenzoic acid, esters of benzoic acid, and esters of benzoic 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, 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, toluene, xylene, or mixtures of various mixtures thereof, At least one diamine selected from 2,2 ', 5, 5', 6,6 '-hexafluorotolidine and 4, 4' -diaminotetrabiphenyl.

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

[ chemical formula 28]

[ chemical formula 29]

Further, as a preferable example, a diamine having at least two alkylene glycol units in the main chain can be cited. The diamine is preferably a diamine containing two or more ethylene glycol chains or propylene glycol chains in total in one molecule, and more preferably a diamine containing no aromatic ring. Specific examples thereof include JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (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 30]

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 with-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 two or more of these. 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 preferred. In particular, the 2-valent organic group represented by formula (61) is more preferable from the viewpoint of i-ray transmittance and ready availability.

[ chemical formula 31]

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

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 32]

In the 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, and 4, 4' -diaminooctafluorobiphenyl. One of these may be used, or two or more of these may be used in combination.

When the specific resin contains the repeating unit represented by the formula (1) (for example, when the specific resin is a polyimide precursor), the specific resin preferably contains the repeating unit represented by the formula (1) in an amount of 1 to 90% by mass, more preferably 10 to 80% by mass, and still more preferably 20 to 70% by mass, based on the total mass of the specific resin.

When the specific resin is a polyimide precursor, the specific resin may be a form that does not substantially contain the repeating unit represented by formula (1), and in this form, the content of the repeating unit represented by formula (1) is preferably 5% by mass or less, and more preferably 1% by mass or less, relative to the total mass of the specific resin.

When the specific resin is a polyimide precursor, the total content of the repeating unit represented by the formula (1-3), the repeating unit represented by the formula (1-3B), the repeating unit represented by the formula (1-4C), the repeating unit represented by the formula (2-1), and the repeating unit represented by the formula (1) contained in the specific resin (in the repeating units, the repeating unit not contained may be present) is preferably 50 to 100% by mass, more preferably 60 to 99% by mass, and still more preferably 70 to 95% by mass, based on the total mass of the specific resin.

[ contents ]

The content of the specific resin in the curable resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, relative to the total solid content of the curable resin composition, from the viewpoint of improving the elongation at break of the obtained cured film.

The upper limit of the content is preferably 99.5% by mass or less, more preferably 99% by mass or less, still more preferably 98% by mass or less, yet more preferably 97% by mass or less, and still more preferably 95% by mass or less, from the viewpoint of improving the resolution of the curable resin composition.

[ physical Properties of specific resins ]

Molecular weight-

The weight average molecular weight (Mw) of the specific resin 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) of the specific resin 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 specific resin 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).

Acid value-

When the curable resin composition is used for solvent development described later, the acid value of the specific resin is preferably 1mmol/g or less, more preferably 0.5mmol/g or less, and still more preferably 0.3 mmol/g. The lower limit of the acid value is not particularly limited as long as it is 0mmol/g or more.

When the curable resin composition is used for the alkali development described later, the acid value of the specific resin is preferably 1.2 to 7mmol/g, more preferably 1.5 to 6mmol/g, and still more preferably 2 to 5 mmol/g.

In the present invention, the acid value means the amount (mmol) of an acid group contained in 1g of the specific resin.

The acid group represents a group neutralized with a base (for example, sodium hydroxide) having a pH of 12 or higher. The acid group is preferably a group having a pKa of 10 or less.

The above acid value is measured by a known method, for example, by JIS K0070: 1992.

[ preferred embodiment of the specific resin ]

The specific resin is at least one resin selected from the group consisting of polyimide and polyimide precursor.

In the following description, the compound represented by the formula (1-3) and L⁴The repeat unit of formula (L4-1) is referred to as repeat unit PI-1.

Represented by the formula (1-3B) and L^B4The repeat unit of formula (L4-1) is referred to as repeat unit PI-2.

Represented by the formula (1-4C) and L^B4The repeat unit of formula (L4-1) is referred to as repeat unit PI-3.

Represented by the formula (2-1) and L⁴The repeat unit of formula (L4-1) is designated as repeat unit PI-4.

Represented by the formula (1-3) and L⁴The repeat unit of formula (L4-2) is referred to as repeat unit PIP-1.

Represented by the formula (1-3B) and L^B4The repeat unit of formula (L4-2) is referred to as repeat unit PIP-2.

Represented by the formula (1-4C) and L^B4The repeat unit of formula (L4-2) is referred to as repeat unit PIP-3.

Represented by the formula (2-1) and L⁴The repeat unit of formula (L4-2) is referred to as repeat unit PIP-4.

Polyimide-

When the specific resin is a polyimide, the specific resin is preferably a polyimide described in any one of PI1 to PI 3.

PI 1: polyimide comprising repeating units PI-1

PI 2: polyimide comprising repeating units PI-2 and PI-4

PI 3: polyimide comprising repeating units PI-3 and PI-4

The polyimide described in PI1 may further contain a repeating unit PIP-1.

The polyimide described in PI2 may further contain at least one selected from the group consisting of a repeating unit PIP-2 and a repeating unit PIP-4.

The polyimide described in PI3 may further contain at least one selected from the group consisting of a repeating unit PIP-3 and a repeating unit PIP-4.

The polyimide described in PI1 may further contain a repeating unit PI-4. The polyimide described in PI1 may further contain a repeating unit PI-4.

The polyimide described in PI1 to PI3 may further contain another repeating unit such as a repeating unit represented by formula (4). When the polyimide described in PI1 to PI3 contains a repeating unit represented by formula (4), the polyimide may further contain a repeating unit represented by formula (1).

When the specific resin is a polyimide, the ring closure ratio of the specific resin is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more.

The ring-closure ratio of the specific resin when the specific resin is polyimide is represented by the following formula cr (pi).

Formula CR (PI):

the ring closure ratio (%) of the specific resin (molar amount of imide ring in the specific resin)/(molar amount of imide ring in the specific resin + molar amount of structure capable of forming imide ring by ring closure in the specific resin) × 100

For example, when the specific resin is a resin including a repeating unit PI-1, a repeating unit PIP-1, a repeating unit represented by formula (4), and a repeating unit represented by formula (1), the ring closure ratio is a value represented by the following formula CR (PI) 1.

Formula CR (PI) 1:

the ring closure ratio (%) of the specific resin is (molar amount of the repeating unit PI-1 + molar amount of the repeating unit represented by formula (4))/(molar amount of the repeating unit PI-1 + molar amount of the repeating unit PIP-1 + molar amount of the repeating unit represented by formula (4)) + molar amount of the repeating unit represented by formula (1))

Polyimide precursors

When the specific resin is a polyimide precursor, the specific resin is preferably a polyimide described in any one of PIP1 to PIP5 described below.

PIP 1: polyimide precursor comprising repeating unit PIP-1

PIP 2: comprising the repeating unit PIP-2, L in the formula (1-3B)^B4Is represented by formula (L4-2), R in formula (L4-2)¹¹³And R¹¹⁴At least one of which comprises a polymerizable groupImide precursor

PIP 3: polyimide precursor comprising repeating unit PIP-2 and repeating unit PIP-4

PIP 4: comprising the repeating unit PIP-3, L in formula (1-3B)^B4Is represented by formula (L4-2), R in formula (L4-2)¹¹³And R¹¹⁴A polyimide precursor having at least one polymerizable group

PIP 5: polyimide precursor comprising repeating unit PIP-3 and repeating unit PIP-4

[ specific examples ]

Specific examples of the specific resin include specific resins used in the following examples.

[ Synthesis method ]

The specific resin is synthesized, for example, by the synthesis method shown in the synthesis examples in the examples described below.

When the specific resin is the polyimide described in PI1, the specific resin is synthesized by sequentially performing the steps described in, for example, (1) to (2) below.

(1) A step of obtaining a polyimide by reacting a diamine having a functional group such as a carboxyl group, a hydroxyl group, or an amino group with a dicarboxylic acid or a dicarboxylic acid derivative, and then forming an imide ring by a method such as thermal imidization or chemical imidization (for example, by promoting a cyclization reaction by the action of a catalyst) after the reaction

(2) A step of reacting a compound having a group capable of bonding to the functional group (e.g., a hydroxyl group, a carboxyl group which may be halogenated, an isocyanate group, etc.), a polyalkyleneoxy group, and a polymerizable group (e.g., a polyalkylene glycol monomethacrylate, etc.) with the functional group in the polyimide obtained in the above (1)

As the compound having a group capable of bonding to the functional group, a polyalkyleneoxy group and a polymerizable group, commercially available products can be used, and examples of the commercially available products include BLEMMER PE-90, PE-200, PE-350, PP-1000, PP-500, PP-800, AE-90U, AE-200, AE-400, AP-200, AP-400, AP-550 and AP-800 (all manufactured by NOF CORPORATION).

When the specific resin is the polyimide described in PI2, the specific resin is synthesized by sequentially performing the steps described in, for example, (3) to (4) below.

(3) A step of obtaining a polyimide by reacting a diamine having a polyalkyleneoxy group (e.g., bis (2- (3-aminopropoxy) ethyl) ether, a diamine having a functional group such as a carboxyl group, a hydroxyl group, an amino group, and a dicarboxylic acid or a dicarboxylic acid derivative, followed by formation of an imide ring by thermal imidization, chemical imidization (e.g., promotion of cyclization reaction by the action of a catalyst), or the like

(4) A step of reacting a compound having a group capable of bonding to the functional group (e.g., a hydroxyl group, a carboxyl group which may be halogenated, an isocyanate group, etc.) and a polymerizable group (e.g., methacryloyl chloride, etc.) with the functional group in the polyimide obtained in the above (1)

When the specific resin is the polyimide described in PI3, the specific resin is synthesized by sequentially performing the steps described in, for example, (5) to (6) below.

