JP7492003B2 - CURABLE RESIN COMPOSITION, CURED FILM, LAMINATE, METHOD FOR PRODUCING CURED FILM, AND SEMICONDUCTOR DEVICE - Google Patents

Description

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

Polyimide or polybenzoxazole has excellent heat resistance and insulating properties, and is therefore used in a variety of applications. The applications are not particularly limited, but for example, in the case of semiconductor devices for mounting, it can be used as an insulating film or sealing material, or as a protective film. It is also used as a base film or coverlay for flexible substrates.

For example, in the above-mentioned applications, the polyimide or polybenzoxazole is used in the form of a curable resin composition containing at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor.
Such a curable resin composition is applied to a substrate by, for example, coating to form a resin film, and then, if necessary, exposure, development, heating, etc. are performed to form a cured film on the substrate.
The polyimide precursor and the polybenzoxazole precursor are cyclized, for example, by heating, to become polyimide and polybenzoxazole, respectively, in the cured film.
Since the curable resin composition can be applied by a known coating method, etc., it can be said to have excellent adaptability in manufacturing, for example, high degree of freedom in designing the shape, size, application position, etc., of the applied curable resin composition. In addition to the high performance of polyimide, polybenzoxazole, etc., from the viewpoint of such excellent adaptability in manufacturing, the industrial application development of the above-mentioned curable resin composition is expected to continue.

For example, Patent Document 1 describes an adhesive composition for adhering a semiconductor element to a support member, the adhesive composition containing (A) a thermoplastic resin having a carboxyl group and/or a hydroxyl group, (B) a compound having an oxazoline group in the molecule, and (C) a thermosetting resin.
For example, Patent Document 2 describes a polyimide having a specific structure.

JP 2008-260907 A JP 2016-113498 A

In the production of a cured film made of a curable resin composition that is to come into contact with a metal, there is a demand for improved adhesion between the cured film and the metal.
Examples of the metal include metals contained in a metal layer such as a conductive layer. Examples of the metal include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper, aluminum, and alloys containing these metals are preferred, copper or alloys containing copper are more preferred, and copper is even more preferred.
For example, in a laminate including a metal layer and a cured film in contact with the metal layer, there is a demand for improved adhesion between the metal layer and the cured film.

The present invention aims to provide a curable resin composition that can give a cured film having excellent adhesion to metals, 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.

Examples of typical embodiments of the present invention are given below.
<1> At least one resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, a polyimide, and a polybenzoxazole;
Compounds having an oxazoline group, and
Compounds containing an acid group and an alkoxysilyl group are included.
A curable resin composition.
<2> The curable resin composition according to <1>, wherein the resin has a carboxy group content of 1.0 mmol/g or less.
<3> The curable resin composition according to <1> or <2>, wherein the compound having an oxazoline group is a compound containing two or more oxazoline groups in the structure.
<4> The curable resin composition according to any one of <1> to <3>, wherein the compound having an oxazoline group includes at least one selected from the group consisting of an alkoxysilyl group, a radically polymerizable group, and an azole group.
<5> The curable resin composition according to any one of <1> to <4>, wherein the compound having an oxazoline group is a resin.
<6> The curable resin composition according to any one of <1> to <5>, wherein the compound containing an acid group and an alkoxysilyl group is a resin.
<7> The curable resin composition according to any one of <1> to <6>, wherein the compound containing an acid group and an alkoxysilyl group contains at least one group selected from the group consisting of a radical polymerizable group and an azole group.
<8> The curable resin composition according to any one of <1> to <7>, further comprising at least one compound selected from the group consisting of a thermal base generator, a photobase generator, and an onium salt.
<9> The curable resin composition according to any one of <1> to <8>, which is used for forming an interlayer insulating film for a redistribution layer.
<10> A cured film obtained by curing the curable resin composition according to any one of <1> to <9>.
<11> A laminate comprising two or more layers of the cured film according to <10>, and a metal layer between any two adjacent layers of the cured films.
<12> A method for producing a cured film, comprising a film-forming step of applying the curable resin composition according to any one of <1> to <9> to a substrate to form a film.
<13> The method for producing the cured film according to <12>, comprising: an exposure step of exposing the film to light; and a development step of developing the film.
<14> The method for producing a cured film according to <12> or <13>, further comprising a heating step of heating the film at 50 to 450° C.
<15> A semiconductor device comprising the cured film according to <10> or the laminate according to <11>.

According to the present invention, there are provided a curable resin composition which gives a cured film having excellent adhesion to metal, 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.

The main embodiments of the present invention will be described below, however, the present invention is not limited to the embodiments explicitly described.
In this specification, a numerical range expressed using the symbol "to" means a range that includes the numerical values before and after "to" as the lower limit and upper limit, respectively.
In this specification, the term "step" includes not only an independent step, but also a step that cannot be clearly distinguished from another step, so long as the intended effect of the step can be achieved.
In the description of groups (atomic groups) in this specification, when there is no indication of whether they are substituted or unsubstituted, the term encompasses both unsubstituted groups (atomic groups) and substituted groups (atomic groups). For example, an "alkyl group" encompasses not only alkyl groups without a substituent (unsubstituted alkyl groups) but also alkyl groups with a substituent (substituted alkyl groups).
In this specification, unless otherwise specified, the term "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, electron beams, and other actinic rays or radiation.
In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", "(meth)acrylic" means both or either of "acrylic" and "methacrylic", and "(meth)acryloyl" means both or either of "acryloyl" and "methacryloyl".
In this specification, in the structural formulae, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In this specification, the total solid content refers to the total mass of all components of the composition excluding the solvent, and in this specification, the solid content concentration refers to the mass percentage of the other components excluding the solvent with respect to the total mass of the composition.
In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise stated. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined, for example, by using HLC-8220GPC (manufactured by Tosoh Corporation) and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise stated, these molecular weights were measured using THF (tetrahydrofuran) as the eluent. In addition, the detection in the GPC measurement was performed using a UV (ultraviolet) wavelength 254 nm detector, unless otherwise stated.
In this specification, when the positional relationship of each layer constituting the laminate is described as "upper" or "lower", it is sufficient that there is another layer above or below the reference layer among the multiple layers being noted. In other words, a third layer or element may be interposed between the reference layer and the other layer, and the reference layer does not need to be in contact with the other layer. In addition, unless otherwise specified, the direction in which the layers are stacked on the substrate is referred to as "upper", or, in the case of a photosensitive layer, the direction from the substrate to the photosensitive layer is referred to as "upper", and the opposite direction is referred to as "lower". Note that such a vertical direction is set for the convenience of this specification, and in an actual embodiment, the "upper" direction in this specification may be different from the vertical upward direction.
In this specification, unless otherwise specified, the composition may contain, as each component contained in the composition, two or more compounds corresponding to that component. Furthermore, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component.
In this specification, unless otherwise specified, the temperature is 23° C., the pressure is 101,325 Pa (1 atm), and the relative humidity is 50% RH.
As used herein, combinations of preferred aspects are more preferred aspects.

(Curable resin composition)
The curable resin composition of the present invention contains at least one resin (hereinafter also referred to as the "specific resin") selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, a polyimide, and a polybenzoxazole, a compound having an oxazoline group, and a compound containing an acid group and an alkoxysilyl group.

The curable resin composition of the present invention may be a negative curable resin composition or a positive curable resin composition, but is preferably a negative curable resin composition.
The negative curable resin composition refers to a composition in which, when a layer formed from the curable resin composition is exposed to light, the unexposed portion is removed by a developer.
The positive curable resin composition refers to a composition in which, when a layer formed from the curable resin composition is exposed to light, the exposed portion (exposed area) is removed by a developer.

In addition, from the viewpoint of the film strength of the obtained cured film, it is preferable that the curable resin composition of the present invention contains at least one compound selected from the group consisting of a thermal base generator, a photobase generator, and an onium salt, which will be described later.

According to the curable resin composition of the present invention, a cured film having excellent adhesion to metals can be obtained.
The mechanism by which the above effects are obtained is unclear, but is speculated to be as follows.

The curable resin composition of the present invention contains a compound having an oxazoline group, and a compound containing an acid group and an alkoxysilyl group, and thus the obtained cured film has excellent adhesion to metal.
In the formation of the cured film, the resin having a siloxane bond formed by the bond of the alkoxysilyl group contained in the cured film obtained by the reaction of the acid group with the oxazoline group contains a structure derived from the oxazoline group. It is presumed that the interaction between the structure derived from the oxazoline group and the specific resin results in a cured film with excellent adhesion.
In particular, when the oxazoline group is bifunctional or higher, a crosslinked structure can be formed between the acid groups in the compound having an acid group and an alkoxysilyl group, or between the acid groups in the compound having an acid group and an alkoxysilyl group and the acid groups in the specific resin, which is considered to result in even better adhesion.
When the compound having an oxazoline group has a polymerizable group other than an oxazoline group, it is considered that the adhesion is further improved because a structure derived from the oxazoline group is contained in a resin formed by polymerization of the specific resin or the polymerizable compound by polymerization of the compounds having oxazoline groups together, or by polymerization of, for example, a crosslinking agent (also referred to as a polymerizable compound) or a specific resin having a polymerizable group and a compound having an oxazoline group.
When the compound having an oxazoline group contains an azole group, it is considered that the adhesion to metals is further improved because the azole group is coordinated to the metal.
In addition, it is believed that the oxazoline group also crosslinks with the acid group in the specific resin, thereby improving chemical resistance.

Here, Patent Documents 1 and 2 do not describe or suggest a curable resin composition containing a compound having an oxazoline group and a compound containing an acid group and an alkoxysilyl group.

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

<Specific resin>
The curable resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor.
The curable resin composition of the present invention preferably contains a polyimide or a polyimide precursor as the specific resin, and more preferably contains a polyimide precursor.

In addition, the specific resin preferably has a polymerizable group.
Examples of the polymerizable group in the specific resin include known polymerizable groups such as a radical polymerizable group, an epoxy group, an oxetanyl group, a methylol group, and an alkoxymethyl group.
The radically polymerizable group is preferably a group having an ethylenically unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a group having an optionally substituted vinyl group directly bonded to an aromatic ring, such as a vinyl group, an allyl group, or a vinylphenyl group, a (meth)acrylamide group, or a (meth)acryloyloxy group, with a (meth)acryloyloxy group being preferred.
When the compound having an oxazoline group contains a polymerizable group, the specific resin preferably has a polymerizable group polymerizable with the compound having an oxazoline group.
Examples of combinations of polymerizable groups that can be polymerized include combinations in which a specific resin has a radical polymerizable group and a compound having an oxazoline group has a radical polymerizable group, or combinations in which a specific resin has an epoxy group and a compound having an oxazoline group has an epoxy group.
According to the above embodiment, it is believed that the adhesion of the obtained cured film to metal is further improved by polymerization of the polymerizable group in the specific resin and the polymerizable group in the compound having an oxazoline group in the cured film.

Furthermore, when the compound containing an acid group and an alkoxysilyl group has a polymerizable group, the specific resin preferably has a polymerizable group polymerizable with the polymerizable group in the compound containing an acid group and an alkoxysilyl group.
Examples of combinations of polymerizable groups that can be polymerized include combinations in which a specific resin has a radical polymerizable group and a compound containing an acid group and an alkoxysilyl group has a radical polymerizable group, or combinations in which a specific resin has an epoxy group and a compound containing an acid group and an alkoxysilyl group has an epoxy group.
According to the above aspect, in the cured film, the polymerizable group in the specific resin and the polymerizable group in the compound containing an acid group and an alkoxysilyl group are polymerized, and further, the acid group in the compound containing an acid group and an alkoxysilyl group and the oxazoline group in the compound having an oxazoline group are bonded to each other. This is considered to further improve the adhesion of the obtained cured film to metal.
Furthermore, in the above embodiment, the compound having an oxazoline group preferably has an alkoxysilyl group.
According to the above aspect, in the cured film, the polymerizable group in the specific resin and the polymerizable group in the compound containing an acid group and an alkoxysilyl group are polymerized, and the alkoxysilyl group in the compound containing an acid group and an alkoxysilyl group and the alkoxysilyl group in the compound having an oxazoline group are condensed, so that the bond between the compounds becomes strong, and it is considered that the adhesion of the obtained cured film to metal is further improved.

In addition, the specific resin preferably contains a radically polymerizable group.
When the specific resin has a radical polymerizable group, the curable resin composition preferably contains a photoradical polymerization initiator described later as a photosensitizer, more preferably contains a photoradical polymerization initiator described later as a photosensitizer and a radical crosslinking agent described later, and further preferably contains a photoradical polymerization initiator described later as a photosensitizer, a radical crosslinking agent described later, and a sensitizer described later. For example, a negative type photosensitive layer is formed from such a curable resin composition.
The specific resin may also have a polarity conversion group such as an acid-decomposable group.
When the specific resin has an acid decomposable group, the curable resin composition preferably contains a photoacid generator as described below as a photosensitizer. From such a curable resin composition, for example, a chemically amplified positive-type photosensitive layer or negative-type photosensitive layer is formed.

It is also preferable that the content of the carboxy group in the specific resin is 1.0 mmol/g or less.
According to the above aspect, the developability is improved when a developer containing an organic solvent is used as the developer.
The content of the carboxy group in the specific resin is preferably 0.001 to 1.0 mmol/g, and more preferably 0.01 to 0.8 mmol/g.
According to the above aspect, the developability is improved when a developer containing an organic solvent is used as the developer, and it becomes possible for the compound having an oxazoline group to form a bond with the specific resin. Therefore, it is considered that the adhesion of the obtained cured film to metal is also excellent.

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

In formula (2), ^A1 and ^A2 each independently represent an oxygen atom or NH, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, and ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group.

In formula (2), A ¹ and A ² each independently represent an oxygen atom or NH, and preferably an oxygen atom.
R ¹¹¹ in formula (2) represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and a group containing an aromatic group. A linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group consisting of a combination thereof is preferred, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferred. A particularly preferred embodiment of the present invention is exemplified by a group represented by -Ar-L-Ar-. Here, each Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ₂ -, or NHCO-, or a group consisting of a combination of two or more of the above. The preferred ranges of these are as described above.

R ¹¹¹ is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, or two or more types may be used.
Specifically, it is preferable that the diamine contains a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group consisting of a combination thereof, and it is more preferable that the diamine contains a group consisting of an aromatic group having 6 to 20 carbon atoms. Examples of the aromatic group include the following.

In the formula, A is preferably a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -SO ₂ -, NHCO-, or a group selected from these combinations, 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-, or -SO ₂ -, and further preferably -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -, or -C(CH ₃ ) ₂ -.
In the formula, * represents a bonding site with other structures.

Specific examples of diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3-, or 1,4-diaminocyclohexane, 1,2-, 1,3-, or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane, and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diamino Biphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- and 3,3'-diaminodiphenylmethane, 4,4'- and 3,3'-diaminodiphenyl sulfone, 4,4'- and 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxyphenyl)propane, bis(4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoparaterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy 4,4'-diaminophenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy )phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetonitrile, Guanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)phenyl and at least one diamine selected from 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolidine, and 4,4'-diaminoquaterphenyl.

Also preferred are the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of WO 2017/038598.

In addition, the following diamines can also be suitably used.

Diamines having two or more alkylene glycol units in the main chain, as described in paragraphs 0032 to 0034 of WO 2017/038598, are also preferably used.

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

From the viewpoint of i-line transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoints of i-line transmittance and ease of availability, R 111 is more preferably a divalent organic group represented by formula (61).
Equation (51)

In formula (51), R ⁵⁰ to R ⁵⁷ each independently represent a hydrogen atom, a fluorine atom, or a monovalent organic group, and at least one of R ⁵⁰ to R ⁵⁷ represents a fluorine atom, a methyl group, or a trifluoromethyl group.
Examples of the monovalent organic group for R ⁵⁰ to R ⁵⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

In formula (61), R ⁵⁸ and R ⁵⁹ each independently represent a fluorine atom or a trifluoromethyl group.
Examples of diamine compounds that give the structure of formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. These may be used alone or in combination of two or more.

Furthermore, R ¹¹¹ may be a structure containing a polymerizable group.
For example, R ¹¹¹ may have a structure derived from a diamine compound having a polymerizable group.
The diamine compound having a polymerizable group is not particularly limited, but is preferably a compound containing an aromatic ring structure, and more preferably a compound having a structure in which a structure containing an amino group and a polymerizable group is directly bonded to the aromatic ring structure.
As the polymerizable group, a group containing an ethylenically unsaturated group, a cyclic ether group, a methylol group, or an alkoxymethyl group is preferable, a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloxy group, a maleimide group, a vinylphenyl group, an epoxy group, an oxetanyl group, a methylol group, or an alkoxymethyl group is more preferable, and a (meth)acryloxy group, a (meth)acrylamide group, an epoxy group, a methylol group, or an alkoxymethyl group is even more preferable.

When R ¹¹¹ is a structure containing a polymerizable group, R ¹¹¹ is preferably a structure represented by the following formula (1-1).

In formula (1-1), ^Y1 represents an (n+2) valent group containing an aromatic hydrocarbon group, ^P1 represents a group containing a polymerizable group, n represents an integer of 1 or more, and * represents a bonding site with the nitrogen atom to which ^R111 in formula (2) is bonded.

^-Y1-
In formula (1-1), ^Y1 represents an (n+2) valent group containing an aromatic hydrocarbon group.
The aromatic hydrocarbon group for ^Y1 is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, still more preferably a group in which two or more hydrogen atoms have been removed from a benzene ring, and particularly preferably a group in which three or more hydrogen atoms have been removed from a benzene ring.
In formula (1-1), it is preferable that the bonding sites of ^Y1 to the two * in formula (1-1) are both aromatic hydrocarbon groups. That is, it is preferable that the two * in formula (1-1) are directly bonded to the aromatic hydrocarbon ring structure contained in ^Y1 .
In addition, in formula (1-1), it is preferable that the bonding sites of ^Y1 to ^P1 are all aromatic hydrocarbon groups. That is, it is preferable that ^P1 is directly bonded to the aromatic hydrocarbon ring structure contained in ^Y1 .

^Y1 preferably contains at least one structure selected from the group consisting of structures represented by the following formulas (A2-1) to (A2-5), and more preferably contains at least one structure selected from the group consisting of structures represented by the above formulas (A2-1) to (A2-5).
^{In formulas ( A2-1 ) to ( A2-5 ) , R to R , ... ​ ​ ​ ​} At least one of ^A248 and at least one of R ^A251 to R ^A258 may be a bonding site with ^P1 in the above formula (1-1), and * each independently represents a bonding site with another structure.

Among these, from the viewpoint of solvent solubility, ^Y1 preferably contains a structure represented by any one of formulas (A2-1) to (A2-4), and more preferably contains a structure represented by formula (A2-2) or formula (A2-4).

In formulas ( ^{A2-1 )} to (A2-5), R to ^R , R to ^R , R to R , R ^{to R} do not contain a bonding site with the carbonyl group in the above formula ( ^1-1 ), and ^at least one of R to ^R , at ^least one of R , ^at least one of R ^, at ^least one of R , at ^least one of R , at ^least one of R , at least one of ^R , at least one of ^R , at least one of ^R , at ^least one of R , at least one of ^R , at least one of R , at least ^one of R .
In formula (A2-1), when R ^A211 to R ^A214 are not bonding sites to ^P1 , it is preferable that R ^A211 to R ^A214 each independently represent 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 hydroxy group, a cyano group, a halogenated alkyl group having 1 to 3 carbon atoms, or a halogen atom, and from the viewpoint of solvent solubility, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom is more preferable.
The halogen atom in the halogenated alkyl group in R ^A211 to R ^A214 or the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a chlorine atom or a bromine atom is preferable.
In formula (A2-2), R ^A221 to R ^A224 have the same meanings as R ^A211 to R ^A214 in formula (A2-1), respectively, and preferred embodiments are also the same.
In formula (A2-3), ^{it is preferable} that R ^to R each independently represent 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 hydroxy group, a cyano group, a halogenated alkyl group having 1 to 3 carbon atoms, or a halogen atom, and from the viewpoint of solvent solubility, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogenated alkyl group having 1 to 3 carbon atoms is more preferable, and a hydrogen atom or an alkyl group having 1 to 6 carbon atoms is more preferable.
The halogen atom in the halogenated alkyl group in R ^A231 to R ^A238 or the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, with a chlorine atom or a bromine atom being preferred.
In formula (A2-3), L ^A231 preferably represents a single bond, a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, a divalent unsaturated hydrocarbon group having 5 to 24 carbon atoms, -O-, -S-, -NR ^N -, a heterocyclic group, or a halogenated alkylene group having 1 to 6 carbon atoms, preferably a single bond, a saturated hydrocarbon group having 1 to 6 carbon atoms, -O- or a heterocyclic group, and more preferably a single bond or -O-.
The above R ^N represents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, still more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.
The divalent unsaturated hydrocarbon group may be a divalent aliphatic unsaturated hydrocarbon group or a divalent aromatic hydrocarbon group, but is preferably a divalent aromatic hydrocarbon group.
The heterocyclic group is, for example, preferably a group in which two hydrogen atoms have been removed from an aliphatic or aromatic heterocycle, more preferably a group in which two hydrogen atoms have been removed from an aliphatic or aromatic heterocycle, and more preferably a group in which two hydrogen atoms have been removed from a ring structure such as a pyrrolidine ring, a tetrahydrofuran ring, a tetrahydrothiophene ring, a pyrrole ring, a furan ring, a thiophene ring, a piperidine ring, a tetrahydropyran ring, a pyridine ring, a morpholine ring, etc. These heterocycles may further form a condensed ring with another heterocycle or a hydrocarbon ring.
The heterocycle preferably has 5 to 10 ring members, and more preferably 5 or 6 ring members.
The heteroatom in the heterocyclic group is preferably an oxygen atom, a nitrogen atom, or a sulfur atom.
Examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a chlorine atom or a bromine atom being preferred.
In formula (A2-4), R ^A241 to R ^A248 and L ^A241 have the same meanings as R ^A231 to R ^A238 and L ^A231 in formula (A2-3), respectively, and preferred embodiments are also the same.
In formula (A2-5), R ^A251 to R ^A258 have the same meanings as R ^A211 to R ^A214 in formula (A2-1), respectively, and preferred embodiments are also the same.

In formula (A2-1), it is preferable that at least one of R ^{to R} is a bonding site to ^P1 in formula ( ^{1-1 )} , it is more preferable that one of R to ^R is a bonding site to ^P1 , and it is preferable that R is a bonding site to ^P1 .
In formula (A2-2), it is preferable that at least one of R ^{to R} is a bonding site with ^P1 in formula ( ^{1-1 )} , it is more preferable that one of R to R is a bonding site with ^P1 , ^and it is preferable that R is a bonding site with ^P1 .
In formula (A2-3), it is preferable that at least one of R ^{to R} is a bonding site with ^P1 in formula ( ^1-1 ), it is more preferable that two of R to ^R are bonding sites with the above-mentioned ^P1 , it is even more preferable that a total of two, one of ^{R to R} and one of R ^to R, are bonding sites with the above-mentioned ^P1 , and it is particularly preferable that two of ^R and ^R are bonding sites with the above-mentioned ^P1 .
In formula (A2-4), it is preferable that at least one of R ^{to R} is a bonding site with ^P1 in formula ( ^1-1 ), it is more preferable that two of R to ^R are bonding sites with the above-mentioned ^P1 , it is even more preferable that a total of two, one of ^{R to R} and one of R ^to R, are bonding sites with the above-mentioned ^P1 , and it is particularly preferable that two of ^R and ^R are bonding sites with the above-mentioned ^P1 .
In formula (A2-5), it is preferable that at least one of R ^{to R} is a bonding site with ^P1 in formula ( ^1-1 ), it is more preferable that two of R to ^R are bonding sites with the above-mentioned ^P1 , it is even more preferable that a total of two, one of R ^{to R} and one of R ^{to R} , are bonding sites with the above-mentioned ^P1 , and it is particularly preferable that two, ^R and ^R , are bonding sites with the above-mentioned ^P1 .

In formulae (A2-1) to (A2-5), each of the two *'s is preferably the *'s in formula (1-1). That is, it is preferable that the two nitrogen atoms to which R ¹¹¹ in formula (2) is bonded are directly bonded to the positions represented by the two *'s in formulae (A2-1) to (A2-5).

Among these, Y ¹ is preferably a group represented by the following formula (Y-1) or (Y-2).

In formula (Y-1), R ^Y11 , R ^Y12 and R ^Y13 have the same meanings as R ^A211 , R ^A212 and R ^A214 in formula (A2-1), respectively, and preferred embodiments are also the same.
In formula (Y-2), R ^Y21 to R ^Y26 have the same definitions as R ^A242 to R ^A247 in formula (A2-4), respectively, and preferred embodiments are also the same.
In formula (Y-1) or formula (Y-2), * indicates a bonding site to the two nitrogen atoms to which R ¹¹¹ in formula (2) is bonded, and # indicates a bonding site to P ¹ in formula (1-1).

^-P1-
In formula (1-1), ^P1 represents a group containing a polymerizable group.
As the polymerizable group, a group containing an ethylenically unsaturated group, a cyclic ether group, a methylol group, or an alkoxymethyl group is preferable, a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloxy group, a maleimide group, a vinylphenyl group, an epoxy group, an oxetanyl group, a methylol group, or an alkoxymethyl group is more preferable, and a (meth)acryloxy group, a (meth)acrylamide group, an epoxy group, a methylol group, or an alkoxymethyl group is even more preferable.
The number of polymerizable groups contained in ^P1 is 1 or more, preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, particularly preferably 1 or 2, and most preferably 1.

In addition, ^P1 is preferably a group represented by the following formula (P-1).

In formula (P-1), ^L1 represents a single bond or an (m+1)-valent linking group, ^A2 represents a polymerizable group, m represents an integer of 1 or more, and * represents a bonding site with ^Y1 .
In formula (P-1), L ¹ is preferably a single bond, a hydrocarbon group, an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, -NR ^N -, or a group having two or more of these bonded together, and more preferably a single bond, a hydrocarbon group, an ether bond, a carbonyl group, -NR ^N -, or a group having two or more of these bonded together.
The above R ^N represents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, still more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.
The hydrocarbon group for ^L1 is preferably a saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a group represented by a combination thereof, and more preferably a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a group in which two or more hydrogen atoms have been removed from a benzene ring, or a group represented by a bond thereof.

In formula (P-1), ^A2 is preferably a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloxy group, a maleimide group, a vinylphenyl group, an epoxy group, an oxetanyl group, a methylol group, or an alkoxymethyl group, and more preferably a (meth)acryloxy group, a (meth)acrylamide group, an epoxy group, a methylol group, or an alkoxymethyl group.

In formula (P-1), m is preferably an integer from 1 to 15, more preferably an integer from 1 to 10, even more preferably an integer from 1 to 5, particularly preferably 1 or 2, and most preferably 1.

In addition, ^P1 is preferably a group represented by the following formula (P-2) or formula (P-3).

In formula (P-2), ^A2 represents a polymerizable group, and * represents a bonding site with ^Y1 .
In formula (P-2), ^A2 has the same meaning as ^A2 in formula (P-1), and preferred embodiments are also the same.
In formula (P-3), ^A2 represents a polymerizable group, ^L2 represents a hydrocarbon group, or a hydrocarbon group and an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, -NR ^N -, or a group in which two or more of these are bonded together, ^Z1 represents an ether bond, an ester bond, a urethane bond, a urea bond, an amide bond, or a carbonate bond, and * represents the bonding site with ^Y1 . R ^N is as defined above.
In formula (P-3), ^A2 has the same meaning as ^A2 in formula (P-1), and preferred embodiments are also the same.
In formula (P-3), ^L2 is preferably a hydrocarbon group, a (poly)alkyleneoxy group, or a group represented by a combination thereof. The hydrocarbon group is preferably an alkylene group, a divalent aromatic hydrocarbon group, or a group represented by a combination thereof, and more preferably an alkylene group.
In this specification, the term "(poly)alkyleneoxy group" refers to an alkyleneoxy group or a polyalkyleneoxy group. In addition, in the present invention, the term "polyalkyleneoxy group" refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the multiple alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different. When the polyalkyleneoxy group contains multiple types of alkyleneoxy groups with different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, an arrangement having blocks, or an arrangement having a pattern such as alternating.
The alkylene group is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 20 carbon atoms, and even more preferably an alkylene group having 1 to 10 carbon atoms.
The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, further preferably a phenylene group or naphthylene group, and particularly preferably a phenylene group.
The alkylene group in the (poly)alkyleneoxy group is preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, more preferably an ethylene group or propylene group, and even more preferably an ethylene group.
The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2-20, more preferably 2-10, even more preferably 2-5, and particularly preferably 2-4.
In formula (P-3), ^Z1 represents an ether bond, an ester bond, a urethane bond, a urea bond, an amide bond, or a carbonate bond, and is more preferably an ester bond, a urethane bond, a urea bond, or an amide bond.
In the present invention, when simply describing "ester bond", "urethane bond", "amide bond", etc., the orientation of these bonds is not limited. For example, when ^Z1 is an ester bond, the bonding site of ^Z1 with ^L2 may be a carbon atom or an oxygen atom in the ester bond.

In formula (2), R ¹¹⁵ represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.
In formula (5) or (6), each * independently represents a bonding site to another structure.

In formula (5), R ¹¹² is preferably a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ₂ -, NHCO-, or a group selected from combinations thereof, more preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, and SO ₂ -, and still more preferably a divalent group selected from the group consisting of -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S-, and SO ₂ -.

Specific examples of R ¹¹⁵ include tetracarboxylic acid residues remaining after removal of an anhydride group from a tetracarboxylic dianhydride, etc. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used.
The tetracarboxylic dianhydride is preferably represented by the following formula (O).

In formula (O), R ¹¹⁵ represents a tetravalent organic group. The preferred range of R ¹¹⁵ is the same as that of R ¹¹⁵ in formula (2), and the preferred range is also the same.

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

Furthermore, the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598 are also preferred examples.

It is also preferable that at least one of R ¹¹¹ and R ¹¹⁵ has an OH group. More specifically, R ¹¹¹ may be a residue of a bisaminophenol derivative.

R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, and it is preferable that at least one of R ¹¹³ and R ¹¹⁴ contains a polymerizable group, and it is more preferable that both contain a polymerizable group. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, radicals, etc., and is preferably a radically polymerizable group. Specific examples of the polymerizable group in the specific resin include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, a methylol group, and an amino group. As the radically polymerizable group of the polyimide precursor or the like, a group having an ethylenically unsaturated bond is preferable.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, and a group represented by the following formula (III), with the group represented by the following formula (III) being preferred.

In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and preferably a hydrogen atom.
In formula (III), * represents a bonding site with another structure.
In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, —CH ₂ CH(OH)CH ₂ —, or a polyalkyleneoxy group.
Suitable examples of R ²⁰¹ include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a 1,2-butanediyl group, a 1,3-butanediyl group, a pentamethylene group, a hexamethylene group, an octamethylene group, a dodecamethylene group, -CH ₂ CH(OH)CH ₂ -, and a polyalkyleneoxy group, of which an ethylene group, a propylene group, a trimethylene group, -CH ₂ CH(OH)CH ₂ -, and a polyalkyleneoxy group are more preferable, and a polyalkyleneoxy group is even more preferable.
In the present invention, the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the multiple alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
When the polyalkyleneoxy group contains multiple types of alkyleneoxy groups having different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, an arrangement having blocks, or an arrangement having a pattern such as alternating.
The number of carbon atoms in the alkylene group (including the number of carbon atoms of the substituent, when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 5, still more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2.
The alkylene group may have a substituent, and preferred examples of the substituent include an alkyl group, an aryl group, and a halogen atom.
The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2-20, more preferably 2-10, and even more preferably 2-6.
From the viewpoint of solvent solubility and solvent resistance, the polyalkyleneoxy group is preferably a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, more preferably a polyethyleneoxy group or a polypropyleneoxy group, and even more preferably a polyethyleneoxy group.In the group in which multiple ethyleneoxy groups and multiple 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 alternating.The preferred embodiment of the number of repetitions of the ethyleneoxy groups in these groups is as described above.

R ¹¹³ and R ¹¹⁴ are each independently a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include aromatic groups and aralkyl groups in which an acidic group is bonded to one, two or three, preferably one, of the carbon atoms constituting the aryl group. Specific examples include aromatic groups having 6 to 20 carbon atoms and having an acidic group, and aralkyl groups having 7 to 25 carbon atoms and having an acidic group. More specific examples include a phenyl group having an acidic group and a benzyl group having an acidic group. The acidic group is preferably an OH group.
It is also more preferable that R ¹¹³ or R ¹¹⁴ is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl or 4-hydroxybenzyl.

From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. The monovalent organic group preferably contains 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 in the alkyl group is preferably 1 to 30. The alkyl group may be linear, branched, or cyclic. Examples of linear or branched alkyl groups 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 t-butyl group, a 1-ethylpentyl group, a 2-ethylhexyl group, a 2-(2-(2-methoxyethoxy)ethoxy)ethoxy group, a 2-(2-(2-ethoxyethoxy)ethoxy)ethoxy group, a 2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy group, and a 2-(2-(2-(2-ethoxyethoxy)ethoxy)ethoxy)ethoxy group. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic cyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a camphenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a campholoyl group, a dicyclohexyl group, and a pinenyl group. Among them, the cyclohexyl group is the most preferable from the viewpoint of compatibility with high sensitivity. In addition, the alkyl group substituted with an aromatic group is preferably a linear alkyl group substituted with an aromatic group as described below.
Specific examples of the aromatic group include a substituted or unsubstituted benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indacene ring, a perylene ring, a pentacene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, a chrysene ring, a triphenylene ring, a fluorene ring, a biphenyl ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, A pyrimidine ring, a pyridazine ring, an indolizine ring, an indole ring, a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, a quinolizine ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinoxazoline ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxathiin ring, a phenothiazine ring, or a phenazine ring. A benzene ring is most preferred.

In formula (2), when R ¹¹³ is a hydrogen atom or when R ¹¹⁴ is a hydrogen atom, the polyimide precursor may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

At least one of R ¹¹³ and R ¹¹⁴ may be a polarity conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, etc. are preferred, and from the viewpoint of exposure sensitivity, an acetal group is more preferred.
Specific examples of the acid-decomposable group include a tert-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tert-butoxycarbonylmethyl group, a trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.

It is also preferable that the polyimide precursor has fluorine atoms in the structural units. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more and 20% by mass or less.

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

The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having a repeating unit represented by formula (2-A). By adopting such a structure, it is possible to further widen the width of the exposure latitude.
Formula (2-A)

In formula (2-A), A ¹ and A ² represent an oxygen atom, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, and at least one of R ¹¹³ and R ¹¹⁴ is a group containing a polymerizable group, and it is preferable that both are polymerizable groups.

A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ each independently have the same definition as A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (2), and the preferred ranges are also the same.
R ¹¹² has the same definition as R ¹¹² in formula (5), and the preferred range is also the same.

The polyimide precursor may contain one type of repeating structural unit represented by formula (2), or may contain two or more types. It may also contain a structural isomer of the repeating unit represented by formula (2). It goes without saying that the polyimide precursor may contain other types of repeating structural units in addition to the repeating unit of formula (2).

An example of one embodiment of the polyimide precursor of the present invention is a polyimide precursor in which 50 mol % or more, further 70 mol % or more, and particularly 90 mol % or more of the total repeating units are repeating units represented by formula (2).