(5) A step of obtaining a polyimide by reacting a diamine having a functional group such as a carboxyl group, a hydroxyl group, or an amino group with a dicarboxylic acid or a dicarboxylic acid derivative, and then forming an imide ring by a method such as thermal imidization or chemical imidization (for example, by promoting a cyclization reaction by the action of a catalyst) after the reaction

(6) A step of reacting a compound having a group capable of bonding to the functional group (e.g., a hydroxyl group, a carboxyl group which may be halogenated, an isocyanate group, etc.) and a polyalkyleneoxy group (e.g., a polyalkylene glycol monoalkyl ether, etc.) and a compound having a group capable of bonding to the functional group (e.g., a hydroxyl group, a carboxyl group which may be halogenated, an isocyanate group, etc.) and a polymerizable group (e.g., hydroxyethyl methacrylate, etc.) with the functional group in the polyimide obtained in the above (1)

As a method for synthesizing the specific resin as a polyimide precursor, for example, a method of reacting a diamine with a dicarboxylic acid derivative in which at least one of a polyalkyleneoxy group and a polymerizable group is introduced to a part of a carboxylic acid is mentioned.

As the diamine, a diamine having a polyalkyleneoxy group may be used.

< other resins >

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

Examples of the other resin include polyimide, polyimide precursor, and the like, which are different from the specific resin.

When the specific resin is polyimide, the other resin is preferably polyimide.

When the specific resin is a polyimide precursor, the other resin is preferably a polyimide precursor.

[ polyimide (other resin) ]

The polyimide as the other resin preferably has a repeating unit represented by the above formula (4) from the viewpoint of the film strength of the obtained cured film.

In the polyimide, the number of the repeating units represented by the formula (4) may be one, or two or more. The polyimide may contain other kinds of repeating units in addition to the repeating unit of the above formula (4).

An embodiment of the polyimide of the present invention is a polyimide precursor having 50 mol% or more, more preferably 70 mol% or more, and particularly 90 mol% or more of the total repeating units of the repeating units represented by the formula (4). The upper limit is actually 100 mol% or less.

The polyimide preferably has a weight average molecular weight (Mw) of 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 is preferably 1.5 to 3.5, and more preferably 2 to 3.

The polyimide is obtained by, for example, cyclizing a polyimide precursor which is another resin described later by heating or the like.

[ polyimide precursor (other resin) ]

From the viewpoint of the film strength of the cured film obtained, the polyimide precursor preferably has a repeating unit represented by the above formula (1).

In the polyimide precursor, the number of the repeating units represented by the formula (1) may be one, or two or more. Further, the structural isomer of the repeating unit represented by the formula (1) may be contained. 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 50 mol% or more, more preferably 70 mol% or more, and particularly 90 mol% or more of the total repeating units represented by the formula (1). 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, and more preferably 2 to 3.

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

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

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

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

When the curable resin composition of the present invention contains another resin, the content of the other resin is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 5% by mass or more, and further preferably 10% by mass or more, based on the total solid content of the curable resin composition. The content of the other resin in the curable resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% 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 one kind of other resin, or may contain two or more kinds. When two or more are contained, the total amount is preferably in the above range.

< polymerization initiator >

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

The polymerization initiator is preferably a photopolymerization initiator.

[ 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, an active agent that produces some action with a photo-excited sensitizer and produces an active radical may be used.

The photo radical polymerization initiator preferably contains at least one compound having at least about 50 L.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 use an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer, manufactured by Varian Medical Systems, Inc.),and measured 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. Specifically, the descriptions of paragraphs 0165 to 0182 of Japanese patent laid-open publication No. 2016 and 027357 and paragraphs 0138 to 0151 of International publication No. 2015/199219 can be referred to, and the contents thereof are incorporated in the present specification.

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

In one embodiment of the present invention, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be preferably used as the photo radical polymerization initiator. More specifically, for example, an aminoacetophenone-based initiator described in Japanese patent laid-open No. 10-291969 and an acylphosphine oxide-based initiator described in Japanese patent No. 4225898 can be used.

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

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

As the aminoacetophenone-based initiator, a compound described in Japanese patent laid-open 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 more effectively improved. Among oxime compounds, oxime compounds are particularly preferable 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 preferably used as the photoradical polymerization initiator. The oxime-based photopolymerization initiator has a linking group having > C — N — O — C (═ O) -in the molecule.

[ chemical formula 33]

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.

Oxime compounds 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 and 36 to 40 described in section 0345 of Japanese patent application laid-open No. 2014-500852, and the compound (C-3) described in section 0101 of Japanese patent application laid-open No. 2013-164471.

The most preferable oxime compounds include an oxime compound having a specific substituent as shown in Japanese patent laid-open Nos. 2007-269779 and an oxime compound having a thioaryl group as shown in Japanese patent laid-open No. 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.

The photo radical polymerization initiator is preferably a trihalomethyl triazine compound, an α -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, a benzophenone compound, or an acetophenone compound, more preferably at least one compound selected from the group consisting of a trihalomethyl triazine compound, an α -aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound, still more preferably a metallocene compound or an oxime compound, and still more preferably an oxime compound.

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 34]

In the formula (I), R^I00R is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, a phenyl group or a biphenyl group substituted with at least one of an alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms and an alkyl group having 1 to 4 carbon atoms, R is^I01Is a group of the formula (II), or is a group 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 35]

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

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

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

[ thermal polymerization initiator ]

The curable resin composition of the present invention may contain a thermal polymerization initiator as a polymerization initiator, and particularly may contain a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates radicals by the energy of heat and initiates or accelerates the polymerization reaction of a compound having polymerizability. By adding the thermal radical polymerization initiator, when the specific resin is a polyimide precursor, the precursor can be cyclized, and the specific resin and the polymerizable compound are also subjected to a polymerization reaction, so that 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 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 polymerization initiator may contain only one kind, or may contain two or more kinds. When two or more thermal polymerization initiators are contained, the total amount thereof is preferably in the above range.

< polymerizable Compound >

[ radically polymerizable Compound ]

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

As the 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 the radical polymerizable groups of the radical polymerizable compound may be one or two or more, and the radical polymerizable compound preferably has two or more radical polymerizable groups, and more preferably has three or more radical polymerizable groups. The upper limit is preferably fifteen or less, more preferably ten or less, and further preferably eight 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 one 2-or more-functional radically polymerizable compound containing two or more radically polymerizable groups, and more preferably contains at least one 3-or more-functional radically polymerizable compound. 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 two 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 preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds and amides of unsaturated carboxylic acids and polyhydric amine compounds. Further, addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxyl group, an amino group, or a mercapto group with monofunctional or polyfunctional isocyanates or 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 or amides having electrophilic substituent groups such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having dissociative substituent groups such as halogen groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also preferable. As another example, instead of the unsaturated carboxylic acid, a compound group such as unsaturated phosphonic acid, a vinyl benzene derivative such as styrene, vinyl ether, allyl ether, or the like may 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 (acryloyloxypropyl) ether, tris (acryloyloxyethyl) isocyanurate, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylating, urethanes of (meth) acrylic acid esters described in Japanese patent publication No. 48-041708, Japanese patent publication No. 50-006034, Japanese patent publication No. 51-037193, urethane esters of (meth) acrylic acid described in Japanese patent publication No. 51-037193, and the like, The polyester acrylates described in Japanese unexamined patent publication No. 48-064183, Japanese Kokoku publication No. 49-043191 and Japanese Kokoku publication No. 52-030490, and the polyfunctional acrylates or methacrylates such as epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of Japanese patent laid-open No. 2008-292970 are also preferable. Further, there can be mentioned polyfunctional (meth) acrylates obtained by reacting a compound having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth) acrylate with a polyfunctional carboxylic acid.

Further, as a preferable radical polymerizable compound other than the above, compounds having a fluorene ring and having two or more ethylenically unsaturated bond-containing groups 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, the compounds described in paragraphs 0048 to 0051 of Japanese patent application laid-open No. 2015-034964 and the compounds described in paragraphs 0087 to 0131 of International publication No. 2015/199219 can be preferably used, and these contents are incorporated in the present specification.

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

Further, as other radical polymerizable compounds, the compounds described in paragraphs 0104 to 0131 of Japanese patent application laid-open No. 2015-187211 can be used, and the contents thereof 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 four ethyleneoxy chains, SR-209, 231, 239 (manufactured by Inc.) which is a Sartomer Company having 2-functional methyl acrylate having four ethyleneoxy chains, DPCA-60 (manufactured by Ltd.) which is a 6-functional acrylate having six pentyleneoxy chains, TPA-330 (manufactured by Ltd.) which is a 3-functional acrylate having three isobutylene oxy chains, urethane oligomer UAS-10, UAB-140 (NIN PAPPO. STRIES CO., manufactured by LTD.), NK ester M-40G, NK (manufactured by NIN PAPER INRIES CO., LTD.), 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Co., Ltd.), and DPHA-40H (manufactured by Nippon INyaU Co., LTPU. CO., manufactured by Ltd.), and Chemical UA-306-H UA-306T, UA-306I, AH-600, T-600, AI-600(Kyoeisha chemical Co., Ltd.), BLEMMER PME400(NOF CORPORATION), and the like.