The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and even more preferably 22,000 to 25,000. The number average molecular weight (Mn) of the polyimide precursor is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.
The molecular weight dispersity of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and even more preferably 2.8 or more. The upper limit of the molecular weight dispersity of the polyimide precursor is not particularly specified, but is, for example, preferably 4.5 or less, more preferably 4.0 or less, even more preferably 3.8 or less, even more preferably 3.2 or less, even more preferably 3.1 or less, even more preferably 3.0 or less, and particularly preferably 2.95 or less.
In this specification, the dispersity of molecular weight is a value calculated by weight average molecular weight/number average molecular weight.

[Polyimide]
The polyimide used in the present invention may be an alkali-soluble polyimide, or may be a polyimide that is soluble in a developer containing an organic solvent as a main component.
In this specification, the alkali-soluble polyimide refers to a polyimide that dissolves at 0.1 g or more in 100 g of a 2.38 mass % aqueous tetramethylammonium solution at 23° C., and from the viewpoint of pattern formability, a polyimide that dissolves at 0.5 g or more is preferable, and a polyimide that dissolves at 1.0 g or more is more preferable. The upper limit of the dissolution amount is not particularly limited, but it is preferably 100 g or less.
From the viewpoint of the film strength and insulating properties of the resulting organic film, the polyimide is preferably a polyimide having a plurality of imide structures in the main chain.
In this specification, the term "main chain" refers to the relatively longest bonding chain in the molecule of the polymer compound constituting the resin, and the term "side chain" refers to any other bonding chain.

-Fluorine atom-
From the viewpoint of the film strength of the resulting organic film, the polyimide preferably contains fluorine atoms.
The fluorine atom is preferably contained, for example, in R ¹³² in the repeating unit represented by formula (4) described later or in R ¹³¹ in the repeating unit represented by formula (4) described later, and more preferably contained as a fluorinated alkyl group in R ¹³² in the repeating unit represented by formula (4) described later or in R ¹³¹ in the repeating unit represented by formula (4) described later.
The amount of fluorine atoms relative to the total mass of the polyimide is preferably from 1 to 50 mol/g, and more preferably from 5 to 30 mol/g.

-Silicon atom-
From the viewpoint of the film strength of the resulting organic film, it is preferable that the polyimide contains a silicon atom.
The silicon atom is preferably contained in R ¹³¹ in the repeating unit represented by formula (4) described later, and more preferably contained in R ¹³¹ in the repeating unit represented by formula (4) described later as an organically modified (poly)siloxane structure described later.
The silicon atom or the organic modified (poly)siloxane structure may be contained in a side chain of the polyimide, but is preferably contained in the main chain of the polyimide.
The amount of silicon atoms relative to the total mass of the polyimide is preferably 0.01 to 5 mol/g, and more preferably 0.05 to 1 mol/g.

- Ethylenically unsaturated bond -
From the viewpoint of the film strength of the resulting organic film, the polyimide preferably has an ethylenically unsaturated bond.
The polyimide may have an ethylenically unsaturated bond at the end of the main chain or in a side chain, but preferably in the side chain.
The ethylenically unsaturated bond is preferably radically polymerizable.
The ethylenically unsaturated bond is preferably contained in R ¹³² in the repeating unit represented by formula (4) described later or in R ¹³¹ in the repeating unit represented by formula (4) described later, and more preferably contained as a group having an ethylenically unsaturated bond in R ¹³² in the repeating unit represented by formula (4) described later or in R ¹³¹ in the repeating unit represented by formula (4) described later.
Among these, the ethylenically unsaturated bond is preferably contained in R ¹³¹ in the repeating unit represented by formula (4) described later, and more preferably contained as a group having an ethylenically unsaturated bond in R ¹³¹ in the repeating unit represented by formula (4) described later.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (IV).

In formula (IV), R ²⁰ represents a hydrogen atom or a methyl group, and preferably a methyl group.

In formula (IV), R ²¹ represents an alkylene group having 2 to 12 carbon atoms, -O-CH ₂ CH(OH)CH ₂ -, -C(=O)O-, -O(C=O)NH-, a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3), or a group consisting of a combination of two or more of these.

Among these, R ²¹ is preferably a group represented by any one of the following formulae (R1) to (R3), and more preferably a group represented by formula (R1).

In formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group in which two or more of these are bonded together; X represents an oxygen atom or a sulfur atom; * represents a bonding site with another structure; and ● represents a bonding site with the oxygen atom to which R ²⁰¹ in formula (III) is bonded.
In formulas (R1) to (R3), preferred aspects of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms for L are the same as the preferred aspects of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms for ^R21 described above.
In formula (R1), X is preferably an oxygen atom.
In formulae (R1) to (R3), * has the same meaning as * in formula (IV), and preferred embodiments are also the same.
The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having an isocyanato group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate).
The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate, etc.).
The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate, etc.).
From the viewpoint of solvent solubility and solvent resistance, the polyalkyleneoxy group is preferably a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, more preferably a polyethyleneoxy group or a polypropyleneoxy group, and even more preferably a polyethyleneoxy group.In the group in which multiple ethyleneoxy groups and multiple 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 alternating.The preferred embodiment of the number of repetitions of the ethyleneoxy groups in these groups is as described above.

In formula (IV), * represents a bonding site with other structures, and is preferably a bonding site with the main chain of the polyimide.

The amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.05 to 10 mol/g, and more preferably 0.1 to 5 mol/g.
From the viewpoint of manufacturability, the amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol/g, and more preferably 0.0005 to 0.05 mol/g.

- Crosslinkable group other than ethylenically unsaturated bond -
The polyimide may have a crosslinkable group other than the ethylenically unsaturated bond.
Examples of crosslinkable groups other than ethylenically unsaturated bonds include epoxy groups, cyclic ether groups such as oxetanyl groups, alkoxymethyl groups such as methoxymethyl groups, and methylol groups.
A crosslinkable group other than an ethylenically unsaturated bond is preferably contained in, for example, R ¹³¹ in the repeating unit represented by formula (4) described below.
The amount of crosslinkable groups other than ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.05 to 10 mol/g, and more preferably 0.1 to 5 mol/g.
From the viewpoint of manufacturability, the amount of crosslinkable groups other than ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol/g, and more preferably 0.001 to 0.05 mol/g.

- Polarity conversion group -
The polyimide may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the polyimide is the same as the acid-decomposable group described in R ¹¹³ and R ¹¹⁴ in the above formula (2), and preferred embodiments are also the same.

-Acid value-
When the polyimide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of the polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and even more preferably 70 mgKOH/g or more.
The acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less.
When the polyimide is subjected to development using a developer containing an organic solvent as a main component (for example, "solvent development" described later), the acid value of the polyimide is preferably from 2 to 35 mgKOH/g, more preferably from 3 to 30 mgKOH/g, and even more preferably from 5 to 20 mgKOH/g.
The acid value is measured by a known method, for example, the method described in JIS K 0070:1992.
The acid group contained in the polyimide is preferably an acid group having a pKa of 0 to 10, more preferably 3 to 8, from the viewpoint of achieving both storage stability and developability.
pKa is the equilibrium constant Ka of a dissociation reaction in which a hydrogen ion is released from an acid, expressed as its negative common logarithm pKa. In this specification, pKa is a value calculated using ACD/ChemSketch (registered trademark) unless otherwise specified. Alternatively, the value listed in "Revised 5th Edition Chemistry Handbook: Basics" edited by the Chemical Society of Japan may be referenced.
Furthermore, when the acid group is a polyvalent acid such as phosphoric acid, the pKa is the first dissociation constant.
As such an acid group, the polyimide preferably contains at least one type selected from the group consisting of a carboxy group and a phenolic hydroxy group, and more preferably contains a phenolic hydroxy group.

-Phenol hydroxy group-
From the viewpoint of ensuring an appropriate development speed with an alkaline developer, the polyimide preferably has a phenolic hydroxy group.
The polyimide may have a phenolic hydroxy group at the end of the main chain or on a side chain.
The phenolic hydroxy group is preferably contained, for example, in R ¹³² in the repeating unit represented by formula (4) described below, or in R ¹³¹ in the repeating unit represented by formula (4) described below.
The amount of the phenolic hydroxy group relative to the total mass of the polyimide is preferably from 0.1 to 30 mol/g, and more preferably from 1 to 20 mol/g.

The polyimide used in the present invention is not particularly limited as long as it is a polymeric compound having an imide ring, but it preferably contains a repeating unit represented by the following formula (4), and more preferably is a compound containing a repeating unit represented by formula (4) and having a polymerizable group.
Equation (4)

In formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group.
When the polyimide has a polymerizable group, the polymerizable group may be located at least one of R ¹³¹ and R ¹³² , or may be located at the end of the polyimide as shown in the following formula (4-1) or formula (4-2).
Formula (4-1)

In formula (4-1), R ¹³³ is a polymerizable group, and the other groups are the same as those in formula (4).
Formula (4-2)

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

The polymerizable group has the same meaning as the polymerizable group described above in relation to the polymerizable group contained in the polyimide precursor or the like.
R ¹³¹ represents a divalent organic group. Examples of the divalent organic group include the same as those of R ¹¹¹ in formula (2), and the preferred range is also the same.
R ¹³¹ may be a diamine residue remaining after removal of the amino group of the diamine. The diamine may be an aliphatic, cyclic aliphatic, or aromatic diamine. Specific examples include the example of R ¹¹¹ in the formula (2) of the polyimide precursor.

R ¹³¹ is preferably a diamine residue having at least two alkylene glycol units in the main chain in order to more effectively suppress the occurrence of warping during firing, more preferably a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and even more preferably a diamine residue not containing an aromatic ring.

Examples of diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule include, but are not limited to, Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (all trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.

R ¹³² represents a tetravalent organic group. Examples of the tetravalent organic group include the same as those of R ¹¹⁵ in formula (2), and the preferred range is also the same.
For example, the four bonds of the tetravalent organic group exemplified as R ¹¹⁵ bond to the four —C(═O)— portions in the above formula (4) to form a condensed ring.

Furthermore, R ¹³² may be a tetracarboxylic acid residue remaining after removal of the anhydride group from a tetracarboxylic dianhydride. A specific example is R ¹¹⁵ in the formula (2) of the polyimide precursor. From the viewpoint of the strength of the organic film, R ¹³² is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

It is also preferable that at least one of R ¹³¹ and R ¹³² has an OH group. More specifically, preferred examples of R ¹³¹ include 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18), and more preferred examples of R ¹³² include the above (DAA-1) to (DAA-5).

It is also preferable that the polyimide has fluorine atoms in its structural units. The content of fluorine atoms in the polyimide is preferably 10% by mass or more, and is preferably 20% by mass or less.

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

In addition, in order to improve the storage stability of the composition, it is preferable to cap the main chain ends of the polyimide with a terminal capping agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound. Of these, it is more preferable to use a monoamine, and preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy 5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

-Imidization rate (ring closure rate)-
From the viewpoints of the film strength, insulating properties, etc. of the resulting organic film, the imidization rate of the polyimide (also referred to as the "ring closure rate") is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.
There is no particular upper limit to the imidization rate, and it is sufficient if it is 100% or less.
The imidization rate is measured, for example, by the following method.
The infrared absorption spectrum of the polyimide is measured to determine the peak intensity P1 near 1377 cm ⁻¹ , which is an absorption peak derived from the imide structure. Next, the polyimide is heat-treated at 350° C. for 1 hour, and then the infrared absorption spectrum is measured again to determine the peak intensity P2 near 1377 cm ⁻¹ . Using the obtained peak intensities P1 and P2, the imidization rate of the polyimide can be calculated based on the following formula.
Imidization rate (%)=(peak intensity P1/peak intensity P2)×100

The polyimide may contain repeating structural units of the above formula (4) all containing one type of R ¹³¹ or R ¹³² , or may contain repeating units of the above formula (4) containing two or more different types of R ¹³¹ or R ^132. Furthermore, the polyimide may contain other types of repeating structural units in addition to the repeating units of the above formula (4).

Polyimides can be synthesized, for example, by reacting a tetracarboxylic dianhydride with a diamine compound (partially substituted with a terminal blocking agent which is a monoamine) at low temperature, by reacting a tetracarboxylic dianhydride (partially substituted with a terminal blocking agent which is an acid anhydride, a monoacid chloride compound, or a monoactive ester compound) with a diamine compound at low temperature, by obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then reacting the diamine (partially substituted with a terminal blocking agent which is a monoamine) in the presence of a condensing agent, by obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then converting the remaining dicarboxylic acid into an acid chloride and reacting the diamine (partially substituted with a terminal blocking agent which is a monoamine), or by using a method in which a polyimide precursor is obtained and then completely imidized by a known imidization reaction method, or by stopping the imidization reaction midway and partially introducing an imide structure, or by blending a completely imidized polymer with the polyimide precursor to partially introduce an imide structure.
Examples of commercially available polyimide products include Durimide (registered trademark) 284 (manufactured by Fujifilm Corporation) and Matrimide 5218 (manufactured by HUNTSMAN Corporation).

The weight average molecular weight (Mw) of the polyimide is 4,000 to 100,000, preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By making the weight average molecular weight 5,000 or more, the folding resistance of the film after curing can be improved. In order to obtain an organic film with excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. In addition, when two or more types of polyimides are contained, it is preferable that the weight average molecular weight of at least one type of polyimide is in the above range.

[Polybenzoxazole precursor]
The polybenzoxazole precursor used in the present invention is not particularly limited with respect to its structure, but preferably contains a repeating unit represented by the following formula (3).
Equation (3)

In formula (3), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group.

In formula (3), R ¹²³ and R ¹²⁴ each have the same definition as R ¹¹³ in formula (2), and the preferred range is also the same. That is, it is preferable that at least one of them is a polymerizable group.
In formula (3), R ¹²¹ represents a divalent organic group. The divalent organic group is preferably a group containing at least one of an aliphatic group and an aromatic group. The aliphatic group is preferably a linear aliphatic group. R ¹²¹ is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.

As the dicarboxylic acid residue, a dicarboxylic acid residue containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferred, and a dicarboxylic acid residue containing an aromatic group is more preferred.
The dicarboxylic acid containing an aliphatic group is preferably a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group, and more preferably a dicarboxylic acid consisting of a linear or branched (preferably linear) aliphatic group and two -COOH groups. The number of carbon atoms in the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, even more preferably 3 to 20, even more preferably 4 to 15, and particularly preferably 5 to 10. The linear aliphatic group is preferably an alkylene group.
Dicarboxylic acids containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, and 2,2,6,6-tetramethylpimelic acid. , suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanediacid, heneicosanediacid, docosanediacid, tricosanediacid, tetracosanediacid, pentacosanediacid, hexacosanediacid, heptacosanediacid, octacosanediacid, nonacosanediacid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and further dicarboxylic acids represented by the following formula.

(In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer from 1 to 6.)

As dicarboxylic acids containing an aromatic group, the following dicarboxylic acids having an aromatic group are preferred, and the following dicarboxylic acids consisting of only an aromatic group and two -COOH groups are more preferred.

In the formula, A represents a divalent group selected from the group consisting of -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, -C(CF ₃ ) ₂ -, and -C(CH ₃ ) ₂ -, and each * independently represents a bonding site to another structure.

Specific examples of dicarboxylic acids containing aromatic groups include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.

In formula (3), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same meaning as R ¹¹⁵ in formula (2) above, and the preferred range is also the same.
R ¹²² is also preferably a group derived from a bisaminophenol derivative. Examples of the group derived from a bisaminophenol derivative include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(4-amino-4-hydroxyphenyl)hexafluoropropane, and the like. Examples of the bisaminophenols include 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, and 1,3-diamino-4,6-dihydroxybenzene. These bisaminophenols may be used alone or in combination.

Among the bisaminophenol derivatives, the following bisaminophenol derivatives having aromatic groups are preferred:

In the formula, _X1 represents -O-, -S-, -C( _CF3 ) _2- , _-CH2- , _-SO2- or -NHCO-, and * and # each represent a bonding site with another structure. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom or an alkyl group. It is also preferable that ^R122 represents a structure represented by the above formula. When R ¹²² is a structure represented by the above formula, of the total of four * and #, it is preferable that any two are bonding sites with the nitrogen atom to which R ¹²² in formula (3) is bonded, and the other two are bonding sites with the oxygen atom to which R ¹²² in formula (3) is bonded, and the two * are bonding sites with the oxygen atom to which R ¹²² in formula (3) is bonded, and the two # are bonding sites with the nitrogen atom to which R ¹²² in formula (3) is bonded, or it is more preferable that the two * are bonding sites with the nitrogen atom to which R ¹²² in formula (3) is bonded, and the two # are bonding sites with the oxygen atom to which R ¹²² in formula (3) is bonded, and it is even more preferable that the two * are bonding sites with the oxygen atom to which R ¹²² in formula (3) is bonded, and the two # are bonding sites with the nitrogen atom to which R ¹²² in formula (3) is bonded.

In formula (A-s), R ₁ is a hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, a single bond, or an organic group selected from the group represented by the following formula (A-sc). R ₂ is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different. R ₃ is any one of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different.

(In formula (A-sc), * indicates bonding to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by formula (A-s) above.)

In the above formula (A-s), having a substituent at the ortho position of the phenolic hydroxy group, i.e., at _R3 , is considered to bring the distance between the carbonyl carbon of the amide bond and the hydroxy group closer, and is particularly preferred in that the effect of achieving a high cyclization rate when cured at a low temperature is further enhanced.

In addition, in the above formula (As), it is preferable that R ₂ is an alkyl group and R ₃ is an alkyl group, since this can maintain the effects of high transparency to i-line and a high cyclization rate when cured at a low temperature.

In the above formula (A-s), it is further preferred that R ₁ is an alkylene or a substituted alkylene. Specific examples of the alkylene and substituted alkylene for R ₁ include linear or branched alkyl groups having 1 to 8 carbon atoms, of which -CH ₂ -, -CH(CH ₃ )-, and -C(CH ₃ ) ₂ - are more preferred in that they can provide a well-balanced polybenzoxazole precursor that has sufficient solubility in solvents while maintaining the effects of high transparency to i-line and a high cyclization rate when cured at low temperature.