As the radical polymerizable compound, urethane acrylates such as those disclosed in Japanese patent publication No. 48-041708, Japanese patent publication No. 51-037193, Japanese patent publication No. 02-032293 and Japanese patent publication No. 02-016765, urethane compounds having an ethylene oxide skeleton as disclosed in Japanese patent publication No. 58-049860, Japanese patent publication No. 56-017654, Japanese patent publication No. 62-039417 and Japanese patent publication No. 62-039418 are also preferable. Further, as the radical polymerizable compound, compounds having an amino structure or a sulfide structure in the molecule as described in Japanese patent application laid-open Nos. 63-277653, 63-260909 and 01-105238 can be used.

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

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 excellent. Further, the polymerizability is good. The acid value was measured in accordance with JIS K0070: 1992.

The curable resin composition of the present invention can preferably use a monofunctional radical polymerizable compound as the radical polymerizable compound from the viewpoint of suppressing warpage associated with elastic modulus control 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, and (meth) acrylic acid derivatives such as glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, 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 Compounds other than the above-mentioned radically polymerizable Compounds ]

The curable resin composition of the present invention may further contain 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 36]

(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 37]

(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 38]

(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, 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, Honshu Chemical Industry Co., manufactured by Ltdy), NIKALAC MX-290 (trade name, Sanwa Chemical Co., manufactured by Ltd), 2, 6-dimethylmethy-4-t-butylphenol (2, 6-dimethoxymethyl-4-t-butylphenol), 2, 6-dimethylmethy-p-cresol (2, 6-dimethoxymethyl-4-t-butylphenol), 2, 6-dimethylmethy-4-dimethylmethane-2, 6-dimethylmethane-cresol (2, 6-dimethylmethane-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., 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., Ltd.).

Epoxy compound (compound having epoxy group) -

The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group does not cause dehydration reaction due to crosslinking while undergoing a crosslinking reaction at 200 ℃ or lower, and therefore, shrinkage of the film is not easily caused. Therefore, the epoxy compound is contained, and it is demonstrated that the low-temperature curing and warpage of the curable resin composition can be effectively suppressed.

The epoxy compound preferably comprises a polyethylene oxide group. This further lowers 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-4850-150, EPICLON EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822 (trade name, DIC-6322 (registered trademark), BEO-60E (registered trademark), NEOPA-4003, EP-40052, EP-4000, EP-40052, etc., manufactured by ADEKA CORPORATION), and the like. Among them, an epoxy resin containing a polyethylene oxide group is preferable from the viewpoint 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 two 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, and 1, 4-benzenedicarboxylic acid-bis [ (3-ethyl-3-oxetanyl) methyl ] ester. 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 can be used alone or in combination of two or more.

-benzoxazine compound (compound having benzoxazolyl group) -

The benzoxazine compound is preferable because a crosslinking reaction due to a 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 (hereinafter, trade name: Shikoku Chemicals Corporation), benzoxazine adduct of polyhydroxystyrene resin, and novolak type dihydrobenzoxazine compound. These may be used alone or in combination of two or more.

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

< solvent >

The curable resin composition of the present invention 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.

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

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

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

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

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

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 two or more forms from the viewpoint of improvement of the properties of the coated surface.

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

From the viewpoint of coatability, 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. The solvent content may be adjusted depending on the desired thickness of the coating film and the coating method.

The solvent may contain only one kind, or may contain two or more kinds. When two or more solvents are contained, the total amount thereof is preferably in the above range.

< thermal acid generating agent >

The curable resin composition of the present invention preferably contains a thermal acid generator.

The thermal acid generator has an effect of generating an acid by heating and promoting a crosslinking reaction of at least one compound selected from the group consisting of a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound and a benzoxazole compound, or a hydroxymethyl group contained in a specific resin.

When the curable resin composition of the present invention contains a thermal acid generator, the specific resin preferably contains a methylol group as a polymerizable group.

The thermal decomposition initiation temperature of the thermal acid generator is preferably 50 to 270 ℃, more preferably 50 to 250 ℃. Further, it is preferable to select, as the thermal acid generator, one which does not generate an acid in drying (prebaking: about 70 to 140 ℃) after the curable resin composition is applied to a substrate and generates an acid in final heating (curing: about 100 to 400 ℃) after patterning by subsequent exposure and development, because a decrease in sensitivity in development can be suppressed.

The thermal decomposition initiation temperature was determined as the peak temperature of the lowest exothermic peak when the thermal acid generator was heated to 500 ℃ at 5 ℃/min in the pressure-resistant capsule.

Examples of the apparatus used for measuring the thermal decomposition initiation temperature include Q2000 (manufactured by TA instruments).

The acid generated from the thermal acid generator is preferably a strong acid, and is preferably an aromatic sulfonic acid such as p-toluenesulfonic acid or benzenesulfonic acid, an alkanesulfonic acid such as methanesulfonic acid, ethanesulfonic acid or butanesulfonic acid, or a haloalkanesulfonic acid such as trifluoromethanesulfonic acid. Examples of such a thermal acid generator include those described in paragraph 0055 of Japanese patent laid-open publication No. 2013-072935.

Among these, an alkanesulfonic acid having 1 to 4 carbon atoms or a haloalkanesulfonic acid having 1 to 4 carbon atoms is more preferably generated from the viewpoint that the residue in the cured film is small and the physical properties of the cured film are not easily lowered, and the thermal acid generator is preferably a (4-hydroxyphenyl) dimethylsulfonium methanesulfonate salt, a (4- ((methoxycarbonyl) oxy) phenyl) dimethylsulfonium methanesulfonate salt, a benzyl (4-hydroxyphenyl) methylsulfonium methanesulfonate salt, a benzyl (4- ((methoxycarbonyl) oxy) phenyl) methylsulfonium methanesulfonate salt, a (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium methanesulfonate salt, a (4-hydroxyphenyl) dimethylsulfonium trifluoromethanesulfonate salt, a (4- ((methoxycarbonyl) oxy) phenyl) dimethylsulfonium trifluoromethanesulfonate salt, a benzyl (4-hydroxyphenyl) methylsulfonium trifluoromethanesulfonate salt, a (2-methylphenyl) methyl) sulfonium trifluoromethanesulfonate, a (4-hydroxyphenyl) dimethylsulfonium trifluoromethanesulfonate salt, a (4-methoxycarbonyl) oxy) phenyl) dimethylsulfonium trifluoromethanesulfonate, a (4-hydroxyphenyl) methylsulfonium trifluoromethanesulfonate, a (4-methyl sulfonium trifluoromethanesulfonate, a (4-hydroxyphenyl) sulfonium trifluoromethanesulfonate, a, Benzyl (4- ((methoxycarbonyl) oxy) phenyl) methylsulfonium triflate, (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium triflate, 3- (5- (((propylsulfonyl) oxy) imino) thiophen-2 (5H) -ylidene) -2- (o-tolyl) propionitrile, 2-bis (3- (methylsulfonylamino) -4-hydroxyphenyl) hexafluoropropane.

Further, as the thermal acid generator, a compound described in paragraph 0059 of Japanese patent laid-open publication No. 2013-167742 is also preferable.

The content of the thermal acid generator is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more, per 100 parts by mass of the specific resin. The content of 0.01 parts by mass or more promotes the crosslinking reaction, and thus the mechanical properties and chemical resistance of the cured film can be further improved. From the viewpoint of electrical insulation of the cured film, the amount is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less.

< onium salt >

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

In particular, when the specific resin is a polyimide precursor, the curable resin composition 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 or imide salts are preferable from the viewpoint of high thermal stability, and sulfonium salts, iodonium salts, or 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 as different molecules are ionically bonded, and is preferably an intermolecular salt. 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.

The cation in the onium salt is preferably an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation, and more preferably at least one cation selected from the group consisting of a tetraalkylammonium cation, a sulfonium cation and an iodonium cation.

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

The thermal base generator is a compound which generates a base by heating, and examples thereof include an acidic compound which generates a base by heating 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-

The ammonium cation is preferably a quaternary ammonium cation.

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

[ chemical formula 39]

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

In the formula (101), R¹～R⁴The alkyl group 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 compound may have a substituent, and examples 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.

R¹～R⁴When at least two of the above 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 one of the following formulae (Y1-1) and (Y1-2).

[ chemical formula 40]

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), R¹⁰¹Preferably, n hydrogen atoms are removed from an aliphatic hydrocarbon, an aromatic hydrocarbon or a structure formed by bonding these, and more preferably n hydrogen atoms are removed from a saturated aliphatic hydrocarbon having 2 to 30 carbon atoms, benzene or naphthaleneA group of atoms.

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

In the formula (Y1-2), Ar¹⁰¹And Ar¹⁰²Preferably each independently phenyl or naphthyl, more preferably phenyl.

Anions-

The anion in the ammonium salt is preferably one selected from the group consisting of a carboxylate anion, a phenol anion, a phosphate anion and a sulfate anion, and is more preferably a carboxylate anion from the viewpoint of compatibility between the stability and the thermal decomposition property of the salt. 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 two 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 41]

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

In the present embodiment, the electron-withdrawing group means that the Hammett substituent constant σ m represents 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 group (σ m ═ 0.06), Ac group (σ m ═ 0.38),A MeOC (═ O) group (σ m ═ 0.37), a MeC (═ O) CH ═ CH group (σ m ═ 0.21), a PhC (═ O) group (σ m ═ 0.34), H₂NC(＝O)CH₂And a group (σ m ═ 0.06). 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 42]

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 43]

In the formula (XA), L¹⁰Represents a single bond or is selected from the group consisting of alkylene, alkenylene, aromatic, -NR^X-and combinations 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.

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

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 the specific resin 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 of 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 44]

[ Iminium salt ]

In the present invention, an imide salt means a salt of an imide cation and 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 45]

In the formula (102), R⁵And R⁶Each independently represents a hydrogen atom or a hydrocarbon group, R⁷Represents a hydrocarbon group, R⁵～R⁷At least two 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～R⁴The same and the same preferred mode.

In the formula (102), R⁷Preferably with R⁵And R⁶At least one of which is bonded to form a ring. The above rings may also 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 one of the following formulae (Y1-3) to (Y1-5).

[ chemical formula 46]

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 represents an integer of 1 or more, and m represents an integer of 0 or more.

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

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

In the formula (Y1-5), m is preferably 0 to 4, more preferably 1 or 2, and still more preferably 1.

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

[ chemical formula 47]

[ sulfonium salt ]

In the present invention, sulfonium salt means a salt of a sulfonium cation and 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-

The sulfonium cation is preferably a tertiary sulfonium cation, and more preferably a triarylsulfonium cation.

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

[ chemical formula 48]

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

R⁸～R¹⁰Preferably, each of the groups is independently 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～R¹⁰The compound may have a substituent, and examples 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 are preferably the same from the viewpoint of synthetic compatibility.

[ 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 diaryl iodonium cation is preferable.

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

[ chemical formula 49]

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

R¹¹And R¹²Preferably, each of the groups is independently 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 compound may have a substituent, and examples 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.

R¹¹And R¹²The groups may be the same or different, and are preferably the same from the viewpoint of synthetic compatibility.

[ phosphonium salt ]

In the present invention, phosphonium salts mean salts of phosphonium cations and 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 50]

In the formula (105), R¹³～R¹⁶Independently of one another represent hydrogen atomOr a hydrocarbyl group.

R¹³～R¹⁶Preferably, each of the groups is independently 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 compound may have a substituent, and examples 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.

R¹³～R¹⁶The groups may be the same or different, and are preferably the same from the viewpoint of synthetic compatibility.

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.

One or two or more kinds of onium salts can be used. When two or more kinds are used, the total amount is preferably in the above range.

< thermal alkali production agent >

The curable resin composition of the present invention may contain a thermoalcogenide.

In particular, when the specific resin is a polyimide precursor, the curable resin composition preferably contains 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 51]

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 refers to a structure in which all three bonds of a 3-valent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. 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.

In the formulae (B1), (B2), Rb¹、Rb²And Rb³Preferably at least one of these comprises a cyclic structure, more preferably at least two comprise a cyclic structure. The cyclic structure may be either a single ring or a condensed ring, and is preferably a single ring or a condensed ring in which two single rings are condensed. Monocyclic rings are preferably 5-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 having 1 to 24, more preferably 2 to 18, further preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24, more preferably 2 to 18, further preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22, more preferably 6 to 18, further preferably 6 to 10 carbon atoms) or an aralkyl group (preferably having 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. The ring to be formed is preferably 4 to 7-membered nitrogen-containingA heterocyclic ring. 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 3 to 12 carbon atoms), an aryloxy group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), or an aralkyloxy group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, more preferably 7 to 12). Among them, preferred are cycloalkyl groups (preferably having 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 52]

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

Rb¹³An alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms),The alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), the aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), the 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 exhibited. Wherein, Rb is¹³Preferably an aralkyl group.

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.

Rb³⁵The aromatic hydrocarbon compound is preferably an alkyl group (preferably 1 to 24, more preferably 1 to 12, further preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12, more preferably 2 to 12, 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), and preferably an aryl group.

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

[ chemical formula 53]

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

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

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

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

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 54]

[ chemical formula 55]

[ chemical formula 56]

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. One or more than two kinds of the thermal alkali-producing agents can be used. When two or more kinds are used, the total amount is preferably in the above range.

< migration inhibitor >

The curable resin composition of the present invention preferably further contains a migration inhibitor. By containing the migration inhibitor, it is possible to effectively inhibit the metal ions 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 heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, and triazine ring), thiourea compounds, compounds having 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 also be used.

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

Specific examples of the migration inhibitor include the following compounds.

[ chemical formula 57]

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 one kind alone, or two or more kinds thereof. When the number of migration inhibitors is two or more, the total amount thereof is preferably within the above range.

< polymerization inhibitor >

The 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.

The following compound (Me is methyl) can be used.

[ chemical formula 58]

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 one kind alone, or two or more kinds thereof. When the polymerization inhibitor is two or more, the total amount thereof is preferably in the above range.

< modifier for improving adhesion of Metal >

The 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.

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

[ chemical formula 59]

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, per 100 parts by mass of the specific resin. When the lower limit value is not less than the lower limit value, the adhesion between the cured film after the curing step and the metal layer becomes good, and when the upper limit value is not more than the upper limit value, the heat resistance and the mechanical properties of the cured film after the curing step become good. The metal adhesion improver may be one kind only, or two or more kinds. When two or more kinds are used, the total amount thereof is preferably in the above range.

< other additives >

The curable resin composition of the present invention may be blended with various additives, for example, 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, as required. 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.

[ sensitizing agent ]

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

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

As the sensitizer, a sensitizing dye may be used.

Specifically, the sensitizing dye can be described in paragraphs 0161 to 0163 of Japanese patent application laid-open No. 2016-027357, and the contents thereof are incorporated in the present specification.

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. One sensitizer may be used alone, or two or more sensitizers may be used simultaneously.

[ chain transfer agent ]

The curable resin composition of the present invention may also have 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 donate hydrogen to the less reactive radicals to produce radicals, or can produce radicals 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 one kind only, or two or more kinds. When the number of the chain transfer agents is two or more, the total amount thereof is preferably in the above range.

[ surfactant ]

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

[ chemical formula 60]

Further, as the surfactant, the compounds described in paragraphs 0159 to 0165 of International publication No. 2015/199219 can also 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, and 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 surfactant may be one kind only, or two or more kinds. When the number of the surfactants is two or more, the total amount thereof is preferably in 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 biased toward 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 higher fatty acid derivative may be one kind alone, or two or more kinds thereof. When the number of the higher fatty acid derivatives is two or more, the total amount thereof is preferably in the above range.

< restrictions on other substances included >

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 even more preferably less than 0.6% by mass, from the viewpoint of the properties of the coated surface.

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 even 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.

As a method for reducing metal impurities unexpectedly contained in the curable resin composition of the present invention, the following methods can be mentioned: selecting a raw material having a small metal content as a raw material constituting the curable resin composition of the present invention; filtering a raw material constituting the curable resin composition of the present invention with a filter; polytetrafluoroethylene or the like is lined in the apparatus to conduct distillation under conditions that inhibit contamination as much as possible.

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

As the container for the 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 described 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 one previously cleaned with an organic solvent. In the filtration step of the filter, a plurality of filters may be used in series or in parallel. 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. Further, the filtration may be performed after the 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 with impurity removal treatment using an adsorbent material. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

< 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 manufacturing 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 has 2 or more cured films and a metal layer between the cured films. The laminate of the present invention includes 2 or more cured films, and preferably includes a metal layer between any of the cured films. For example, a laminate having a layer structure in which at least 3 layers of a first cured film, a metal layer, and a second cured film are sequentially stacked is preferable. The first cured film and the second cured film are both the cured film of the present invention, and for example, a preferable embodiment is one in which the first cured film and the second cured film are both films obtained by curing the curable resin composition of the present invention. The curable resin composition of the present invention for forming the first cured film and the curable resin composition of the present invention for forming the second cured film may be the same composition or may be different compositions, and from the viewpoint of production suitability, compositions having the same composition are preferred. Such a metal layer can be preferably used as a metal wiring of a rewiring layer or the like.

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, and a stress buffer film. In addition, a sealing film, a substrate material (a base film, a cover film, or an interlayer insulating film of a flexible printed circuit board), or a pattern formed by etching an insulating film for the above-described actual mounting use may be mentioned. For these uses, for example, reference can be made to Science & Technology co, ltd, "high functionalization and application Technology of polyimide" 4 months 2008, persimmon benayl & tomb/prison, CMC technical library, "foundation and development of polyimide material" 11 months 2011 issue, japan polyimide aromatic system polymer research institute/compilation "latest polyimide foundation and application" NTS, 8 months 2010, and the like.

The cured film of the present invention can also be used for the production of printing plates such as offset printing plates and screen printing plates, the use of etching molding modules, the production of protective varnish 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.

Further, the method for producing a cured film of the present invention includes the above-described film forming step, and more preferably further includes an exposure step of exposing the above-described film to light and a development step of developing the above-described film (subjecting the above-described film to a development treatment).

Further, the method for producing a cured film of the present invention includes the above-described film forming step (and, if necessary, the above-described developing step), and more preferably further includes a heating step of heating the above-described 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), and the steps (a) to (d) are further performed again. In particular, the above steps are performed a plurality of times in sequence, and for example, 2 to 5 times (i.e., 3 to 6 times in total) is preferable. 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 provided with the cured film or between the cured films or at both positions. In addition, in the production of the laminate, it is not necessary to repeat all the steps (a) to (d), and a laminate of cured films can be obtained by performing at least the steps (a), preferably the steps (a) to (c) or the steps (a) to (d) a plurality of times as described above.

< film formation step (layer formation step) >

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

Specifically, examples of the method to be applied 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 in the case of a circular substrate such as a wafer, a spin coating method, a spray coating method, an ink jet method, or the like is preferable, and in the case of a rectangular substrate, a slit coating method, a spray coating method, an ink jet method, or the like is preferable. In the case of spin coating, the coating can be applied at a rotation speed of 500 to 2,000rpm (revolutions per minute) for about 10 seconds to 1 minute.