For a method for producing the bisaminophenol derivative represented by the above formula (A-s), reference can be made to, for example, paragraphs [0085] to [0094] and Example 1 (paragraphs [0189] to [0190]) of JP 2013-256506 A, the contents of which are incorporated herein by reference.

Specific examples of the structure of the bisaminophenol derivative represented by the above formula (A-s) include those described in paragraphs 0070 to 0080 of JP 2013-256506 A, the contents of which are incorporated herein by reference. Needless to say, the invention is not limited to these.

The polybenzoxazole precursor may contain other types of repeating structural units in addition to the repeating unit of formula (3) above.
In terms of being able to suppress the occurrence of warping due to ring closure, it is preferable that the resin composition contains a diamine residue represented by the following formula (SL) as another type of repeating structural unit.

In formula (SL), Z has an a-structure and a b-structure, R ^1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R ^2s is a hydrocarbon group having 1 to 10 carbon atoms, and at least one of R ^3s , R ^4s , R ^5s , and R ^6s is an aromatic group, and the remaining are a hydrogen atom or an organic group having 1 to 30 carbon atoms, which may be the same or different. Polymerization of the a-structure and the b-structure may be block polymerization or random polymerization. The mol % of the Z portion is 5 to 95 mol % for the a-structure, 95 to 5 mol % for the b-structure, and a+b is 100 mol %.

In formula (SL), preferred Z includes those in which R ^5s and R ^6s in the b structure are phenyl groups. The molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the molecular weight within the above range, it is possible to more effectively reduce the elastic modulus of the polybenzoxazole precursor after dehydration ring closure, and to simultaneously achieve the effect of suppressing warpage and the effect of improving solvent solubility.

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

When used in a composition described later, the polybenzoxazole precursor has a weight average molecular weight (Mw) of preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and even more preferably 22,000 to 28,000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.
The polybenzoxazole precursor has a molecular weight dispersity of preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. The upper limit of the molecular weight dispersity of the polybenzoxazole precursor is not particularly specified, but is, for example, preferably 2.6 or less, more preferably 2.5 or less, even more preferably 2.4 or less, even more preferably 2.3 or less, and even more preferably 2.2 or less.

[Polybenzoxazole]
The polybenzoxazole is not particularly limited as long as it is a polymeric compound having a benzoxazole ring, but is preferably a compound represented by the following formula (X), and more preferably a compound represented by the following formula (X) having a polymerizable group. The polymerizable group is preferably a radically polymerizable group. Alternatively, it may be a compound represented by the following formula (X) having a polarity conversion group such as an acid-decomposable group.

In formula (X), R ¹³³ represents a divalent organic group, and R ¹³⁴ represents a tetravalent organic group.
When a polarity conversion group such as a polymerizable group or an acid-decomposable group is present, the polarity conversion group such as a polymerizable group or an acid-decomposable group may be located at least one of R ¹³³ and R ¹³⁴ , or may be located at an end of the polybenzoxazole as shown in the following formula (X-1) or formula (X-2).
Formula (X-1)

In formula (X-1), at least one of R ¹³⁵ and R ¹³⁶ is a polarity conversion group such as a polymerizable group or an acid-decomposable group, and when it is not a polarity conversion group such as a polymerizable group or an acid-decomposable group, it is an organic group, and the other groups are as defined in formula (X).
Formula (X-2)

In formula (X-2), R ¹³⁷ is a polarity conversion group such as a polymerizable group or an acid-decomposable group, and the others are substituents, and the other groups have the same meanings as in formula (X).

The polarity conversion group, such as a polymerizable group or an acid-decomposable group, is synonymous with the polymerizable group described above as the polymerizable group possessed by the polyimide precursor, etc.

R ¹³³ represents a divalent organic group. The divalent organic group may be an aliphatic or aromatic group. Specific examples include the examples of R ¹²¹ in the formula (3) of the polybenzoxazole precursor. In addition, preferred examples thereof are the same as R ¹²¹ .

R ¹³⁴ represents a tetravalent organic group. Examples of the tetravalent organic group include the examples of R ¹²² in the formula (3) of the polybenzoxazole precursor. Preferred examples thereof are the same as those of R ¹²² .
For example, the four bonds of the tetravalent organic group exemplified as R ¹²² bond to the nitrogen atom and oxygen atom in the above formula (X) to form a condensed ring. For example, when R ¹³⁴ is the following organic group, the following structure is formed.

The polybenzoxazole preferably has an oxazolization rate of 85% or more, and more preferably 90% or more. By having an oxazolization rate of 85% or more, the film shrinkage caused by ring closure that occurs when the film is oxazolized by heating is reduced, and warping can be more effectively suppressed.

The polybenzoxazole may contain repeating structural units of the above formula (X) all containing one type of R ¹³¹ or R ¹³² , or may contain repeating units of the above formula (X) containing two or more different types of R ¹³¹ or R ^132. Furthermore, the polybenzoxazole may contain other types of repeating structural units in addition to the repeating units of the above formula (X).

Polybenzoxazole can be obtained, for example, by reacting a bisaminophenol derivative with a dicarboxylic acid containing R ¹³³ or a compound selected from dicarboxylic acid dichlorides and dicarboxylic acid derivatives of the above dicarboxylic acid to obtain a polybenzoxazole precursor, which is then oxazolized using a known oxazolization reaction method.
In the case of dicarboxylic acids, in order to increase the reaction yield, etc., it is also possible to use an active ester type dicarboxylic acid derivative which has been reacted in advance with 1-hydroxy-1,2,3-benzotriazole or the like.

The weight average molecular weight (Mw) of the polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By making the weight average molecular weight 5,000 or more, the folding resistance of the film after curing can be improved. In order to obtain an organic film with excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. In addition, when two or more types of polybenzoxazole are contained, it is preferable that the weight average molecular weight of at least one type of polybenzoxazole is in the above range.

[Method for producing polyimide precursor, etc.]
The polyimide precursor or the like can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine, preferably by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting the halogenated dicarboxylic acid or a dicarboxylic acid derivative with a diamine.
In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent during the reaction. The organic solvent may be one type or two or more types.
The organic solvent can be appropriately selected depending on the raw materials, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone.
The polyimide may be produced by synthesizing a polyimide precursor and then cyclizing it by a method such as thermal imidization or chemical imidization (e.g., promoting the cyclization reaction by the action of a catalyst), or the polyimide may be synthesized directly.

It is also preferable to synthesize the compound using a non-halogenated catalyst without using the halogenating agent. As the non-halogenated catalyst, any known amidation catalyst that does not contain a halogen atom can be used without any particular restrictions, and examples of the non-halogenated catalyst include boroxine compounds, N-hydroxy compounds, tertiary amines, phosphate esters, amine salts, urea compounds, and carbodiimide compounds. Examples of the carbodiimide compounds include N,N'-diisopropylcarbodiimide and N,N'-dicyclohexylcarbodiimide.

-End-capping agent-
In the method for producing a polyimide precursor or the like, in order to further improve the storage stability of the composition, it is preferable to cap the ends of the polyimide precursor or the like with an end-capping agent such as an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, a monoactive ester compound, etc. As the end-capping agent, it is more preferable to use a monoamine, and preferred examples of the monoamine compound include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5 ... aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 4-aminostyrene, etc. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

-Solid precipitation-
The production of the polyimide precursor or the like may include a step of precipitating a solid. Specifically, the polyimide precursor or the like in the reaction solution is precipitated in water, and then dissolved in a solvent in which the polyimide precursor or the like is soluble, such as tetrahydrofuran, to precipitate the solid.
Thereafter, the polyimide precursor or the like is dried to obtain a powdered polyimide precursor or the like.

〔Content〕
The content of the specific resin in the composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the composition. The content of the resin in the composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the composition.
The composition of the present invention may contain only one specific resin, or may contain two or more specific resins. When two or more specific resins are contained, the total amount is preferably within the above range.

The curable resin composition of the present invention preferably contains at least two types of resins.
Specifically, the curable resin composition of the present invention may contain a total of two or more types of the specific resin and the other resin described later, or may contain two or more types of the specific resin, but it is preferable that the curable resin composition contains two or more types of the specific resin.
When the curable resin composition of the present invention contains two or more specific resins, it is preferable that the composition contains, for example, two or more polyimide precursors having different dianhydride-derived structures (R ¹¹⁵ in the above formula (2)).

<Other resins>
The composition of the present invention may contain the above-mentioned specific resin and another resin (hereinafter, simply referred to as "another resin") different from the specific resin.
Examples of other resins include polyamideimide, polyamideimide precursors, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, and acrylic resins.
For example, by further adding an acrylic resin, a composition with excellent coatability can be obtained, and an organic film with excellent solvent resistance can be obtained.
For example, by adding an acrylic resin having a weight-average molecular weight of 20,000 or less and a high polymerizable group value to the composition in place of or in addition to the polymerizable compound described later, the coatability of the composition and the solvent resistance of the organic film can be improved.

When the composition of the present invention contains other resins, the content of the other resins is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, even more preferably 1 mass% or more, still more preferably 2 mass% or more, even more preferably 5 mass% or more, and even more preferably 10 mass% or more, based on the total solid content of the composition.
In addition, the content of other resins in the composition of the present invention is preferably 80 mass % or less, more preferably 75 mass % or less, even more preferably 70 mass % or less, still more preferably 60 mass % or less, and even more preferably 50 mass % or less, based on the total solid content of the composition.
In addition, as a preferred embodiment of the composition of the present invention, the content of the other resin may be low. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the composition. The lower limit of the content is not particularly limited, and may be 0% by mass or more.
The composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more types are contained, it is preferable that the total amount is in the above range.

<Compounds Having an Oxazoline Group>
The curable resin composition of the present invention contains a compound having an oxazoline group.
In the present invention, the hydrogen atom in the oxazoline group may be substituted with a known substituent. In addition, an embodiment in which the compound having an oxazoline group has an unsubstituted oxazoline group as the oxazoline group is also one of the preferred embodiments of the present invention.
In the present invention, the oxazoline group is preferably a group represented by the following formula (1-1).

In formula (1-1), R ¹ to R ⁴ each independently represent a hydrogen atom or a substituent, and * represents a bonding site to another structure.
In formula (1-1), R ¹ to R ⁴ are preferably all hydrogen atoms or alkyl groups.
The alkyl group may be an alkyl group having 1 to 10 carbon atoms.

The compound having an oxazoline group may be a compound containing only one oxazoline group in its structure, but from the viewpoint of adhesion of the cured film to the metal, it is preferable that the compound contains two or more oxazoline groups in its structure.

The compound having an oxazoline group preferably contains a polymerizable group.
Examples of the polymerizable group include known polymerizable groups such as a radical polymerizable group, an alkoxysilyl group, an epoxy group, an oxetanyl group, a methylol group, an alkoxymethyl group, and a (blocked) isocyanate group.
Among these, from the viewpoint of adhesion of the cured film to metal, it is preferable that the compound having an oxazoline group contains, as the polymerizable group, at least one group selected from the group consisting of a radically polymerizable group and an alkoxysilyl group.

The alkoxysilyl group may be any one of a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group. From the viewpoint of adhesion of the cured film to metal, a trialkoxysilyl group is preferred.
The alkoxy group in the alkoxysilyl group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and even more preferably an ethoxy group.

The radically polymerizable group is preferably a group having an ethylenically unsaturated bond.
Preferred examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a group having an optionally substituted vinyl group directly bonded to an aromatic ring, such as a vinylphenyl group, a (meth)acrylamide group, and a (meth)acryloyloxy group.

The compound having an oxazoline group preferably contains an azole group.
According to the above embodiment, it is believed that the azole group coordinates with a metal such as copper, thereby further improving adhesion to the metal.
The azole group in the compound having an oxazoline group may be a five-membered heterocyclic compound containing one or more nitrogen atoms as ring members and having a structure in which one or more hydrogen atoms have been removed from a five-membered heterocyclic compound which may have a substituent or a condensed ring structure, but is preferably a five-membered heterocyclic compound containing only one or more nitrogen atoms and one or more carbon atoms as ring members and having a structure in which one or more hydrogen atoms have been removed from a five-membered heterocyclic compound which may have a substituent.
From the viewpoint of adhesion of the cured film to metal, the azole group is preferably a group having a structure in which one or more hydrogen atoms have been removed from a pyrrole ring, a pyrazole ring, an indazole ring, an imidazole ring, a benzimidazole ring, a 1,2,3-triazole ring, a 1,2,4-triazole ring, a benzotriazole ring, or a tetrazole ring, and more preferably a group having a structure in which one or more hydrogen atoms have been removed from an imidazole ring, a benzimidazole ring, a 1,2,4-triazole ring, or a benzotriazole ring.

The azole group in the compound having an oxazoline group is preferably a group represented by the following formula (B-1) or (B-2).

In formula (B-1), R ^B1 represents a bonding site with another structure, a hydrogen atom, or a monovalent organic group, Z ^B1 to Z ^B4 each independently represent ═CR ^B7 — or a nitrogen atom, R ^B7 represents a bonding site with another structure, a hydrogen atom, or a monovalent organic group, and at least one of R ^B1 and R ^B7 included in formula (B-1) represents a bonding site with another structure;
In formula (B-2), ^R to ^R each independently represent a bonding site with another structure, a hydrogen atom, or a monovalent organic group, Z and ^Z each independently represent ^═CR — or a ^nitrogen atom, ^R represents a bonding site with another structure, a hydrogen atom, or ^{a monovalent organic} group, and at least one of R to R and ^R included in formula (B-2) represents a bonding site with another structure.

In formula (B-1), R ^B1 represents a bonding site to another structure, a hydrogen atom or a monovalent organic group, and more preferably a bonding site to another structure.
The monovalent organic group in R ^B1 is not particularly limited and may be any known organic group as long as the effects of the present invention are obtained, but is preferably a hydrocarbon group or a carboxy group, and more preferably an alkyl group or a carboxy group. The number of carbon atoms in the hydrocarbon group or alkyl group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 4.

In formula (B-1), Z ^B1 to Z ^B4 each independently represent ═CR ^B7 — or a nitrogen atom.
Among these, an embodiment in which two of Z ^B1 to Z ^B4 are nitrogen atoms and two are =CR ^B7 --, an embodiment in which one of Z ^B1 to Z ^B4 is a nitrogen atom and three are =CR ^B7 --, or an embodiment in which three of Z ^B1 to Z ^B4 are nitrogen atoms and one is =CR ^B7 --, is preferred.
Among these, an embodiment in which ^ZB1 and ^ZB3 are nitrogen atoms and ZB2 and ^ZB4 are = ^CRB7- ; an embodiment in which ^ZB1 and ^ZB2 are nitrogen atoms and ^ZB3 and ^ZB4 are = ^CRB7- ; an embodiment in which ^ZB2 is a nitrogen atom and ZB1, ^ZB3 and ^ZB4 are = ^CRB7- ; or an embodiment in which ^ZB1 , ^ZB2 and ^ZB3 are nitrogen atoms and ^ZB4 is = ^CRB7- is preferred, and an embodiment ⁱⁿ which ^ZB1 and ^ZB3 are nitrogen ^atoms and ^ZB2 and ^ZB4 are = ^CRB7- is more preferred.
The above R ^B7 is preferably a hydrogen atom or a monovalent organic group.
Furthermore, when Z ^B1 , Z ^B2 and Z ^B3 are nitrogen atoms and Z ^B4 is ═CR ^B7 —, R ^B7 is preferably a bonding site to another structure.
Preferred embodiments of the monovalent organic group in R ^B7 are the same as the preferred embodiments of the monovalent organic group in R ^B1 described above.

At least one of R ^B1 and R ^B7 included in formula (B-1) represents a bonding site with another structure, and it is preferred that at least R ^B1 represents a bonding site with another structure. In addition, in formula (B-1), an embodiment in which only R ^B1 represents a bonding site with another structure, and R ^B7 each independently represents a hydrogen atom or a monovalent organic group, is also one of the preferred embodiments of the present invention.

In formula (B-2), Z ^B5 and Z ^B6 each independently represent ═CR ^B8 — or a nitrogen atom.
Among these, an embodiment in which both Z ^B5 and Z ^B6 represent a nitrogen atom, or an embodiment in which Z ^B5 represents a nitrogen atom and Z ^B6 represents =CR ^B8 -, respectively, is preferable.
In formula (B-2), when both Z ^B5 and Z ^B6 represent nitrogen atoms, it is preferable that R ^B6 represents a bonding site with another structure. In addition, in formula (B-2), an embodiment in which both Z ^B5 and Z ^B6 represent nitrogen atoms and only R ^B6 represents a bonding site with another structure is also one of the preferred embodiments of the present invention.
In formula (B-2), when Z ^B5 represents a nitrogen atom and Z ^B6 represents =CR ^B8 --, it is preferable that R ^B8 represents a bonding site with another structure. In addition, in formula (B-2), an embodiment in which Z ^B5 represents a nitrogen atom and Z ^B6 represents =CR ^B8 --, and only R ^B8 represents a bonding site with another structure, is also one of the preferred embodiments of the present invention.

In formula (B-2), R ^B2 to R ^B5 each independently represent a hydrogen atom or a monovalent organic group. Preferred embodiments of the monovalent organic group in R ^B2 to R ^B5 are the same as the preferred embodiments of the monovalent organic group in R ^B1 described above.
In formula (B-2), when ^Z represents a nitrogen atom and ^Z represents = ^CR -, ^R preferably represents a hydrogen atom or a monovalent organic group. Preferred embodiments of the monovalent organic group in ^R are the same as the preferred embodiments of the monovalent organic group in ^R.
In other cases, it is preferable that R ^B6 represents a bonding site with another structure. In particular, when Z ^B5 represents a nitrogen atom and Z ^B6 represents =CR ^B8 -, it is preferable that R ^B8 represents a bonding site with another structure.
In formula (B-2), R ^B8 preferably represents a bonding site to another structure.
When both Z ^B5 and Z ^B6 represent ═CR ^B8 —, it is preferred that one R ^B8 represents a bonding site with another structure, and the other represents a hydrogen atom or a monovalent organic group. Preferred embodiments of the monovalent organic group in R ^B8 are the same as the preferred embodiments of the monovalent organic group in R ^B1 described above.