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

As the transfer method, the production methods 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 be preferably employed 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), then performing a film forming step (layer forming step), and then drying the film to remove the solvent. The preferable drying temperature is 50 to 150 ℃, more preferably 70 to 130 ℃, and further preferably 90 to 110 ℃. The drying time is, for example, 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.

< Exposure Process >

The production method of the present invention may further 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, the exposure amount 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.

< developing Process >

The production method of the present invention may further include a development step of performing a development treatment 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 liquid immersion, spraying, dipping, or ultrasonic waves can be used.

The development is performed using a developer. The developer is not particularly limited in use as long as an unexposed portion (unexposed portion) can be removed.

In the present invention, the case where an alkali developer is used as the developer is referred to as alkali development, and the case where a developer containing 50 mass% or more of an organic solvent is used as the developer is referred to as solvent development.

In the alkaline development, the content of the organic solvent in the developer is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 1% by mass or less, and particularly preferably contains no organic solvent, based on the total mass of the developer.

The developing solution in the alkaline development is preferably an aqueous solution with a pH of 9-14.

Examples of the alkaline compound contained in the developer for alkaline development include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, potassium metasilicate, ammonia, and amine. Examples of the amine include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, quaternary ammonium hydroxide, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, and tetrabutylammonium hydroxide. Among them, a metal-free basic compound is preferable, and an ammonium compound is more preferable.

The basic compound may be one kind only, or two or more kinds. When the number of the basic compounds is two or more, the total amount thereof is preferably in the above range.

In the solvent development, the developer more preferably contains 90% or more of an organic solvent. In the present invention, the developer preferably contains an organic solvent having a ClogP value of-1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be determined as a calculated value by inputting the structural formula by chembidraw (chemibiological diagram).

As the organic solvent, preferable examples of the esters include ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ -butyrolactone, 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, etc., and as ketones, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as aromatic hydrocarbons, toluene, xylene, anise ether, limonene, etc., are preferably cited, and as sulfoxides, dimethyl sulfoxide is preferably cited.

In the present invention, cyclopentanone and γ -butyrolactone are particularly preferable, and cyclopentanone is more 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, the developer may be an organic solvent in an amount of 100% by mass.

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

After the treatment with the developer, the substrate may be further rinsed.

For solvent development, it is preferable to perform rinsing using an organic solvent different from the developer.

For the alkali development, it is preferable to perform rinsing using pure water.

The rinsing time is preferably 5 seconds to 1 minute.

< heating Process >

The production method of the present invention preferably includes a 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.

The curable resin composition of the present invention contains a polymerizable compound other than the specific resin, but in this step, it is possible to cause a curing reaction of an unreacted polymerizable compound other than the specific resin, a curing reaction of an unreacted polymerizable group in the specific resin, or the like.

When the specific resin is a polyimide precursor and the curable resin composition contains a thermal alkali generator, the thermal alkali generator is decomposed in the heating step, for example, to generate a base and cause a cyclization reaction of the polyimide precursor.

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, particularly preferably 150 ℃ or higher, further preferably 160 ℃ or higher, and most preferably 170 ℃ or higher. The upper limit is preferably 450 ℃ or lower, more preferably 350 ℃ or lower, still more preferably 250 ℃ or lower, and particularly 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 heating rate is set to 1 ℃/min or more, whereby productivity can be ensured, excessive volatilization of amine can be prevented, and the residual stress of the cured film can be relaxed by setting the heating rate to 12 ℃/min or less.

The temperature at the start of heating is preferably 20 to 150 ℃, more preferably 20 to 130 ℃, and still more preferably 25 to 120 ℃. The temperature at the start of heating 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 30 to 200 ℃ lower 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, from the viewpoint of adhesion between the layers of the cured film, the heating is preferably performed at a heating temperature of 180 to 320 ℃, and more preferably at 180 to 260 ℃. The reason for this is not clear, but it is considered that the reason is that the polymerizable groups in the specific resin between layers are crosslinked with each other by setting the temperature to this 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 still more preferably 120 to 185 ℃. In this pretreatment step, it is also preferable to perform treatment while irradiating ultraviolet rays as described in U.S. Pat. No. 9159547. These pretreatment steps can improve the film properties. The pretreatment step may be performed in a short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be carried out in two or more stages, 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 ℃.

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

The heating step is preferably performed in an environment of low oxygen concentration by charging an inert gas such as nitrogen, helium, or argon, and the like, in order to prevent the decomposition of the specific resin. 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 can be cited.

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 developing 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 step (d) may be performed every time, or the heating step (d) may be performed collectively after the lamination step is performed a predetermined number of times. It is needless to say that the lamination step may further include the drying step, the heating step, and the like as appropriate.

When the lamination step is further performed after the lamination step, the surface activation treatment step may be further performed after the heating step, after the exposure step, or after the metal layer forming step. As the surface activation treatment, plasma treatment may be 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 is preferably 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, it is particularly preferable to form a cured film (resin layer) of the curable resin composition so as to further cover the metal layer after the metal layer is provided. 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 finally or intermediately collectively providing the heating step (d). 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.

Also disclosed in the present invention is a semiconductor device comprising the cured film or laminate of the present 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-.

(polyimide or polyimide precursor)

The polyimide or polyimide precursor of the present invention preferably contains a structure represented by the following formula (1-1).

[ chemical formula 61]

The above formula (1-1) has the same meaning as the formula (1-1) in the specific resin, and preferred modes are also the same.

The polyimide or the polyimide precursor of the present invention is the same as the polyimide or the polyimide precursor in the specific resin, except that the formula (1-1) is used as an essential condition, and the preferable embodiment is also the same.

< use >)

The polyimide or the polyimide precursor of the present invention is preferably used as a resin contained in the curable resin composition.

Further, for example, a composition using a conventional polyimide or polyimide precursor such as a composition for an interlayer insulating film is not particularly limited, and the polyimide or polyimide precursor of the present invention can be used in place of a part or all of a conventional polyimide or polyimide precursor.

The composition containing the polyimide or the polyimide precursor of the present invention is considered to be excellent in coatability, and therefore the polyimide or the polyimide precursor of the present invention is preferably used in a composition used for forming a coating film by coating, such as a composition for forming an insulating film.

Examples

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

(Synthesis of specific resin)

< Synthesis example 1: synthesis of polyimide (PI-1)

In a dry reactor equipped with a flat bottom adapter equipped with a stirrer, a condenser and an internal thermometer, 15.21g (100 mmol) of 3, 5-diaminobenzoic acid was dissolved in 130.0g of N-methylpyrrolidone (NMP) while removing water. Next, 31.02g (100 mmol) of oxydiphthalic dianhydride was added, and the mixture was stirred at 40 ℃ for 2 hours. Subsequently, 50mL of toluene was added, and the mixture was stirred for 4 hours while the temperature was raised to 180 ℃ with nitrogen being introduced at a flow rate of 200 mL/min. After the reaction mixture was cooled to 25 ℃, 28.4g (100 mmol) of BLEMER PE-200 (manufactured by NOF CORPORATION), 0.61g (5 mmol) of N, N' -dimethylaminopyridine, 0.06g of p-methoxyphenol, and 130.0g of N-methylpyrrolidone were added and dissolved, and the mixture was cooled to 0 ℃. Subsequently, 12.6g (100 mmol) of diisopropylcarbodiimide was added thereto, and the mixture was stirred at 10 ℃ or lower for 5 hours and then warmed to room temperature. Next, the polyimide was precipitated in 2 liters of water, and the water-polyimide mixture was stirred at 2,000rpm for 30 minutes. The polyimide precursor resin was removed by filtration, stirred again in 1.5 liters of methanol for 30 minutes and filtered again. Then, the obtained polyimide was dried at 40 ℃ for 1 day under reduced pressure, to obtain PI-1. PI-1 had a weight average molecular weight (Mw) of 29,500 and a number average molecular weight (Mn) of 13,500.

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

The square brackets indicate the content ratio (molar ratio) of each repeating unit, and m is 91 and q is 9.

[ chemical formula 62]

< Synthesis example 2: synthesis of polyimide (PI-2)

In a dry reactor equipped with a flat bottom adapter equipped with a stirrer, a condenser and an internal thermometer, 15.21g (100 mmol) of 3, 5-diaminobenzoic acid was dissolved in 130.0g of N-methylpyrrolidone (NMP) while removing water. Next, 31.02g (100 mmol) of oxydiphthalic dianhydride was added, and the mixture was stirred at 40 ℃ for 2 hours. Subsequently, 50mL of toluene was added, and the mixture was stirred for 4 hours while the temperature was raised to 180 ℃ with nitrogen being introduced at a flow rate of 200 mL/min. After the reaction mixture was cooled to 25 ℃, 33.6g (80 mmol) of BLEMER AP-400 (manufactured by NOF CORPORATION), 0.61g (5 mmol) of N, N' -dimethylaminopyridine, 0.06g of p-methoxyphenol and 130.0g of N-methylpyrrolidone were added and dissolved, and the mixture was cooled to 0 ℃. Subsequently, 12.6g (90 mmol) of diisopropylcarbodiimide was added thereto, and the mixture was stirred at 10 ℃ or lower for 5 hours and then warmed to room temperature. Next, the polyimide was precipitated in 2 liters of water, and the water-polyimide mixture was stirred at 2,000rpm for 30 minutes. The polyimide precursor resin was removed by filtration, stirred again in 1.5 liters of methanol for 30 minutes and filtered again. Then, the obtained polyimide was dried at 40 ℃ for 1 day under reduced pressure, to obtain PI-2. PI-2 had a weight average molecular weight (Mw) of 25,100 and a number average molecular weight (Mn) of 12,100.