At least one of R ^B2 to R ^B6 and R ^B8 included in formula (B-2) represents a bonding site with another structure, and it is preferred that at least R ^B6 or R ^B8 represents a bonding site with another structure. Another preferred embodiment of the present invention is one in which only one of R ^B6 and R ^B8 represents a bonding site with another structure, and the other of R ^B6 and R ^B8 and R ^B2 to R ^B5 each independently represent a hydrogen atom or a monovalent organic group.

Among these, the azole group is preferably a group represented by any one of the following formulas (B-3) to (B-6).

In formulae (B-3) to (B-6), R ^B9 to R ^B20 each independently represent a hydrogen atom or a monovalent organic group, and * represents a bonding site to another structure.
In formulae (B-3) to (B-6), preferred embodiments of the monovalent organic group in R ^B9 to R ^B20 are the same as the preferred embodiments of the monovalent organic group in R ^B1 described above.

The compound having an oxazoline group may be a compound having a molecular weight of less than 2,000 (hereinafter also referred to as an "oxazoline group-containing low molecular weight compound"), or may be a resin (hereinafter also referred to as an "oxazoline group-containing resin").
From the viewpoint of adhesion of the cured film to metal, it is also preferable that the curable resin composition contains both an oxazoline group-containing low molecular weight compound and an oxazoline group-containing resin.
From the viewpoint of adhesion, the compound having an oxazoline group is preferably a resin.

[Oxazoline group-containing low molecular weight compound]
The molecular weight of the oxazoline group-containing low molecular weight compound is less than 2,000, preferably 1,500 or less, and more preferably 1,000 or less.

The number of oxazoline groups in the oxazoline group-containing low molecular weight compound is preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.
From the viewpoint of adhesion, the number of oxazoline groups in the oxazoline group-containing low molecular weight compound is preferably 2 to 10, more preferably 2 to 4, and even more preferably 2.

As the oxazoline group-containing low molecular weight compound, a compound represented by the following formula (BL-1) or formula (BL-2) is preferable.

In formula (BL-1), R ¹ to R ⁴ each independently represent a hydrogen atom or a substituent, and R ⁵ represents a substituent.
In formula (BL-2), R ¹ to R ⁴ each independently represent a hydrogen atom or a substituent, L ¹ represents a single bond or an (n+1)-valent linking group, and n represents an integer of 2 or greater.
In formula (BL-1), R ¹ to R ⁴ each independently have the same meaning as R ¹ to R ⁴ in formula (1-1), and preferred embodiments are also the same.
In formula (BL-1), R ⁵ represents a substituent, and is preferably the above-mentioned azole group or a group containing the above-mentioned polymerizable group, more preferably the above-mentioned group containing the polymerizable group. In addition, an embodiment in which R ⁵ is a vinyl group is one of the preferred embodiments of the present invention.
In formula (BL-2), R ¹ to R ⁴ each independently have the same meaning as R ¹ to R ⁴ in formula (1-1), and preferred embodiments are also the same.
In formula (BL-2), ^L1 represents a single bond or a n+1-valent linking group, and is preferably a single bond or a hydrocarbon group. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, but is preferably an aromatic hydrocarbon group or a saturated aliphatic hydrocarbon group, more preferably an aromatic hydrocarbon group, and even more preferably a group in which n+1 hydrogen atoms have been removed from a benzene ring.
In formula (BL-2), n represents an integer of 2 or more, and is preferably an integer of 2 to 10, more preferably an integer of 2 to 4, and even more preferably 2.

[Oxazoline Group-Containing Resin]
The weight average molecular weight of the oxazoline group-containing resin is preferably from 3,000 to 150,000, more preferably from 3,000 to 80,000, and even more preferably from 6,000 to 50,000.

The molar amount of oxazoline groups in 1 g of oxazoline group-containing resin is preferably 0.001 to 10 mmol/g, more preferably 0.1 to 10 mmol/g, and even more preferably 0.5 to 9 mmol/g.

The oxazoline group-containing resin is preferably a resin having a repeating unit containing an oxazoline group.
The repeating unit containing an oxazoline group is preferably a repeating unit represented by the following formula (BO-1).
In formula (BO-1), L 1 ^B represents a single bond or a divalent linking group, X 1 ^B represents an oxazoline group, and R ^{1 B} represents a hydrogen atom or a methyl group.
In formula (BO-1), L 3 ^B is preferably a single bond. When L ^{3 B} is a divalent linking group, it is preferably a hydrocarbon group or a group represented by a bond between a hydrocarbon group and at least one group selected from the group consisting of -O-, -S-, -C(=O)-, -S(=O) ₂ - and -NR ^N -.
The above R ^N represents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, still more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.
In formula (BO-1), the details of the oxazoline group represented by ^XB are as described above, and the group represented by formula (1-1) is preferred.
In formula (BO-1), R ^{3 B} is preferably a methyl group.

The oxazoline group-containing resin preferably further contains another repeating unit different from the repeating unit containing the oxazoline group.
Examples of the other repeating units include a repeating unit containing an azole group and a repeating unit containing a polymerizable group.

--Repeating unit containing an azole group--
The oxazoline group-containing resin preferably contains a repeating unit represented by the following formula (BA-1) as a repeating unit containing an azole group.

In formula (BA-1), ^L3 represents a single bond or a divalent linking group, ^X3 represents an azole group, and R represents a hydrogen atom or a methyl group.
In formula (BA-1), ^L3 represents a single bond or a divalent linking group.
The divalent linking group is preferably a hydrocarbon group or a group represented by a bond between a hydrocarbon group and at least one group selected from the group consisting of -O-, -S-, -C(=O)-, -S(=O) ₂ - and -NR ^N -, and is more preferably a hydrocarbon group.
The ^RN is as described above.
The above-mentioned hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, more preferably an alkylene group.
The hydrocarbon group or alkylene group preferably has 2 to 20 carbon atoms, and more preferably has 2 to 10 carbon atoms.
Among these, ^L3 is preferably a single bond, a group represented by the following formula (BA-1-1) or a group represented by the following formula (BA-1-2).

In formula (BA-1-1) or formula (BA-1-2), ^L4 represents a divalent linking group, ^L5 represents a single bond or a divalent linking group, ^L6 represents a divalent linking group, ^L7 represents a single bond or a divalent linking group, * represents a bonding site with the carbonyl group in formula (BA-1), ^A1 and ^A2 represent -O- or -NR ^N -, and # represents a bonding site with ^X3 in (BA-1).

In formula (BA-1-1), L ⁴ is preferably a hydrocarbon group or a group represented by a bond between a hydrocarbon group and at least one group selected from the group consisting of -O-, -S-, -C(=O)-, -S(=O) ₂ - and -NR ^N -, and more preferably a hydrocarbon group.
The ^RN is as described above.
The above-mentioned hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, more preferably an alkylene group.
The hydrocarbon group or alkylene group preferably has 2 to 20 carbon atoms, and more preferably has 2 to 10 carbon atoms.

In formula (BA-1-1), L ⁵ is preferably a single bond. When L ⁵ is a divalent linking group, L ⁵ is preferably a hydrocarbon group or a group represented by a bond between a hydrocarbon group and at least one group selected from the group consisting of -O-, -S-, -C(=O)-, -S(=O) ₂ - and -NR ^N -, and more preferably a hydrocarbon group.

In formula (BA-1-2), L ⁶ has the same meaning as L ⁴ in formula (BA-1-1), and preferred embodiments are also the same.

In formula (BA-1-2), ^L7 is preferably a divalent linking group. When ^L7 is a divalent linking group, preferred embodiments of ^L7 are the same as the preferred embodiments when ^L5 in formula (BA-1-1) is a divalent linking group.

In formula (BA-1-1) or formula (BA-1-2), A ¹ and A ² represent -O- or -NR ^N -, preferably ^-O- .

In formula (BA-1), preferred embodiments of the azole group for ^X3 are as described above. The bonding site of the azole group to other structures corresponds to the bonding site to ^L3 in formula (BA-1).

The oxazoline group-containing resin may contain only one type of repeating unit represented by formula (BA-1), or may contain two or more types.
When the oxazoline group-containing resin contains a repeating unit containing an azole group, the molar amount of the azole group per 1 g of the oxazoline group-containing resin is preferably 0.001 to 10 mmol/g, and more preferably 0.1 to 8 mmol/g.

--Repeating unit containing a polymerizable group--
The oxazoline group-containing resin preferably contains a repeating unit represented by the following formula (BA-2) as a repeating unit containing a polymerizable group.

In formula (BA-2), A ³ represents —O— or —NR ^N —, L ^P1 represents a divalent linking group, X ^P1 represents a polymerizable group, and R represents a hydrogen atom or a methyl group.

In formula (BA-2), ^A3 represents -O- or -NR ^N -, and is preferably ^-O- .

In formula (BA-2), L ^P1 represents a divalent linking group, preferably a hydrocarbon group or a group represented by a bond between a hydrocarbon group and at least one group selected from the group consisting of -O-, -S-, -C(=O)-, -S(=O) ₂ - and -NR ^N -, more preferably a hydrocarbon group.
The ^RN is as described above.
The above-mentioned hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, more preferably an alkylene group.
The hydrocarbon group or alkylene group preferably has 2 to 20 carbon atoms, and more preferably has 2 to 10 carbon atoms.

X ^P1 represents a polymerizable group, preferably an alkoxysilyl group, an epoxy group, an oxetanyl group or a radically polymerizable group, more preferably an alkoxysilyl group. Preferred embodiments of the alkoxysilyl group and the radically polymerizable group are as described above.

The oxazoline group-containing resin may contain only one type of repeating unit represented by formula (BA-2), or may contain two or more types.
In particular, it is one of the preferred embodiments of the present invention that the oxazoline group-containing resin contains multiple types of repeating units represented by formula (BA-2) having different polymerizable groups. In the above embodiment, the oxazoline group-containing resin preferably contains a repeating unit represented by formula (BA-2) containing an alkoxysilyl group as the polymerizable group, and a repeating unit represented by formula (BA-2) containing a group other than the alkoxysilyl group as the polymerizable group.
When the oxazoline group-containing resin contains a repeating unit containing a polymerizable group, the molar content of the polymerizable group per 1 g of the oxazoline group-containing resin is preferably 0.001 to 10 mmol/g, and more preferably 0.01 to 5 mmol/g.

-Other repeating units-
The oxazoline group-containing resin may further have a repeating unit other than the repeating unit represented by the above formula (BA-1) or formula (BA-2).
Examples of other repeating units include repeating units derived from styrene or substituted styrene.

〔Concrete example〕
Specific examples of the compound having an oxazoline group include the compounds used in the examples, but are not limited thereto.

〔Content〕
The content of the compound having an oxazoline group is preferably 0.05 to 10 mass %, more preferably 0.10 to 5 mass %, and even more preferably 0.15 to 2 mass %, based on the total solid content of the curable resin composition of the present invention.
The curable resin composition of the present invention may contain only one type of compound having an oxazoline group, or may contain two or more types. When two or more types of compounds having an oxazoline group are contained, the total amount is preferably within the above range.

<Compound containing an acid group and an alkoxysilyl group>
The curable resin composition of the present invention comprises a compound containing an acid group and an alkoxysilyl group.
As the acid group in the compound containing an acid group and an alkoxysilyl group, a carboxy group, a phenolic hydroxy group, or an aromatic thiol group is preferred, and a carboxy group is more preferred.
Preferred embodiments of the alkoxysilyl group in the compound containing an acid group and an alkoxysilyl group are the same as the preferred embodiments of the alkoxysilyl group in the compound having an oxazoline group described above.

It is also preferable that the compound containing an acid group and an alkoxysilyl group contains a polymerizable group different from the alkoxysilyl group.
Examples of the polymerizable group other than an alkoxysilyl group include known polymerizable groups such as a radical polymerizable group, an epoxy group, an oxetanyl group, a methylol group, an alkoxymethyl group, and a (blocked) isocyanate group. Of these, a radical polymerizable group or an epoxy group is preferred, and a radical polymerizable group is more preferred.
It is also preferred that the compound containing an acid group and an alkoxysilyl group contains an azole group.
The azole group may be the same as those described above for the compound having an oxazoline group, and preferred embodiments are also the same.
Among these, from the viewpoint of adhesion of the cured film to metal, it is preferable that the compound containing an acid group and an alkoxysilyl group contains at least one group selected from the group consisting of a radically polymerizable group and an azole group.

The compound containing an acid group and an alkoxysilyl group may be a compound having a molecular weight of less than 2,000 (hereinafter also referred to as "low molecular weight compound C"), or may be a resin (hereinafter also referred to as "resin C").
From the viewpoint of adhesion of the cured film to metal, it is also preferable that the curable resin composition contains both the low molecular weight compound C and the resin C.
From the viewpoint of adhesion, the compound containing an acid group and an alkoxysilyl group is preferably a resin.

[Low molecular weight compound C]
The molecular weight of the low molecular weight compound C is less than 2,000, preferably 1,500 or less, and more preferably 1,000 or less.

The number of acid groups in the low molecular weight compound C is preferably 1 to 10, more preferably 1 to 4, further preferably 1 or 2, and particularly preferably 1.
The number of alkoxysilyl groups in the low molecular weight compound C is preferably 1 to 10, more preferably 1 to 4, further preferably 1 or 2, and particularly preferably 1.

[Resin C]
The weight average molecular weight of Resin C is preferably from 3,000 to 100,000, more preferably from 5,000 to 80,000, and even more preferably from 5,000 to 50,000.

The molar amount of acid groups in 1 g of resin C is preferably 0.01 mmol/g to 15 mmol/g, more preferably 0.05 mmol/g to 10 mmol/g, and even more preferably 0.1 to 3 mmol/g.
The molar amount of the alkoxysilyl group in 1 g of Resin C is preferably 0.001 to 10 mmol/g, more preferably 0.01 to 10 mmol/g, and further preferably 0.1 to 5 mmol/g.

Resin C is preferably a resin having a repeating unit containing an acid group and a repeating unit containing an alkoxysilyl group, or a resin having a repeating unit containing an acid group and an alkoxysilyl group, and more preferably a resin having a repeating unit containing an acid group and a repeating unit containing an alkoxysilyl group.

-Repeating unit containing an acid group-
The repeating unit containing an acid group is preferably a repeating unit represented by the following formula (CA-1) or formula (CA-2).

In formula (CA-1) or formula (CA-2), A 1 ^C represents —O— or —NR ^N —, L 1 ^C represents a divalent linking group, X 1 ^C represents an acid group, and R represents a hydrogen atom or a methyl group.
In formula (CA-2), A 3 ^C is preferably —O—.
In formula (CA-2), L ^C is preferably a hydrocarbon group, or a group represented by a bond between a hydrocarbon group and at least one group selected from the group consisting of -O-, -S-, -C(=O)-, -S(=O) ₂ - and -NR ^N -.
The ^RN is as described above.
The above-mentioned hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, more preferably an alkylene group.
The hydrocarbon group or alkylene group preferably has 2 to 20 carbon atoms, and more preferably has 2 to 10 carbon atoms.
In formula (CA-2), X ^{3 C} is preferably a carboxy group, a phenolic hydroxy group or an aromatic thiol group, and more preferably a carboxy group.

--Repeating unit containing an alkoxysilyl group--
Preferred examples of the repeating unit containing an alkoxysilyl group in Resin C include the repeating unit represented by formula (BA-2) above, in which X ^P1 is an alkoxysilyl group.

--Repeating unit containing an azole group--
Resin C may have a repeating unit containing an azole group.
Preferred examples of the repeating unit containing an azole group in Resin C include the repeating unit represented by formula (BA-1) above.
When Resin C has a repeating unit containing an azole group, the molar amount of the azole group per 1 g of Resin C is preferably 0.001 to 10 mmol/g, and more preferably 0.1 to 5 mmol/g.

-Other repeating units-
Resin C may further contain other repeating units.
Examples of other repeating units include repeating units represented by the above formula (BA-2), in which X ^P1 is a polymerizable group other than an alkoxysilyl group.

〔Concrete example〕
Specific examples of the compound containing an acid group and an alkoxysilyl group include the compounds used in the examples, but are not limited thereto.

〔Content〕
The content of the compound containing an acid group and an alkoxysilyl group is preferably 0.05 to 10 mass%, more preferably 0.10 to 5 mass%, and even more preferably 0.15 to 2 mass%, based on the total solid content of the curable resin composition of the present invention.
The curable resin composition may contain only one type of compound containing an acid group and an alkoxysilyl group, or may contain two or more types. When the curable resin composition contains two or more types of compounds containing an acid group and an alkoxysilyl group, the total amount is preferably within the above range.

<Other compounds having an azole group>
The curable resin composition may further contain a compound having an azole group, which does not fall into any of the above-mentioned compounds having an oxazoline group and compounds containing an acid group and an alkoxysilyl group (also referred to as "another compound having an azole group").
The preferred embodiments of the azole group in other compounds having an azole group are the same as the preferred embodiments of the azole group in the compound having an oxazoline group described above.
In addition, the other compound having an azole group is preferably a compound having no polymerizable group. The details of the polymerizable group are the same as those of the polymerizable group in the compound having an oxazoline group described above.

The other compound having an azole group is preferably a compound represented by the following formula (AZ-1) or (AZ-2).

In formula (AZ-1), Z ¹ to Z ⁴ each independently represent ═CR ⁷ — or a nitrogen atom, R ¹ represents a hydrogen atom or a monovalent organic group, R ⁷ represents a hydrogen atom or a monovalent organic group, and the structure represented by formula (AZ-1) does not contain a polymerizable group;
In formula (AZ-2), ^Z5 to ^Z6 each independently represent = ^CR8- or a nitrogen atom, ^R2 to ^R6 each independently represent a hydrogen atom or a monovalent organic group, ^R8 represents a hydrogen atom or a monovalent organic group, and the structure represented by formula (AZ-2) does not contain a polymerizable group.