The structure of PI-2 is presumed to be represented by the following formula (PI-2).

The parenthesis indicates the content ratio (molar ratio) of each repeating unit, and m is 85 and q is 15.

[ chemical formula 63]

In the above (PI-2), C₃H₆The above-mentioned publication contains 1-methylethylene (hereinafter, referred to as "P1") and 2-methylethylene (hereinafter, referred to as "P2") at random. In the following formulae (P1) and (P2),*¹bonded to the carbonyl-side structure of the formula (PI-2)²Bonded to the acryloyloxy side structure in the formula (PI-7).

[ chemical formula 64]

< Synthesis example 3: synthesis of polyimide (PI-3)

In a dry reactor equipped with a flat-bottomed adapter equipped with a stirrer, a condenser and an internal thermometer, 14.3g (50 mmol) of bis (4-amino-3-carboxyphenyl) methane was dissolved in 100.0g of N-methylpyrrolidone (NMP) while removing water. Then, 9.31g (30 mmol) of oxydiphthalic dianhydride and 8.88g (20 mmol) of 4, 4' - (hexafluoroisopropylidene) diphthalic dianhydride were added thereto, and the mixture was stirred at 40 ℃ for 2 hours. Subsequently, 50mL of toluene was added, and the mixture was stirred for 5 hours while the temperature was raised to 180 ℃ with nitrogen being introduced at a flow rate of 200 mL/min. The reaction mixture was cooled to 25 ℃ and then dissolved in 14.2g (50 mmol) of BLEMMER PE-200 (manufactured by NOF CORPORATION), 0.61g (5 mmol) of N, N' -dimethylaminopyridine, 0.06g of p-methoxyphenol and 130.0g of N-methylpyrrolidone, followed by cooling to 0 ℃. Subsequently, 6.3g (50 mmol) of diisopropylcarbodiimide was added thereto, and the mixture was stirred at 10 ℃ or lower for 5 hours and then warmed to room temperature. Next, the polyimide was precipitated in 2 liters of water, and the water-polyimide mixture was stirred at 2,000rpm for 30 minutes. The polyimide precursor resin was removed by filtration, stirred again in 1.5 liters of methanol for 30 minutes and filtered again. Then, the obtained polyimide was dried at 40 ℃ for 1 day under reduced pressure, to obtain PI-3. PI-3 had a weight average molecular weight (Mw) of 31,000 and a number average molecular weight (Mn) of 13,900.

The structure of PI-3 is presumed to be represented by the following formula (PI-3). In the formula (PI-3), a represents a bonding site at which R is bonded to an oxygen atom.

[ chemical formula 65]

< Synthesis example 4: synthesis of polyimide (PI-4)

In a dry reactor equipped with a flat bottom adapter equipped with a stirrer, a condenser and an internal thermometer, 15.21g (100 mmol) of 3, 5-diaminobenzoic acid was dissolved in 130.0g of N-methylpyrrolidone (NMP) while removing water. Then, 15.51g (50 mmol) of oxydiphthalic dianhydride and 22.1g (50 mmol) of 4, 4' - (hexafluoroisopropylidene) diphthalic dianhydride were added thereto, and the mixture was stirred at 40 ℃ for 2 hours. Subsequently, 50mL of toluene was added, and the mixture was stirred for 4 hours while the temperature was raised to 180 ℃ with nitrogen being introduced at a flow rate of 200 mL/min. After the reaction solution was cooled to 25 ℃, 7.80g (60 mmol) of 2-hydroxyethyl methacrylate, 13.6g (40 mmol) of hexaethyleneglycol monomethyl ether, 0.61g (5 mmol) of N, N' -dimethylaminopyridine, 0.06g of p-methoxyphenol, and 130.0g of N-methylpyrrolidone were added and dissolved, and the mixture was cooled to 0 ℃. Subsequently, 12.6g (100 mmol) of diisopropylcarbodiimide was added thereto, and the mixture was stirred at 10 ℃ or lower for 5 hours and then warmed to room temperature. Next, the polyimide was precipitated in 2 liters of water, and the water-polyimide mixture was stirred at 2,000rpm for 30 minutes. The polyimide precursor resin was removed by filtration, and the filtrate was mixed with 1.5 liters of methanol, stirred again for 30 minutes and filtered again. Then, the obtained polyimide was dried at 40 ℃ for 1 day under reduced pressure, to obtain PI-4. PI-4 had a weight average molecular weight (Mw) of 28,300 and a number average molecular weight (Mn) of 13,000.

The structure of PI-4 is presumed to be represented by the following formula (PI-4). In the formula (PI-4), R represents₁A bonding site bonded to an oxygen atom.

The square brackets indicate the content ratio (molar ratio) of each repeating unit, and m is 50 and q is 50.

[ chemical formula 66]

< Synthesis example 5: synthesis of polyimide (PI-5)

In a dry reactor equipped with a flat bottom adapter equipped with a stirrer, a condenser and an internal thermometer, 15.21g (100 mmol) of 3, 5-diaminobenzoic acid was dissolved in 130.0g of N-methylpyrrolidone (NMP) while removing water. Then, 15.5g (50 mmol) of oxydiphthalic dianhydride and 13.3g (30 mmol) of 4, 4' - (hexafluoroisopropylidene) diphthalic dianhydride were added thereto, and the mixture was stirred at 40 ℃ for 2 hours. Subsequently, 50mL of toluene was added, and the mixture was stirred for 4 hours while the temperature was raised to 180 ℃ with nitrogen being introduced at a flow rate of 200 mL/min. After the reaction solution was cooled to 25 ℃, 21.3g (50 mmol) of BLEMER AP-400 (manufactured by NOF CORPORATION), 2.22g (30 mmol) of 1-hydroxy-2, 3-epoxypropane, 0.61g (5 mmol) of N, N' -dimethylaminopyridine, 0.06g of p-methoxyphenol and 130.0g of N-methylpyrrolidone were added and dissolved, and the mixture was cooled to 0 ℃. Subsequently, 12.6g (100 mmol) of diisopropylcarbodiimide was added thereto, and the mixture was stirred at 10 ℃ or lower for 5 hours and then warmed to room temperature. Next, the polyimide was precipitated in 2 liters of water, and the water-polyimide mixture was stirred at 2,000rpm for 30 minutes. The polyimide precursor resin was removed by filtration, and the filtrate was mixed with 1.5 liters of methanol, stirred again for 30 minutes and filtered again. Then, the obtained polyimide was dried at 40 ℃ for 1 day under reduced pressure, to obtain PI-5. PI-5 had a weight average molecular weight (Mw) of 33,300 and a number average molecular weight (Mn) of 15,000.

The structure of PI-5 is presumed to be represented by the following formula (PI-5). In the formula (PI-5), R represents₁A bonding site bonded to an oxygen atom.

[ chemical formula 67]

In the above (PI-5), C₃H₆In the description of (1), 1-methylethylene (above (P1)) and 2-methylethylene (above) are randomly containedThe above (P2)). In the formulae (P1) and (P2)¹And R in the formula (PI-5)₁Structural bonding of the acrylate group side in (1)²And R in the formula (PI-5)₁The structure of the side (a) of (b) is bonded.

< Synthesis example 6: synthesis of polyimide (PI-6)

In a dry reactor equipped with a flat-bottomed adapter equipped with a stirrer, a condenser and an internal thermometer, 6.91g (30 mmol) of bis (2- (3-aminopropoxy) ethyl) ether and 25.6g (70 mmol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane were dissolved in 100.0g of N-methylpyrrolidone (NMP) while removing water. Then, 310.2g (100 mmol) of oxydiphthalic dianhydride and 13.3g (30 mmol) of 4, 4' - (hexafluoroisopropylidene) diphthalic dianhydride were added thereto, and the mixture was stirred at 40 ℃ for 2 hours. Subsequently, after adding 50mL of toluene, nitrogen was introduced at a flow rate of 200mL/min, the temperature was raised to 180 ℃ and the mixture was stirred for 5 hours, and the reaction mixture was cooled to 25 ℃. 12.1g (120 mmol) of triethylamine, 0.06g of p-methoxyphenol and 80.0g of N-methylpyrrolidone were added and dissolved, followed by cooling to 0 ℃. Then, 10.4g (100 mmol) of methacryloyl chloride was added dropwise over 1 hour, and the mixture was stirred at 25 ℃ or lower for 4 hours. Next, the polyimide was precipitated in 2 liters of water, and the water-polyimide mixture was stirred at 2,000rpm for 30 minutes. The polyimide precursor resin was removed by filtration, and the filtrate was mixed with 1.5 liters of methanol, stirred again for 30 minutes and filtered again. Then, the obtained polyimide was dried at 40 ℃ for 1 day under reduced pressure, to obtain PI-6. PI-6 had a weight average molecular weight (Mw) of 29,900 and a number average molecular weight (Mn) of 14,300.

The structure of PI-6 is presumed to be represented by the following formula (PI-6). In the formula (PI-6), a represents a bonding site at which R is bonded to an oxygen atom.

[ chemical formula 68]

< Synthesis example 7: synthesis of polyimide (PI-7)

PI-7 was synthesized in the same manner as PI-6, except that the same molar amount of 4, 6-dihydroxy-1, 3-phenylenediamine was used instead of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane used in the synthesis of PI-6. PI-7 had a weight average molecular weight (Mw) of 27,400 and a number average molecular weight (Mn) of 13,300.

The structure of PI-7 is presumed to be represented by the following formula (PI-7). In the formula (PI-7), a represents a bonding site at which R is bonded to an oxygen atom.