In formula (AZ-1), Z ¹ to Z ⁴ each independently represent ═CR ⁷ — or a nitrogen atom.
Among these, an embodiment in which one of Z ¹ to Z ⁴ is a nitrogen atom and three are =CR ⁷ -, an embodiment in which two of Z ¹ to Z ⁴ are nitrogen atoms and two are =CR ⁷ -, or an embodiment in which three of Z ¹ to Z ⁴ are nitrogen atoms and one is =CR ⁷ -, is preferred.
Among these, an embodiment in which ^Z1 and ^Z3 are nitrogen ^atoms and Z2 and ^Z4 are = ^CR7- , an embodiment in which ^Z1 and ^Z2 are nitrogen atoms and Z3 and ^Z4 are = ^CR7- , or an embodiment in which ^Z1 , ^Z2 and ^Z3 are nitrogen atoms and ^Z4 is = ^CR7- are preferred, and an embodiment in which ^Z1 and ^Z3 are nitrogen atoms and ^Z2 and ^Z4 are = ^CR7- , or an embodiment in which ^Z1 , ^Z2 and ^Z3 are nitrogen atoms and ^{Z4 is} = ^CR7- are more preferred.

In formula (AZ-1), R ¹ is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.
The above hydrocarbon group or alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 4 carbon atoms.

In formula (AZ-1), preferred embodiments of ^R7 are the same as those of ^R1 .

In formula (AZ-2), Z ⁵ and Z ⁶ each independently represent ═CR ⁸ — or a nitrogen atom.
Among these, an embodiment in which both Z ⁵ and Z ⁶ represent a nitrogen atom, or an embodiment in which Z ⁵ represents a nitrogen atom and Z ⁶ represents ═CR ⁸ —, respectively, is preferred.

In formula (AZ-2), R ² to R ⁶ and R ⁸ each independently preferably represent a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

[Molecular weight]
The molecular weight of the other compound having an azole group is preferably 67-500, and more preferably 68-300.

〔Concrete example〕
Specific examples of other compounds having an azole group include the compounds used in the examples, but are not limited thereto.

〔Content〕
The content of the other compound having an azole group is preferably 0.05 to 10 mass %, more preferably 0.10 to 5 mass %, and even more preferably 0.15 to 2 mass %, based on the total solid content of the curable resin composition of the present invention.
The curable resin composition may contain only one type of other compound having an azole group, or may contain two or more types. When containing two or more types of other compounds having an azole group, the total amount is preferably in the above range.

<Other silane coupling agents>
The curable resin composition of the present invention may contain a silane coupling agent ("other silane coupling agent") that is different from any of the above-mentioned compounds having an oxazoline group and compounds containing an acid group and an alkoxysilyl group.
As the other silane coupling agent, a compound having an alkoxysilyl group and having neither an acid group nor an oxazoline group is preferable.
As another silane coupling agent, a resin containing a repeating unit containing an alkoxysilyl group may be used.
The resin may further include a repeating unit containing a polymerizable group other than alkoxysilyl.
Examples of the repeating unit containing an alkoxysilyl group and the repeating unit containing a polymerizable group other than an alkoxysilyl group include the repeating unit represented by the above formula (BA-2).

Examples of other silane coupling agents include compounds described in paragraph 0167 of WO 2015/199219, compounds described in paragraphs 0062-0073 of JP 2014-191002 A, compounds described in paragraphs 0063-0071 of WO 2011/080992 A, compounds described in paragraphs 0060-0061 of JP 2014-191252 A, compounds described in paragraphs 0045-0052 of JP 2014-041264 A, compounds described in paragraph 0055 of WO 2014/097594 A, compounds having the above-mentioned oxazoline group, and compounds not corresponding to any of the compounds containing an acid group and an alkoxysilyl group. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050-0058 of JP 2011-128358 A.
As other silane coupling agents, it is also preferable to use vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, or the following compounds. In the following formula, Et represents an ethyl group.

〔Content〕
The content of the other silane coupling agent is preferably 0.05 to 10 mass %, more preferably 0.10 to 5 mass %, and even more preferably 0.15 to 2 mass %, based on the total solid content of the curable resin composition of the present invention.
The curable resin composition may contain only one type of other silane coupling agent, or may contain two or more types. When containing two or more types of other silane coupling agents, the total amount is preferably within the above range.

<Solvent>
The curable resin composition of the present invention preferably contains a solvent. Any known solvent can be used as the solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters ... Preferred examples of the cypropionic acid alkyl esters include methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, and propyl 2-alkyloxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, and ethyl 2-ethoxypropionate), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, and diethyl malonate.

Suitable examples of 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, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, and propylene glycol monopropyl ether acetate.

Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

Suitable cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

A suitable example of a sulfoxide is dimethyl sulfoxide.

Suitable amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

Suitable ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

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

It is also preferable to mix two or more types of solvents from the viewpoint of improving the properties of the coating surface.

In the present invention, one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, or a mixed solvent composed of two or more solvents, is preferred. The combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred. Also preferred are combinations of N-methyl-2-pyrrolidone and ethyl lactate, N-methyl-2-pyrrolidone and ethyl lactate, diacetone alcohol and ethyl lactate, and cyclopentanone and γ-butyrolactone.

Of these, the curable resin composition of the present invention preferably contains an ester, and more preferably contains a lactone-based solvent.
The lactone solvent refers to a solvent containing a lactone structure, and examples of such a solvent include γ-butyrolactone, ε-caprolactone, and δ-valerolactone.
The content of the lactone solvent relative to the total mass of the solvent is not particularly limited, but is preferably from 30 to 100% by mass, more preferably from 40 to 95% by mass, and even more preferably from 50 to 90% by mass.

From the viewpoint of coatability, the content of the solvent is preferably an amount that results in a total solids concentration of the curable resin composition of the present invention of 5 to 80% by mass, more preferably an amount that results in a total solids concentration of 5 to 75% by mass, even more preferably an amount that results in a total solids concentration of 10 to 70% by mass, and even more preferably an amount that results in a total solids concentration of 40 to 70% by mass. The solvent content may be adjusted according to the desired thickness of the coating film and the coating method.

The composition may contain only one type of solvent, or two or more types. When two or more types of solvents are contained, it is preferable that the total amount of the solvents is within the above range.

<Photosensitizer>
The composition of the present invention preferably contains a photosensitizer.
The photosensitizer is preferably a photopolymerization initiator.

[Photopolymerization initiator]
The composition of the present invention preferably contains a photopolymerization initiator as a photosensitizer.
The photopolymerization initiator is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet to visible regions is preferable. In addition, it may be an activator that generates active radicals by reacting with a photoexcited sensitizer.
As the photoradical polymerization initiator, an oxime compound described below is preferred.

The photoradical polymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 L·mol ⁻¹ ·cm ⁻¹ in the range of about 300 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to measure it using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g/L using ethyl acetate as a solvent.

Any known compound can be used as the photoradical polymerization initiator. For example, 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, hexaarylbiimidazoles, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. For details of these, please refer to the descriptions in paragraphs 0165 to 0182 of JP 2016-027357 A and paragraphs 0138 to 0151 of WO 2015/199219 A, the contents of which are incorporated herein by reference.

Examples of ketone compounds include the compounds described in paragraph 0087 of JP 2015-087611 A, the contents of which are incorporated herein by reference. As a commercially available product, Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used as the photoradical polymerization initiator. More specifically, for example, aminoacetophenone-based initiators described in JP-A-10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used.

Hydroxyacetophenone initiators that can be used include IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (product names: all manufactured by BASF).

As aminoacetophenone initiators, commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (product names: all manufactured by BASF) can be used.

As an aminoacetophenone-based initiator, the compounds described in JP 2009-191179 A, which have an absorption maximum wavelength matching a wavelength light source such as 365 nm or 405 nm, can also be used.

Examples of acylphosphine initiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. In addition, commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF Corporation) can also be used.

Examples of metallocene compounds include IRGACURE-784 and IRGACURE-784EG (both manufactured by BASF).

As the photoradical polymerization initiator, an oxime compound is more preferably used. By using an oxime compound, it is possible to more effectively improve the exposure latitude. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also function as a photocuring accelerator.

Specific examples of oxime compounds that can be used include the compounds described in JP-A-2001-233842, JP-A-2000-080068, and JP-A-2006-342166.

Preferred oxime compounds include, for example, compounds having the following structure, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. In the composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as a photoradical polymerization initiator. Oxime-based photopolymerization initiators have a linking group of >C=N-O-C(=O)- in the molecule.

Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (manufactured by BASF), and ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in JP-A-2012-014052). TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA ARCLES NCI-831, and ADEKA ARCLES NCI-930 (manufactured by ADEKA Corporation) can also be used. DFI-091 (manufactured by Daito Chemistry Co., Ltd.) can also be used. Oxime compounds having the following structure can also be used.

As the photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of oxime compounds having a fluorene ring include the compounds described in JP-A-2014-137466 and the compounds described in JP-A-06636081.

As the photopolymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring can also be used. Specific examples of such oxime compounds include the compounds described in WO 2013/083505.

It is also possible to use an oxime compound having a fluorine atom. Specific examples of such oxime compounds include the compound described in JP-A-2010-262028, compounds 24, 36 to 40 described in paragraph 0345 of JP-T-2014-500852, and compound (C-3) described in paragraph 0101 of JP-A-2013-164471.

The most preferred oxime compounds include oxime compounds having specific substituents as disclosed in JP-A-2007-269779 and oxime compounds having a thioaryl group as disclosed in JP-A-2009-191061.

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

More preferred photoradical polymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds, with at least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds being even more preferred, with a metallocene compound or an oxime compound being even more preferred, and an oxime compound being even more preferred.

In addition, examples of the photoradical polymerization initiator that can be used include benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenones such as 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-propanone-1, quinones condensed with aromatic rings such as alkylanthraquinones, benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkylbenzoins, and benzyl derivatives such as benzyl dimethyl ketal. Compounds represented by the following formula (I) can also be used.

In formula (I), R ^I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by 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 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, or a biphenyl; R ^I01 is a group represented by formula (II) or is the same group as R ^I00 ; and R ^I02 to R ^I04 are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen.

In the formula, R ^I05 to R ^I07 are the same as R ^I02 to R ^I04 in the above formula (I).

In addition, the photoradical polymerization initiator may be the compound described in paragraphs 0048 to 0055 of WO 2015/125469.

When a photopolymerization initiator is included, its content 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 solids content of the composition of the present invention. Only one type of photopolymerization initiator may be included, or two or more types may be included. When two or more types of photopolymerization initiators are included, it is preferable that the total amount is within the above range.

[Photoacid generator]
The composition of the present invention also preferably contains a photoacid generator as a photosensitizer.
By including a photoacid generator, for example, an acid is generated in the exposed portion of the composition layer, which increases the solubility of the exposed portion in a developer (e.g., an alkaline aqueous solution), thereby obtaining a positive pattern in which the exposed portion is removed by the developer.
In addition, by containing a photoacid generator and a polymerizable compound other than the radically polymerizable compound described below, for example, the acid generated in the exposed area promotes a crosslinking reaction of the polymerizable compound, and the exposed area becomes more difficult to remove with a developer than the non-exposed area. According to such an embodiment, a negative pattern can be obtained.

The photoacid generator is not particularly limited as long as it generates an acid upon exposure to light, but examples include quinone diazide compounds, onium salt compounds such as diazonium salts, phosphonium salts, sulfonium salts, and iodonium salts, and sulfonate compounds such as imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonate.

Examples of quinone diazide compounds include polyhydroxy compounds to which sulfonic acid of quinone diazide is bonded via ester, polyamino compounds to which sulfonic acid of quinone diazide is bonded via sulfonamide, and polyhydroxy polyamino compounds to which sulfonic acid of quinone diazide is bonded via at least one of an ester bond and a sulfonamide bond. In the present invention, for example, it is preferable that 50 mol % or more of the functional groups of these polyhydroxy compounds or polyamino compounds are substituted with quinone diazide.

In the present invention, either a 5-naphthoquinone diazide sulfonyl group or a 4-naphthoquinone diazide sulfonyl group is preferably used as the quinone diazide. 4-naphthoquinone diazide sulfonyl ester compounds have absorption in the i-line region of a mercury lamp, and are suitable for i-line exposure. 5-naphthoquinone diazide sulfonyl ester compounds have absorption extending to the g-line region of a mercury lamp, and are suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength of exposure. In addition, naphthoquinone diazide sulfonyl ester compounds having a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule may be contained, or a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound may be contained.

The naphthoquinone diazide compound can be synthesized by esterification reaction between a compound having a phenolic hydroxyl group and a quinone diazide sulfonic acid compound, and can be synthesized by a known method. The use of these naphthoquinone diazide compounds improves the resolution, sensitivity, and film remaining rate.
Examples of the naphthoquinone diazide compound include 1,2-naphthoquinone-2-diazide-5-sulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonic acid, salts or esters of these compounds.

Examples of onium salt compounds or sulfonate compounds include the compounds described in paragraphs 0064 to 0122 of JP 2008-013646 A.

It is also preferable that the photoacid generator is a compound containing an oxime sulfonate group (hereinafter, also simply referred to as an "oxime sulfonate compound").
The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but is preferably an oxime sulfonate compound represented by the following formula (OS-1), or the below-described formula (OS-103), formula (OS-104), or formula (OS-105).

In formula (OS-1), X ³ represents an alkyl group, an alkoxyl group, or a halogen atom. When a plurality of X ³ are present, they may be the same or different. The alkyl group and alkoxyl group in X ³ may have a substituent. The alkyl group in X 3 is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxyl group in X ³ is preferably a linear or branched alkoxyl group having 1 to 4 carbon ^{atoms. The halogen atom in X 3 is} preferably a chlorine atom or a fluorine atom.
In formula (OS-1), m3 represents an integer of 0 to 3, and is preferably 0 or 1. When m3 is 2 or 3, multiple ^X3s may be the same or different.
In formula (OS-1), R ³⁴ represents an alkyl group or an aryl group, and is preferably an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxyl group having 1 to 5 carbon atoms, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms or a halogenated alkoxyl group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogenated aryl group having 6 to 20 carbon atoms.

In formula (OS-1), a compound in which m3 is 3, ^X3 is a methyl group, the substitution position of ^X3 is the ortho position, and ^R34 is a linear alkyl group having 1 to 10 carbon atoms, a 7,7-dimethyl-2-oxonorbornylmethyl group, or a p-tolyl group is particularly preferred.

Specific examples of the oxime sulfonate compound represented by formula (OS-1) include the following compounds described in paragraphs [0064] to [0068] of JP2011-209692A and paragraphs [0158] to [0167] of JP2015-194674A, the contents of which are incorporated herein by reference.

In formulae (OS-103) to (OS-105), R ^s1 represents an alkyl group, an aryl group, or a heteroaryl group; R ^s2 , which may be present in plurality, each independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom; R ^s6 , which may be present in plurality, each independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group, or an alkoxysulfonyl group; Xs represents O or S; ns represents 1 or 2; and ms represents an integer of 0 to 6.
In formulae (OS-103) to (OS-105), the alkyl group ( ^preferably having 1 to 30 carbon atoms), the aryl group (preferably having 6 to 30 carbon atoms) or the heteroaryl group (preferably having 4 to 30 carbon atoms) represented by R s1 may have a substituent T.

In formulae (OS-103) to (OS-105), R ^s2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms), more preferably a hydrogen atom or an alkyl group. Of the R ^s2 , of which two or more may be present in a compound, it is preferable that one or two are an alkyl group, an aryl group or a halogen atom, more preferably one is an alkyl group, an aryl group or a halogen atom, and particularly preferably one is an alkyl group and the remaining are hydrogen atoms. The alkyl group or aryl group represented by R ^s2 may have a substituent T.
In formula (OS-103), formula (OS-104), or formula (OS-105), Xs represents O or S, and is preferably O. In the above formulas (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered or 6-membered ring.

In formulae (OS-103) to (OS-105), ns represents 1 or 2. When Xs is O, ns is preferably 1, and when Xs is S, ns is preferably 2.
In formulae (OS-103) to (OS-105), the alkyl group (preferably having 1 to 30 carbon atoms) and the alkyloxy group (preferably having 1 to 30 carbon atoms) represented by R ^s6 may have a substituent.
In formulae (OS-103) to (OS-105), ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

Furthermore, the compound represented by formula (OS-103) is particularly preferably a compound represented by formula (OS-106), formula (OS-110) or formula (OS-111) below; the compound represented by formula (OS-104) is particularly preferably a compound represented by formula (OS-107) below; and the compound represented by formula (OS-105) is particularly preferably a compound represented by formula (OS-108) or formula (OS-109) below.

In formulae (OS-106) to (OS-111), R ^t1 represents an alkyl group, an aryl group, or a heteroaryl group; R ^t7 represents a hydrogen atom or a bromine atom; R ^t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or a chlorophenyl group; R ^t9 represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group; and R ^t2 represents a hydrogen atom or a methyl group.
In formulae (OS-106) to (OS-111), R ^t7 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.

In formulae (OS-106) to (OS-111), R ^t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or a chlorophenyl group, and is preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom, or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.

In formulae (OS-106) to (OS-111), R ^t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
R ^t2 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
In the above oxime sulfonate compound, the stereochemical structure of the oxime (E, Z) may be either one or a mixture.
Specific examples of the oxime sulfonate compounds represented by the above formulae (OS-103) to (OS-105) include the compounds described in paragraphs [0088] to [0095] of JP-A-2011-209692 and paragraphs [0168] to [0194] of JP-A-2015-194674, the contents of which are incorporated herein by reference.

Other preferred embodiments of oxime sulfonate compounds containing at least one oxime sulfonate group include compounds represented by the following formulas (OS-101) and (OS-102).