[ chemical formula 69]

< Synthesis example 8: synthesis of polyimide (PI-8)

PI-8 was synthesized in the same manner as PI-4 except that glycerol dimethacrylate (NOF CORPORATION 30 mmol) and BLEMMER PE-200(NOF CORPORATION 70 mmol) were used instead of 2-hydroxyethyl methacrylate and hexaethylene glycol monomethyl ether used for the synthesis of PI-4. PI-8 had a weight average molecular weight (Mw) of 25,900 and a number average molecular weight (Mn) of 12,900.

The structure of PI-8 is presumed to be represented by the following formula (PI-8). In the formula (PI-8), R represents₁A bonding site bonded to an oxygen atom.

[ chemical formula 70]

< Synthesis example 9: synthesis of polyimide (PI-9)

In a dry reactor equipped with a flat bottom adapter equipped with a stirrer, a condenser and an internal thermometer, 4.56g (30 mmol) of 3, 5-diaminobenzoic acid and 7.53g (20 mmol) of 9, 9-bis (4-amino-3-methylphenyl) fluorene were dissolved in 80.0g of N-methylpyrrolidone (NMP) while removing water. Then, 15.51g (50 mmol) of oxydiphthalic dianhydride was added thereto, and the mixture was stirred at 40 ℃ for 2 hours. Then, 30mL of toluene was added, and the mixture was stirred for 5 hours while raising the temperature to 180 ℃ with introducing nitrogen at a flow rate of 200 mL/min. The reaction mixture was cooled to 25 ℃ and then dissolved in 14.2g (50 mmol) of BLEMMER PE-200 (manufactured by NOF CORPORATION), 0.61g (5 mmol) of N, N' -dimethylaminopyridine, 0.06g of p-methoxyphenol and 130.0g of N-methylpyrrolidone, followed by cooling to 0 ℃. Subsequently, 6.3g (50 mmol) of diisopropylcarbodiimide was added thereto, and the mixture was stirred at 10 ℃ or lower for 5 hours and then warmed to room temperature. Subsequently, it was cooled to 25 ℃, precipitated in 1.5 liters of water/methanol (75/25 volume ratio), and stirred at 2,000rpm for 30 minutes. The precipitated polyimide resin was removed by filtration, washed with 1 liter of water, and then the filtrate was mixed with 1.5 liters of methanol, stirred again for 30 minutes and filtered again. The obtained polyimide was dried at 40 ℃ for 1 day under reduced pressure to obtain PI-9. PI-9 had a weight average molecular weight (Mw) of 31,600 and a number average molecular weight (Mn) of 11,500.

The structure of PI-9 is presumed to be represented by the following formula (PI-9).

The structure of PI-9 is presumed to be represented by the following formula (PI-9). In the formula (PI-9), R represents₁A bonding site bonded to an oxygen atom.

The parenthesis indicates the content ratio (molar ratio) of each repeating unit, and m is 3 and q is 2.

[ chemical formula 71]

< Synthesis example 10: synthesis of polyimide precursor (PA-1)

In a dry reactor equipped with a flat bottom adapter equipped with a stirrer, a condenser and an internal thermometer, 20.0g (64.5 mmol) of oxydiphthalic dianhydride was suspended in 140mL of diglyme while removing water. 10.1g (77 mmol) of 2-hydroxyethyl methacrylate, 12.6g (39 mmol) of BLEMER AP-400 (manufactured by NOF CORPORATION), 0.05g of hydroquinone, and 10.7g (135 mmol) of pyridine were added successively, and the mixture was stirred at 60 ℃ for 18 hours. Subsequently, after the mixture was cooled to-20 ℃, 16.1g (135.5 mmol) of thionyl chloride was added dropwise for 90 minutes. A white precipitate of pyridine hydrochloride was obtained. Subsequently, the mixture was warmed to room temperature, stirred for 2 hours, and then added with 9.7g (123 mmol) of pyridine and 25mL of N-methylpyrrolidone (NMP), thereby obtaining a transparent solution. Subsequently, to the obtained transparent solution, a mixture of 11.7g (58.7 mmol) of 4, 4' -diaminodiphenyl ether dissolved in 100mL of NMP was added dropwise for 1 hour. During the addition of the diamine, the viscosity increases. Subsequently, 5.6g (17.5 mmol) of methane and 0.05g of 3, 5-di-tert-butyl-4-hydroxytoluene were added, and the mixture was stirred for 2 hours. Next, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at 500rpm for 15 minutes. The polyimide precursor resin was removed by filtration, and stirred again in 4 liters of water for 30 minutes and filtered again. Subsequently, the obtained polyimide precursor resin was dried at 45 ℃ for 1 day under reduced pressure. The molecular weight of the polyimide precursor PA-1 was 25,100 and Mn was 13,200.

The structure of PA-1 is presumed to be represented by the following formula (PA-1). In the formula (PA-1), R represents a bonding site to which an oxygen atom is bonded.

[ chemical formula 72]

In the above (PA-1), C₃H₆The above-mentioned descriptions of (1) and (2) contain 1-methylethylene group (P1) and 2-methylethylene group (P2) at random. In the formulae (P1) and (P2)¹Bonded to the acryloyloxy side structure of R in the formula (PA-1)²Bonded to the structure on the x side in R in formula (PA-1).

< Synthesis example 11: synthesis of polyimide (A-1) for comparative example

In a drying reactor equipped with a flat-bottomed adapter equipped with a stirrer, a condenser and an internal thermometer, 31.0g (100 mmol) of 4, 4' -diaminodiphenyl ether was dissolved in 180.0g of N-methylpyrrolidone (NMP) while removing water. Subsequently, 44.4g (100 mmol) of 4, 4' - (hexafluoroisopropylidene) diphthalic dianhydride was added, and the mixture was stirred at 40 ℃ for 2 hours. Subsequently, after adding 50mL of toluene, nitrogen was introduced at a flow rate of 200mL/min, and the temperature was raised to 180 ℃ to stir for 6 hours, and cooled to room temperature. Next, 130.0g of N-methylpyrrolidone was added, and after dilution, the polyimide was precipitated in 2 liters of water, and the water-polyimide mixture was stirred at 2000rpm for 30 minutes. The polyimide precursor resin was removed by filtration, and the filtrate was mixed with 1.5 liters of methanol, stirred again for 30 minutes and filtered again. Then, the obtained polyimide was dried at 40 ℃ for 1 day under reduced pressure, to obtain A-1. A-1 had a weight average molecular weight (Mw) of 30,100 and a number average molecular weight (Mn) of 14,500.

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

The polyimide precursor (A-1) for comparative example does not contain a polyalkyleneoxy group and a polymerizable group and does not belong to a specific resin.

[ chemical formula 73]

< Synthesis example 12: synthesis of polyimide (A-2) for comparative example

155.1g of 4, 4' -Oxydiphthalic Dianhydride (ODPA) was placed in a separable flask, and 134.0g of 2-hydroxyethyl methacrylate (HEMA) and 400ml of γ -butyrolactone were added. 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 naturally cooled to room temperature and allowed to stand for a further 16 hours.

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

The obtained reaction liquid was added to 3 liters of ethanol, and a precipitate composed of a crude polymer was produced. The produced crude polymer was recovered by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain 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 recovered by filtration and then vacuum-dried, thereby obtaining a powdery polyimide precursor (a-2) for comparative example. The weight average molecular weight (Mw) of the polyimide precursor (A-2) for the comparative example was measured, and found to be 20,000.

< Synthesis example 13: synthesis of polyimide precursor (A-3) for comparative example

In synthesis example 12, a reaction was carried out in the same manner as in synthesis example 18 except that 147.1g of 3,3 ', 4,4 ' -biphenyltetracarboxylic dianhydride was used instead of 155.1g of 4,4 ' -oxydiphthalic dianhydride, thereby obtaining a polyimide precursor (a-3) for a comparative example. The weight average molecular weight (Mw) of the polyimide precursor (A-3) for the comparative example was measured, and found to be 22,000.

The polyimide precursors (A-2) and (A-3) for the comparative examples do not contain a polyalkyleneoxy group and do not belong to specific resins.

< 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. 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 numerical value in the column of "parts by mass" indicates the content (parts by mass) of each component.

In Table 1, for example, the expressions "PI-1/PI-2" in the column "type" and "16/16" in the column "parts by mass" indicate that 16 parts by mass of PI-1 and 16 parts by mass of PI-2 were used, respectively.

In table 1, the expression "-" indicates that no corresponding component is contained.

The ingredients listed in table 1 are specifically as follows.

[ specific resin or comparative resin ]

PI-1 to PI-8: PI-1 to PI-8 synthesized in the above

PA-1: PA-1 synthesized in the above

A-1 to A-3: a-1 to A-3 synthesized in the above

[ solvent ]

DMSO: dimethyl sulfoxide

GBL: gamma-butyrolactone

Lactic acid Ethyl ester

NMP: n-methyl pyrrolidone

In table 1, the DMSO/GBL is described as DMSO and GBL mixed in a ratio of DMSO: GBL of 20:80 (mass ratio).

In table 1, the NMP/ethyl lactate is described as NMP and ethyl lactate were mixed at a ratio of 80:20 (mass ratio).

[ polymerization initiator ]

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

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

[ polymerizable Compound ]

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

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

SR-239: SR-239 (manufactured by Sartomer Company, Inc)

SR-268: SR-268 (manufactured by Sartomer Company, Inc)

A-DPH: dipentaerythritol hexaacrylate (SHIN-NAKAMURA CHEMICAL CO, manufactured by LTD.)

[ polymerization inhibitor ]

F-1: 1, 4-benzoquinones

F-2: 4-methoxyphenol

F-3: 1, 4-dihydroxy benzene

F-4: 2-nitroso-1-naphthol (Tokyo Chemical Industry Co., Ltd., manufactured by Ltd.)

[ agent for improving adhesion of Metal ]

G-1 to G-4: a compound of the structure. In the following structural formulae, Et represents an ethyl group.

[ chemical formula 74]

(migration inhibitor)

H-1: 1H-tetrazole

H-2: 1,2, 4-triazoles

H-3: 5-phenyltetrazole

[ thermal alkali-producing agent ]

I-1: a compound of the structure

[ chemical formula 75]

[ additives ]

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

< evaluation >

In each of examples and comparative examples, the coating properties and the film strength (elongation at break) were evaluated using the prepared curable resin composition or the comparative composition.

The evaluation method for each evaluation is specifically described below.

[ coatability ]

A silicon step substrate was prepared by forming a total of 10 steps of 100 μm in length, 20 μm in width and 5 μm in depth on one surface of a silicon substrate having a diameter of 4 inches.

Fig. 1 is a schematic view of the formed step substrate.

In fig. 1,5 columns and 2 rows of 10 steps 2 are formed on the surface of a silicon substrate 1.

In fig. 1, the step 2 is a step having a depth of 5 μm with respect to the surface of the portion of the silicon substrate 1 where the step is not formed. In each of the 10 steps, the depth of the step is substantially the same.

In FIG. 1, A represents the longitudinal length of the step 2 and is 100. mu.m.

In FIG. 1, B represents the lateral length of the step 2 and is 20 μm.

In FIG. 1, the intervals of 5 steps arranged in the transverse direction are all 1 mm.

In FIG. 1, the interval between two steps arranged in the longitudinal direction is 2 mm.

Each of the curable resin compositions prepared in examples and comparative examples or the composition for comparison was applied to the step substrate shown in fig. 1 by spin coating, thereby forming a curable resin composition layer.

The silicon wafer to which the obtained curable resin composition layer was applied was dried on a hot plate at 100 ℃ for 5 minutes, and a curable resin composition layer having a uniform thickness of about 15 μm was obtained on the silicon wafer.

The surface of the cured resin composition layer after drying was observed by AFM (atomic force microscope), and the level difference of the film measured by the following formula FL was calculated.

Formula FL: difference in height of film (maximum height of curable resin composition layer) - (minimum height of curable resin composition layer)

The surface of the dried curable resin composition layer was observed with an optical microscope defect inspection apparatus KLA2360 (manufactured by Applied Materials, inc.) and Review SEM Vision G3 (manufactured by Applied Materials, inc.) to calculate the thickness per 1cm²The number of defects of (2).

The coating properties were evaluated according to the following evaluation criteria using the film thickness difference and the number of defects as indices. The evaluation results are shown in the column "coatability" in table 1. The smaller the difference in height of the film and the smaller the number of defects, the more excellent the coatability of the composition.

Evaluation criteria-

A: the height difference of the film is less than 0.3 μm, and the number of defects is less than 5/cm²。

B: the height difference of the film is less than 0.3 μm, and the number of defects is 5/cm²More than and less than 10 pieces/cm²。

C: the height difference of the film is more than 0.3 μm and less than 0.5 μm, and the number of defects is less than 10/cm²。

D: the height difference of the film is more than 0.5 mu m and the number of defects is 10/cm²At least one condition is satisfied in both of the above.

[ film Strength (elongation at Break) ]

Each of the curable resin compositions prepared in examples and comparative examples or the composition for comparison was applied to a silicon wafer by a spin coating method, thereby forming a curable resin composition layer.

The obtained curable resin composition layer (resin layer) was heated at a temperature rise rate of 10 ℃/min under a nitrogen atmosphere, and after reaching the temperature described in the column of "curing conditions" in table 1, it was heated at that temperature for 3 hours.

The cured resin layer (cured film) was immersed in a 4.9 mass% hydrofluoric acid aqueous solution, and the cured film was peeled from the silicon wafer. The peeled cured film was punched out by a punch to prepare a test piece having a width of 3mm and a sample length of 30 mm. The elongation at break (elongation at break) of the film in the longitudinal direction of the film was measured using a tensile tester (Tensilon) under an environment of a crosshead speed of 300 mm/min, 25 ℃ and 65% RH (relative humidity) in accordance with JIS-K6251. In the evaluation, each of examples and comparative examples was carried out 5 times, and the arithmetic mean of the measured values of the elongation at break in the 5 measurements was taken as an index value.

The index value was evaluated according to the following evaluation criteria, and the evaluation results are shown in table 1.

Evaluation criteria-

A: the index value is 60% or more.

B: the index value is 55% or more and less than 60%.

C: the index value is 50% or more and less than 55%.

D: the index value is less than 50%.

From the above results, it is clear that the curable resin composition containing a specific resin of the present invention is excellent in coatability.

The comparative compositions of comparative examples 1 to 2 do not contain a specific resin. The comparative compositions of comparative examples 1 to 2 were found to have poor coatability.

< example 101 >

The curable resin composition described in example 1 was spin-coated on the surface of the copper thin layer in the resin substrate having the copper thin layer formed on the surface thereof, so that the film thickness became 20 μm. The curable resin composition applied to the resin substrate was dried at 100 ℃ for 2 minutes, and then exposed to light using a stepper (NSR 1505 i6, manufactured by Nikon Corporation). The mask having a square pattern (100 μm square pattern in length and width, repetition number 10) was set at 400mJ/cm at a wavelength of 365nm²The exposure is carried out at the exposure dose of (2) to produce a pattern with a residual square. After exposure, development was performed with cyclopentanone for 30 seconds, and the pattern was obtained by rinsing with PGMEA for 20 seconds.

Next, the temperature was increased at a temperature increase rate of 10 ℃/min in a nitrogen atmosphere to the temperature described in the column of "curing conditions" in table 1, and then the resultant was heated at that temperature 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, a semiconductor device was manufactured using the rewiring layer interlayer insulating film, and as a result, it was confirmed that the semiconductor device was operating normally.

Description of the symbols

1-silicon substrate, 2-step difference, longitudinal length of a-step difference, lateral length of B-step difference.

Claims

1. A curable resin composition comprising:

a polymerization initiator;

a polymerizable compound; and

a solvent.

2. The curable resin composition according to claim 1,

the structure having the polyalkyleneoxy group and the polymerizable group includes a structure represented by the following formula (1-1),

3. The curable resin composition according to claim 2,

z is¹At least one group selected from the group consisting of an ethylenically unsaturated group, a cyclic ether group and a methylol group is contained as the polymerizable group.

4. The curable resin composition according to claim 2 or 3,

the resin contains a structure represented by the following formula (1-2) as a structure containing a structure represented by the formula (1-1),

in the formula (1-2), L¹Represents a b +2 valent linking group, X²To representEster, urethane, urea, amide or ether bonds, L²Represents a single bond or an a + 1-valent linking group, X¹Represents a structure represented by the formula (1-1), wherein a represents an integer of 1 or more, b represents an integer of 1 or more, and a plurality of X's are present²、L²、X¹Or a, a plurality of X²、L²、X¹Or a is the same or different.

5. The curable resin composition according to any one of claims 2 to 4,

the repeating unit having a structure represented by the formula (1-1) includes a repeating unit represented by the following formula (1-3),

in the formula (1-3), L¹Represents a b +2 valent linking group, X²Represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond, L²Represents a single bond or an a + 1-valent linking group, X¹Represents a structure represented by the formula (1-1), a represents an integer of 1 or more, b represents an integer of 1 or more, L⁴Represents a structure represented by the following formula (L4-1) or formula (L4-2), wherein X is present in plural²、L²、X¹Or a, a plurality of X²、L²、X¹Or a is the same or different from each other,

6. The curable resin composition according to claim 4 or 5,

said L¹Comprising at least one structure selected from the group consisting of structures represented by the following formulae (A-1) to (A-5),

in the formulae (A-1) to (A-5), R^A11～R^A14、R^A21～R^A24、R^A31～R^A38、R^A41～R^A48And R^A51～R^A58Each independently represents a hydrogen atom, an alkyl group, a cyclic alkyl group, an alkoxy group, a hydroxyl group, a cyano group, a haloalkyl group, a halogen atom, or a group which is related to X in the formula (1-2) or the formula (1-3)²Bonding site of, L^A31And L^A41Each independently represents a single bond, carbonyl group, sulfonyl group, 2-valent saturated hydrocarbon group, 2-valent unsaturated hydrocarbon group, hetero atom, heterocyclic group or halogenated alkylene group, R^A11～R^A14、R^A21～R^A24、R^A31～R^A38、R^A41～R^A48And R^A51～R^A58In each case b are as defined above for formula (1-2) or X in formula (1-3)²The bonding sites of (a) each independently represent a bonding site with another structure.

7. The curable resin composition according to any one of claims 1 to 6, which is used for forming an interlayer insulating film for a rewiring layer.

8. A cured film obtained by curing the curable resin composition according to any one of claims 1 to 7.

9. A laminate having 2 or more layers of the cured films of claim 8 with a metal layer between the cured films.

10. 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 7 to a substrate to form a film.

11. The method for producing a cured film according to claim 10, comprising an exposure step of exposing the film to light and a development step of developing the film.

12. The method for producing a cured film according to claim 10 or 11, which comprises a step of heating the film at 50 to 450 ℃.

13. A semiconductor device comprising the cured film according to claim 8 or the laminate according to claim 9.

14. A polyimide or a polyimide precursor comprising a structure represented by the following formula (1-1),