In formula (OS-101) or formula (OS-102), R ^u9 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxyl group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or a heteroaryl group. An embodiment in which R ^u9 is a cyano group or an aryl group is more preferable, and an embodiment in which R ^u9 is a cyano group, a phenyl group, or a naphthyl group is even more preferable.
In formula (OS-101) or formula (OS-102), R ^u2a represents an alkyl group or an aryl group.
In formula (OS-101) or formula (OS-102), Xu represents -O-, -S-, -NH-, -NR ^u5 -, -CH ₂ -, -CR ^u6 H- or CR ^u6 R ^u7 -, and R ^u5 to R ^u7 each independently represent an alkyl group or an aryl group.

In formula (OS-101) or formula (OS-102), R ^u1 to R ^u4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxyl group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, or an aryl group. Two of R ^u1 to R ^u4 may be bonded to each other to form a ring. In this case, the ring may be condensed to form a condensed ring with the benzene ring. As R ^u1 to R ^u4 , a hydrogen atom, a halogen atom, or an alkyl group is preferable, and an embodiment in which at least two of R ^u1 to R ^u4 are bonded to each other to form an aryl group is also preferable. Among them, an embodiment in which R ^u1 to R ^u4 are all hydrogen atoms is preferable. Any of the above-mentioned substituents may further have a substituent.

The compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102).
In the above oxime sulfonate compound, the stereochemical structures (E, Z, etc.) of the oxime and benzothiazole rings may each be either one or a mixture.
Specific examples of the compound represented by formula (OS-101) include the compounds described in paragraphs [0102] to [0106] of JP-A-2011-209692 and paragraphs [0195] to [0207] of JP-A-2015-194674, the contents of which are incorporated herein by reference.
Among the above compounds, b-9, b-16, b-31 and b-33 are preferable.

In addition, commercially available products may be used as the photoacid generator. Examples of commercially available products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-367, WPAG-370, WPAG-443, WPAG-469, WPAG-638, and WPAG-699 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), Omnicat 250 and Omnicat 270 (all manufactured by IGM Resins B.V.), Irgacure 250, Irgacure 270, and Irgacure 290 (all manufactured by BASF), and MBZ-101 (manufactured by Midori Chemical Co., Ltd.).

Further, compounds represented by the following structural formulas are also preferred examples.

As the photoacid generator, an organic halogenated compound can also be used. Specific examples of the organic halogenated compound include those described in Wakabayashi et al., Bull Chem. Soc Japan, vol. 42, pp. 2924 (1969), U.S. Pat. No. 3,905,815, JP-B-4605, JP-A-48-36281, JP-A-55-32070, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62-212401, JP-A-63-70243, JP-A-63-298339, and M.P. Examples of the compounds include those described in Hutt "Journal of Heterocyclic Chemistry" 1 (No. 3), (1970), and in particular, oxazole compounds substituted with a trihalomethyl group: S-triazine compounds.
More preferably, the s-triazine derivative has at least one mono-, di-, or trihalogen-substituted methyl group bonded to the s-triazine ring, specifically, for example, 2,4,6-tris(monochloromethyl)-s-triazine, 2,4,6-tris(dichloromethyl)-s-triazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s-triazine, riazine, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[1-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, phenyl)-2,4-butadienyl]-4,6-bis(trichloromethyl)-s-triazine, 2-styryl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-i-propyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-nathoxynaphthyl)-4,6- Examples of the bis(trichloromethyl)-s-triazine include bis(trichloromethyl)-s-triazine, 2-phenylthio-4,6-bis(trichloromethyl)-s-triazine, 2-benzylthio-4,6-bis(trichloromethyl)-s-triazine, 2,4,6-tris(dibromomethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, and 2-methoxy-4,6-bis(tribromomethyl)-s-triazine.

As the photoacid generator, an organic borate compound can also be used. Examples of the organic borate compound include those described in JP-A-62-143044, JP-A-62-150242, JP-A-9-188685, JP-A-9-188686, JP-A-9-188710, JP-A-2000-131837, JP-A-2002-107916, Japanese Patent No. 2764769, and Japanese Patent Application No. 2000-310808, and in Kunz, Martin, "Rad Tech'98. Proceedings of April 1998, 19-22, 1998, Chicago", etc.; organic boron sulfonium complexes or organic boron oxosulfonium complexes described in JP-A-6-157623, JP-A-6-175564, and JP-A-6-175561; organic boron iodonium complexes described in JP-A-6-175554 and JP-A-6-175553; organic boron phosphonium complexes described in JP-A-9-188710; and organic boron transition metal coordination complexes described in JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, JP-A-7-292014, etc. are specific examples.

Disulfone compounds can also be used as photoacid generators. Examples of disulfone compounds include the compounds described in JP-A-61-166544 and JP-A-2001-132318, and diazodisulfone compounds.

Examples of the onium salt compounds include diazonium salts described in S. I. Schlesinger, Photogr. Sci. Eng., 18, 387 (1974) and T. S. Bal et al., Polymer, 21, 423 (1980), ammonium salts described in U.S. Pat. No. 4,069,055 and JP-A-4-365049, phosphonium salts described in U.S. Pat. Nos. 4,069,055 and 4,069,056, iodine salts described in European Patent Nos. 104,143, 339,049 and 410,201, JP-A-2-150848 and JP-A-2-296514, and ammonium salts described in U.S. Pat. No. 4,069,055 and JP-A-4-365049. sulfonium salts described in European Patent Nos. 370,693, 390,214, 233,567, 297,443, and 297,442, U.S. Pat. Nos. 4,933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, and 2,833,827, German Patent Nos. 2,904,626, 3,604,580, and 3,604,581; sulfonium salts described in J. V. Crivello et al., Macromolecules, 10(6), 1307 (1977), J. V. Crivello et al., J. Examples of the onium salt include selenonium salts described in Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979), arsonium salts described in C. S. Wen et al., Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct. (1988), and onium salts such as pyridinium salts.

Examples of the onium salt include onium salts represented by the following general formulas (RI-I) to (RI-III).

In formula (RI-I), Ar11 represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, an alkylamide group or arylamide group having 1 to 12 carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. ^Z11- represents a monovalent anion, such as a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, or a sulfate ion, and from the standpoint of stability, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, or a sulfinate ion is preferred. In formula (RI-II), Ar21 and Ar22 each independently represent an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, an alkylamide group or arylamide group having 1 to 12 carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. ^Z21- represents a monovalent anion, and is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, or a sulfate ion, and is preferably a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, or a carboxylate ion in terms of stability and reactivity. In formula (RI-III), R31, R32, and R33 each independently represent an aryl group, an alkyl group, an alkenyl group, or an alkynyl group having 20 or less carbon atoms, which may have 1 to 6 substituents, and is preferably an aryl group in terms of reactivity and stability. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, an alkylamide group or an arylamide group having 1 to 12 carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z31 ^- represents a monovalent anion, and is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, or a sulfate ion, and from the standpoint of stability and reactivity, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, or a carboxylate ion is preferred.

Specific examples include the following:

When a photoacid generator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 2 to 15% by mass, based on the total solids content of the composition of the present invention. Only one type of photoacid generator may be included, or two or more types may be included. When two or more types of photoacid generators are included, it is preferable that the total is within the above range.

[Photobase Generator]
The curable resin composition of the present invention may contain a photobase generator as a photosensitizer.
By containing a photobase generator and a crosslinking agent described later, the curable resin composition can be configured such that, for example, the base generated in the exposed area promotes cyclization of a specific resin, the crosslinking reaction of the crosslinking agent is promoted, etc., so that the exposed area is more difficult to remove by a developer than the non-exposed area. According to such an embodiment, a negative relief pattern can be obtained.

The photobase generator is not particularly limited as long as it generates a base upon exposure to light, and any known photobase generator can be used.
For example, see M. Shirai, and M. Tsunooka, Prog. Polym. Sci., 21, 1 (1996); Masahiro Kadooka, Polymer Processing, 46, 2 (1997); C. Kutal, Coord. Chem. Rev., 211, 353 (2001); Y. Kaneko, A. Sarker, and D. Neckers, Chem. Mater., 11, 170 (1999); H. Tachi, M. Shirai, and M. Tsunooka, J. Photopolym. Sci. Technol., 13, 153 (2000); M. Winkle, and K. Graziano, J. Photopolym. Sci. Technol. , 3, 419 (1990);M. Tsunooka, H. Tachi, and S. Yoshitaka, J. Photopolym. Sci. Technol. , 9, 13 (1996);K. Suyama, H. Araki, M. Shirai, J. Photopolym. Sci. Technol. , 19, 81 (2006), examples of the suitable compounds include ionic compounds in which a base component is neutralized by forming a salt, such as those having a structure of a transition metal compound complex or ammonium salt, and those in which an amidine moiety is rendered latent by forming a salt with a carboxylic acid, and nonionic compounds in which a base component is rendered latent by a urethane bond or oxime bond, such as carbamate derivatives, oxime ester derivatives, and acyl compounds.
In the present invention, preferred examples of the photobase generator include carbamate derivatives, amide derivatives, imide derivatives, α-cobalt complexes, imidazole derivatives, cinnamic acid amide derivatives, and oxime derivatives.

The basic substance generated from the photobase generator is not particularly limited, but examples thereof include compounds having an amino group, particularly monoamines, polyamines such as diamines, and amidines.
From the viewpoint of the imidization rate, the basic substance preferably has a large pKa in DMSO (dimethyl sulfoxide) of the conjugate acid. The pKa is preferably 1 or more, more preferably 3 or more. The upper limit of the pKa is not particularly limited, but is preferably 20 or less.
Here, the pKa refers to the logarithm of the reciprocal of the first dissociation constant of an acid, and can be found in Determination of Organic Structures by Physical Methods (authors: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; editors: Braude, EA, Nachod, FC; Academic Press, New York, 1955) and Data for Biochemical Research (authors: Dawson, RMC et al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, the value calculated from the structural formula using ACD/pKa (manufactured by ACD/Labs) software is used as the pKa.

From the viewpoint of storage stability of the curable resin composition, the photobase generator is preferably a photobase generator that does not contain a salt in the structure, and it is preferable that there is no charge on the nitrogen atom of the base portion generated in the photobase generator. The photobase generator is preferably one in which the generated base is made latent using a covalent bond, and the base generation mechanism is preferably one in which the covalent bond between the nitrogen atom of the generated base portion and the adjacent atom is broken to generate the base. If the photobase generator does not contain a salt in the structure, the photobase generator can be neutralized, so that the solvent solubility is better and the pot life is improved. For these reasons, the amine generated from the photobase generator used in the present invention is preferably a primary amine or a secondary amine.
From the viewpoint of the chemical resistance of the pattern, the photobase generator is preferably a photobase generator containing a salt in its structure.

For the reasons mentioned above, it is preferable that the photobase generator generates a base in a latent form using a covalent bond as described above, and it is preferable that the generated base is latent using an amide bond, a carbamate bond, or an oxime bond.
Examples of the photobase generator according to the present invention include photobase generators having a cinnamic acid amide structure as disclosed in JP 2009-080452 A and WO 2009/123122 A, photobase generators having a carbamate structure as disclosed in JP 2006-189591 A and JP 2008-247747 A, photobase generators having an oxime structure or a carbamoyloxime structure as disclosed in JP 2007-249013 A and JP 2008-003581 A, but are not limited to these, and other known photobase generator structures can also be used.

Other examples of photobase generators include the compounds described in paragraphs [0185] to [0188], [0199] to [0200], and [0202] of JP2012-093746A, the compounds described in paragraphs [0022] to [0069] of JP2013-194205A, the compounds described in paragraphs [0026] to [0074] of JP2013-204019A, and the compounds described in paragraph [0052] of WO2010/064631A.

In addition, commercially available products may be used as the photobase generator. Examples of commercially available products include WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, WPBG-018, WPGB-015, WPBG-041, WPGB-172, WPGB-174, WPBG-166, WPGB-158, WPGB-025, WPGB-168, WPGB-167, and WPBG-082 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), A2502, B5085, N0528, N1052, O0396, O0447, and O0448 (manufactured by Tokyo Chemical Industry Co., Ltd.).

When a photobase generator is included, the content is preferably 0.1 to 30 mass% relative to the total solids content of the curable resin composition of the present invention, more preferably 0.1 to 20 mass%, and even more preferably 2 to 15 mass%. Only one type of photobase generator may be included, or two or more types may be included. When two or more types of photobase generators are included, the total is preferably within the above range.

<Thermal Polymerization Initiator>
The composition of the present invention may contain a thermal polymerization initiator, and in particular may contain a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or promotes the polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can also be advanced in the heating step described below, so that the solvent resistance can be further improved.

Specific examples of thermal radical polymerization initiators include the compounds described in paragraphs 0074 to 0118 of JP 2008-063554 A.

When a thermal polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 5 to 15% by mass, based on the total solids content of the composition of the present invention. Only one type of thermal polymerization initiator may be included, or two or more types may be included. When two or more types of thermal polymerization initiators are included, it is preferable that the total amount is within the above range.

<Thermal Acid Generator>
The compositions of the present invention may also include a thermal acid generator.
The thermal acid generator generates an acid upon heating, and has the effect of promoting the crosslinking reaction of at least one compound selected from a compound having a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group, an epoxy compound, an oxetane compound, and a benzoxazine compound.

The thermal decomposition starting temperature of the thermal acid generator is preferably 50° C. to 270° C., more preferably 50° C. to 250° C. In addition, it is preferable to select as the thermal acid generator a material that does not generate acid during drying (pre-baking: about 70 to 140° C.) after the composition is applied to a substrate, but generates acid during final heating (cure: about 100 to 400° C.) after patterning by subsequent exposure and development, because this can suppress a decrease in sensitivity during development.
The thermal decomposition initiation temperature is determined as the lowest exothermic peak temperature when the thermal acid generator is heated to 500° C. at 5° C./min in a pressure-resistant capsule.
An example of an instrument used to measure the thermal decomposition onset temperature is Q2000 (manufactured by TA Instruments).

The acid generated from the thermal acid generator is preferably a strong acid, for example, an arylsulfonic acid such as p-toluenesulfonic acid or benzenesulfonic acid, an alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid or butanesulfonic acid, or a haloalkylsulfonic acid such as trifluoromethanesulfonic acid. Examples of such thermal acid generators include those described in paragraph 0055 of JP 2013-072935 A.

Among these, from the viewpoint of being less likely to remain in the organic film and less likely to deteriorate the physical properties of the organic film, those which generate alkylsulfonic acids having 1 to 4 carbon atoms or haloalkylsulfonic acids having 1 to 4 carbon atoms are more preferred, and examples thereof include (4-hydroxyphenyl)dimethylsulfonium methanesulfonate, (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium methanesulfonate, benzyl (4-hydroxyphenyl)methylsulfonium methanesulfonate, benzyl (4-((methoxycarbonyl)oxy)phenyl)methylsulfonium methanesulfonate, (4-hydroxyphenyl)methyl ((2-methylphenyl)methyl)sulfonium methanesulfonate, and (4-hydroxyphenyl)dimethylsulfonium trifluoromethanesulfonate. As the thermal acid generator, preferred are fluorine, (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium trifluoromethanesulfonate, benzyl(4-hydroxyphenyl)methylsulfonium trifluoromethanesulfonate, benzyl(4-((methoxycarbonyl)oxy)phenyl)methylsulfonium trifluoromethanesulfonate, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium trifluoromethanesulfonate, 3-(5-(((propylsulfonyl)oxy)imino)thiophene-2(5H)-ylidene)-2-(o-tolyl)propanenitrile, and 2,2-bis(3-(methanesulfonylamino)-4-hydroxyphenyl)hexafluoropropane.

In addition, the compounds described in paragraph 0059 of JP-A-2013-167742 are also preferred as thermal acid generators.

The content of the thermal acid generator is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, per 100 parts by mass of the specific resin. By containing 0.01 parts by mass or more, the crosslinking reaction is promoted, so that the mechanical properties and solvent resistance of the organic film can be further improved. In addition, from the viewpoint of the electrical insulation of the organic film, it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.

<Onium salt>
The curable resin composition of the present invention may further contain an onium salt.
In particular, when the curable resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as the specific resin, it preferably contains an onium salt.
The type of onium salt is not particularly limited, but preferred examples include ammonium salts, iminium salts, sulfonium salts, iodonium salts and phosphonium salts.
Among these, ammonium salts or iminium salts are preferred from the viewpoint of high thermal stability, and sulfonium salts, iodonium salts or phosphonium salts are preferred from the viewpoint of compatibility with the polymer.

Furthermore, an onium salt is a salt of a cation and an anion having an onium structure, and the cation and anion may or may not be bonded via a covalent bond.
That is, the onium salt may be an intramolecular salt having a cationic moiety and an anionic moiety in the same molecular structure, or an intermolecular salt in which a cationic molecule and an anionic molecule, which are separate molecules, are ionic-bonded, but an intermolecular salt is preferable. In addition, in the curable resin composition of the present invention, the cationic moiety or cationic molecule and the anionic moiety or anionic molecule may be bonded by an ionic bond or may be dissociated.
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 be a thermal base generator, which will be described later.
The thermal base generator refers to a compound that generates a base when heated, and examples of such a compound include compounds that generate a base when heated to 40° C. or higher.
Examples of the onium salt include the onium salts described in paragraphs 0122 to 0138 of WO 2018/043262. In addition, onium salts used in the field of polyimide precursors can be used without particular limitation.

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 mass% based on the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5 mass% or more, even more preferably 0.85 mass% or more, and even more preferably 1 mass% or more. The upper limit is more preferably 30 mass% or less, even more preferably 20 mass% or less, and even more preferably 10 mass% or less, and may be 5 mass% or less, or may be 4 mass% or less.
The onium salt may be used alone or in combination of two or more. When two or more types are used, the total amount is preferably within the above range.

<Thermal Base Generator>
The curable resin composition of the present invention may further contain a thermal base generator.
In particular, when the curable resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as the specific resin, it preferably contains a thermal base generator.
The other thermal base generator may be a compound corresponding to the above-mentioned onium salt, or may be a thermal base generator other than the above-mentioned onium salt.
Examples of thermal base generators other than the above-mentioned onium salts include nonionic thermal base generators.
Examples of the nonionic thermal base generator include compounds represented by formula (B1) or formula (B2).

In formula (B1) and formula (B2), Rb ¹ , Rb ² and Rb ³ are each independently an organic group not having a tertiary amine structure, a halogen atom or a hydrogen atom. However, Rb ¹ and Rb ² are not simultaneously hydrogen atoms. In addition, none of Rb ¹ , Rb ² and Rb ³ has a carboxy group. In this specification, the tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon carbon atom. Therefore, this does not apply when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when it forms an amide group together with the nitrogen atom.

In formula (B1) and (B2), it is preferable that at least one of Rb ¹ , Rb ² and Rb ³ contains a cyclic structure, and more preferably at least two of them contain a cyclic structure. The cyclic structure may be either a monocyclic ring or a condensed ring, and is preferably a monocyclic ring or a condensed ring in which two monocyclic rings are condensed. The monocyclic ring is preferably a 5-membered ring or a 6-membered ring, and more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring or a benzene ring, and more preferably a cyclohexane ring.

More specifically, Rb ¹ and Rb ² are preferably a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 25 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms). These groups may have a substituent within the range in which the effects of the present invention are exhibited. Rb ¹ and Rb ² may be bonded to each other to form a ring. The ring formed is preferably a 4- to 7-membered nitrogen-containing heterocycle. In particular, ^Rb1 and ^Rb2 are preferably a linear, branched, or cyclic alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms) which may have a substituent, more preferably a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably having 3 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms) which may have a substituent, and even more preferably a cyclohexyl group which may have a substituent.

Rb ³ is an alkyl group (having 1 to 24 carbon atoms, preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), an aryl group (having 6 to 22 carbon atoms, preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), an alkenyl group (having 2 to 24 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably 2 to 6 carbon atoms), an arylalkyl group (having 7 to 23 carbon atoms, preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms), an arylalkenyl group (having 8 to 24 carbon atoms, preferably 8 to 20 carbon atoms, and more preferably 8 to 16 carbon atoms), an alkoxyl group (having 1 to 24 carbon atoms, preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), an aryloxy group (having 6 to 22 carbon atoms, preferably 6 to 18 carbon atoms, and more preferably 6 to 12 carbon atoms), or an arylalkyloxy group (having 7 to 23 carbon atoms, preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms). Among these, a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably having 3 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferable. ^Rb3 may further have a substituent within the range in which the effects of the present invention are exhibited.

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

In the formula, Rb ¹¹ and Rb ¹² , and Rb ³¹ and Rb ³² are the same as Rb ¹ and Rb ² in formula (B1), respectively.
Rb ¹³ is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), which may have a substituent within the range in which the effects of the present invention are exhibited. Among these, Rb ¹³ is preferably an arylalkyl group.

Rb ³³ and Rb ³⁴ each independently represent a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 8 carbon atoms, and even more preferably having 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 8 carbon atoms, and even more preferably having 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 11 carbon atoms), and a hydrogen atom is preferable.

Rb ³⁵ is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 10 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), and an aryl group is preferable.

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

Rb ¹¹ and Rb ¹² have the same meanings as Rb ¹¹ and Rb ¹² in formula (B1-1).
Rb ¹⁵ and Rb ¹⁶ are each a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and even more preferably having 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 6 carbon atoms, and even more preferably having 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 11 carbon atoms), and a hydrogen atom or a methyl group is preferable.
Rb ¹⁷ is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 10 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), and among these, an aryl group is preferable.

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

Among the onium salts described above, specific examples of compounds that are thermal base generators, or specific examples of thermal base generators other than the onium salts described above, include the following compounds.

The content of the other thermal base generator is preferably 0.1 to 50 mass% based on the total solids content of the curable resin composition of the present invention. The lower limit is more preferably 0.5 mass% or more, and even more preferably 1 mass% or more. The upper limit is more preferably 30 mass% or less, and even more preferably 20 mass% or less. One or more types of thermal base generators can be used. When two or more types are used, it is preferable that the total amount is in the above range.

<Crosslinking Agent>
The curable resin composition of the present invention preferably contains a crosslinking agent.
The crosslinking agent may be a radical crosslinking agent or other crosslinking agent.

<Radical Crosslinking Agent>
The curable resin composition of the present invention preferably further contains a radical crosslinking agent.
The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group having an ethylenically unsaturated bond. The group having an ethylenically unsaturated bond includes a group having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth)acryloyl group.
Among these, the group containing an ethylenically unsaturated bond is preferably a (meth)acryloyl group, and from the viewpoint of reactivity, a (meth)acryloxy group is more preferable.

The radical crosslinking agent may be a compound having one or more ethylenically unsaturated bonds, and more preferably a compound having two or more ethylenically unsaturated bonds.
The compound having two ethylenically unsaturated bonds is preferably a compound having two of the above groups containing an ethylenically unsaturated bond.
From the viewpoint of the film strength of the obtained pattern (cured film), the curable resin composition of the present invention preferably contains a compound having 3 or more ethylenically unsaturated bonds as a radical crosslinking agent. The compound having 3 or more ethylenically unsaturated bonds is preferably a compound having 3 to 15 ethylenically unsaturated bonds, more preferably a compound having 3 to 10 ethylenically unsaturated bonds, and even more preferably a compound having 3 to 6 ethylenically unsaturated bonds.
Furthermore, the compound having three or more ethylenically unsaturated bonds is preferably a compound having three or more groups containing the ethylenically unsaturated bonds, more preferably a compound having 3 to 15 such groups, even more preferably a compound having 3 to 10 such groups, and particularly preferably a compound having 3 to 6 such groups.
In addition, from the viewpoint of film strength of the obtained pattern (cured film), it is also preferable that the curable resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and the compound having three or more ethylenically unsaturated bonds.

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

Specific examples of radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, and sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxy groups, and dehydration condensation reaction products of monofunctional or polyfunctional carboxylic acids are also preferably used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having eliminable substituents such as halogeno groups and tosyloxy groups with monofunctional or polyfunctional alcohols, amines, and thiols are also suitable. As another example, it is also possible to use a compound group in which the above unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an allyl ether, etc. As specific examples, the description in paragraphs [0113] to [0122] of JP2016-027357A can be referred to, and the contents of these are incorporated herein by reference.

In addition, the radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples of such a compound include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol (meth)acrylate, trimethylolpropane tri(acryloyloxypropyl)ether, tri(acryloyloxyethyl)isocyanurate, glycerin, trimethylolethane, and many other compounds. Examples of the polyfunctional acrylates and methacrylates include compounds obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth)acrylating the compound, urethane (meth)acrylates as described in JP-B-48-041708, JP-B-50-006034, and JP-A-51-037193, polyester acrylates as described in JP-A-48-064183, JP-B-49-043191, and JP-A-52-030490, and epoxy acrylates which are reaction products of epoxy resins and (meth)acrylic acid, and mixtures thereof. Compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Examples of the polyfunctional (meth)acrylates include those obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group and an ethylenically unsaturated bond, such as glycidyl (meth)acrylate.

In addition, other preferred radical crosslinking agents that can be used include compounds having a fluorene ring and two or more groups having an ethylenically unsaturated bond, as described in JP-A Nos. 2010-160418, 2010-129825, and Japanese Patent No. 4,364,216, and cardo resins.

Other examples include the specific unsaturated compounds described in JP-B-46-043946, JP-B-01-040337, and JP-B-01-040336, and the vinylphosphonic acid compounds described in JP-A-02-025493. Compounds containing perfluoroalkyl groups described in JP-A-61-022048 can also be used. Furthermore, those introduced as photopolymerizable monomers and oligomers in the Journal of the Japan Adhesion Association, Vol. 20, No. 7, pp. 300-308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP 2015-034964 A and the compounds described in paragraphs 0087 to 0131 of WO 2015/199219 A can also be preferably used, the contents of which are incorporated herein by reference.

In addition, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylating the resulting compound, which are described in JP-A-10-062986 as formula (1) and formula (2) along with specific examples thereof, can also be used as radical crosslinking agents.

Furthermore, the compounds described in paragraphs 0104 to 0131 of JP 2015-187211 A can also be used as radical crosslinking agents, the contents of which are incorporated herein by reference.

As radical crosslinking agents, dipentaerythritol triacrylate (commercially available products include KAYARAD D-330, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available products include KAYARAD D-320, manufactured by Nippon Kayaku Co., Ltd., and A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available products include KAYARAD D-310, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available products include KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., and A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which the (meth)acryloyl groups of these are bonded via ethylene glycol residues or propylene glycol residues are preferred. Oligomer types of these can also be used.

Commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer Corporation; SR-209, 231, and 239, bifunctional methacrylates having four ethyleneoxy chains manufactured by Sartomer Corporation; DPCA-60, a hexafunctional acrylate having six pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd.; TPA-330, a trifunctional acrylate having three isobutyleneoxy chains manufactured by Nippon Kayaku Co., Ltd.; and urethane acrylate having four ethyleneoxy chains manufactured by Nippon Kayaku Co., Ltd. Examples of such an agent include Ligomer UAS-10 and UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, and UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), and Blenmer PME400 (manufactured by NOF Corporation).

As radical crosslinking agents, urethane acrylates as described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, and JP-B-02-016765, and urethane compounds having an ethylene oxide skeleton as described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417, and JP-B-62-039418 are also suitable. Furthermore, as radical crosslinking agents, compounds having an amino structure or a sulfide structure in the molecule as described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238 can also be used.

The radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphate group. The radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent in which an acid group is provided by reacting an unreacted hydroxy group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride. Particularly preferred is a radical crosslinking agent in which an acid group is provided by reacting an unreacted hydroxy group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride, in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include polybasic acid modified acrylic oligomers manufactured by Toagosei Co., Ltd., such as M-510 and M-520.

The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 40 mgKOH/g, and more preferably 5 to 30 mgKOH/g. If the acid value of the radical crosslinking agent is within the above range, the agent has excellent handling properties in manufacturing and excellent developability. It also has good polymerizability. On the other hand, from the viewpoint of the development speed in alkaline development, the acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH/g, and more preferably 1 to 100 mgKOH/g. The acid value is measured in accordance with the description of JIS K 0070:1992.

In terms of pattern resolution and film elasticity, the curable resin composition of the present invention preferably uses a bifunctional methacrylate or acrylate. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, and 1,6-hexanediol diacrylate. , 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, bisphenol A EO adduct diacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, other bifunctional acrylates having a urethane bond, and bifunctional methacrylates having a urethane bond can be used. Two or more of these can be mixed and used as necessary.
In addition, from the viewpoint of suppressing warpage associated with controlling the elastic modulus of the pattern (cured film), a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent. As the monofunctional radical crosslinking agent, (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allyl glycidyl ether, diallyl phthalate, and triallyl trimellitate are preferably used. As the monofunctional radical crosslinking agent, a compound having a boiling point of 100° C. or more under normal pressure is also preferred in order to suppress volatilization before exposure.

When a radical crosslinking agent is contained, the content is preferably more than 0% by mass and not more than 60% by mass based on 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 even more preferably 30% by mass or less.

The radical crosslinking agent may be used alone or in combination of two or more. When two or more types are used in combination, it is preferable that the total amount is within the above range.

<Other crosslinking agents>
The curable resin composition of the present invention preferably contains a crosslinking agent other than the above-mentioned radical crosslinking agent.
In the present invention, the other crosslinking agent refers to a crosslinking agent other than the above-mentioned radical crosslinking agent, and is preferably a compound having, in its molecule, a plurality of groups that promote a reaction to form a covalent bond with another compound in the composition or a reaction product thereof upon exposure to light by the above-mentioned photosensitizer, and is preferably a compound having, in its molecule, a plurality of groups that promote a reaction to form a covalent bond with another compound in the composition or a reaction product thereof under the action of an acid or a base.
The acid or base is preferably an acid or base generated from a photoacid generator or photobase generator, which is a photosensitizer, in the exposure step.
As the other crosslinking agent, a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is preferred, and a compound having a structure in which at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is directly bonded to a nitrogen atom is more preferred.
Other crosslinking agents include, for example, compounds having a structure in which an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is replaced with a methylol group or an alkoxymethyl group.The method for producing these compounds is not particularly limited, and they may be compounds having the same structure as the compounds produced by the above method.In addition, they may be oligomers formed by self-condensation of the methylol groups of these compounds.
As the above amino group-containing compound, a crosslinking agent using melamine is called a melamine-based crosslinking agent, a crosslinking agent using glycoluril, urea or alkylene urea is called a urea-based crosslinking agent, a crosslinking agent using alkylene urea is called an alkylene urea-based crosslinking agent, and a crosslinking agent using benzoguanamine is called a benzoguanamine-based crosslinking agent.
Among these, the curable resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from the group consisting of glycoluril-based crosslinking agents and melamine-based crosslinking agents described below.

Specific examples of melamine-based crosslinking agents include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.

Specific examples of urea-based crosslinking agents include glycoluril-based crosslinking agents such as monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, and tetrabutoxymethylated glycoluril;
Urea-based crosslinking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea;
ethyleneurea-based crosslinking agents such as monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxymethylated ethyleneurea, monoethoxymethylated ethyleneurea, diethoxymethylated ethyleneurea, monopropoxymethylated ethyleneurea, dipropoxymethylated ethyleneurea, monobutoxymethylated ethyleneurea, or dibutoxymethylated ethyleneurea;
propylene urea-based crosslinking agents such as monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monodiethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea;
Examples thereof include 1,3-di(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone and 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone.

Specific examples of benzoguanamine-based crosslinking agents include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

In addition, as the compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group, a compound in which at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is directly bonded to an aromatic ring (preferably a benzene ring) is also preferably used.
Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylidene tris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1,3-benzenedimethanol], and 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol.

Other crosslinking agents may be commercially available, and suitable commercially available products include 46DMOC, 46DMOEP (both manufactured by Asahi Organic Chemicals Co., Ltd.), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, and TriML-35XL. , TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac (registered trademark, the same applies below) MX-290, Nikalac MX-280, Nikalac MX-270, Nikalac MX-279, Nikalac MW-100LM, Nikalac MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.), and the like.

It is also preferable that the curable resin composition of the present invention contains at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds as another crosslinking agent.

[Epoxy Compound (Compound Having an Epoxy Group)]
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a crosslinking reaction at 200° C. or less, and does not undergo a dehydration reaction due to the crosslinking, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in suppressing low-temperature curing and warping of the curable resin composition.

It is preferable that the epoxy compound contains a polyethylene oxide group. This further reduces the elastic modulus and suppresses warping. The polyethylene oxide group means a group having 2 or more repeating ethylene oxide units, and it is preferable that the number of repeating units is 2 to 15.

Examples of epoxy compounds include, but are not limited to, bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and epoxy group-containing silicones such as polymethyl(glycidyloxypropyl)siloxane. Specifically, Epicron (registered trademark) 850-S, Epicron (registered trademark) HP-4032, Epicron (registered trademark) HP-7200, Epicron (registered trademark) HP-820, Epicron (registered trademark) HP-4700, Epicron (registered trademark) EXA-4710, Epicron (registered trademark) HP-4770, Epicron (registered trademark) EXA-859CRP, Epicron (registered trademark) EXA-1514, Epicron (registered trademark) EXA-4880, Epicron (registered trademark) EXA-4850-15 0, Epicron EXA-4850-1000, Epicron (registered trademark) EXA-4816, Epicron (registered trademark) EXA-4822, Epicron (registered trademark) EXA-830LVP, Epicron (registered trademark) EXA-8183, Epicron (registered trademark) EXA-8169, Epicron (registered trademark) N-660, Epicron (registered trademark) N-665-EXP-S, Epicron (registered trademark) N-740, Rikaresin (registered trademark) BEO-20E (all trade names, manufactured by DIC Corporation), Rikaresin (registered trademark) (registered trademark) BEO-60E, LIKARESIN (registered trademark) HBE-100, LIKARESIN (registered trademark) DME-100, LIKARESIN (registered trademark) L-200 (product names, New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (all product names, manufactured by ADEKA Corporation), Celoxide 2021P, 2081, 2000, 3000, EHPE3150, Epolead GT400, Celvinarce B0134, B0177 (all product names, manufactured by Daicel Corporation), NC-300 0, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (all trade names, manufactured by Nippon Kayaku Co., Ltd.).

[Oxetane Compounds (Compounds Having an Oxetanyl Group)]
Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. Specific examples include the Aron Oxetane series (e.g., OXT-121, OXT-221, OXT-191, OXT-223) manufactured by Toagosei Co., Ltd., which may be used alone or in combination of two or more kinds.

[Benzoxazine Compound (Compound Having a Benzoxazolyl Group)]
Benzoxazine compounds are preferred because they undergo a crosslinking reaction derived from a ring-opening addition reaction, so that no degassing occurs during curing, and further, they reduce thermal shrinkage and suppress the occurrence of warping.

Preferred examples of benzoxazine compounds include Ba-type benzoxazine, Bm-type benzoxazine, P-d-type benzoxazine, Fa-type benzoxazine (all trade names, manufactured by Shikoku Chemical Industry Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resins, and phenol novolac-type dihydrobenzoxazine compounds. These may be used alone or in combination of two or more.

The content of the other crosslinking agent is preferably 0.1 to 30 mass% relative to the total solids content of the curable resin composition of the present invention, more preferably 0.1 to 20 mass%, even more preferably 0.5 to 15 mass%, and particularly preferably 1.0 to 10 mass%. Only one type of other crosslinking agent may be contained, or two or more types may be contained. When two or more types of other crosslinking agents are contained, it is preferable that the total is within the above range.

<Compounds Having a Sulfonamide Structure, Compounds Having a Thiourea Structure>
From the viewpoint of improving the adhesion of the obtained pattern (cured film) to a substrate, it is preferable that the curable resin composition of the present invention further contains at least one compound selected from the group consisting of compounds having a sulfonamide structure and compounds having a thiourea structure.

[Compounds having a sulfonamide structure]
The sulfonamide structure is a structure represented by the following formula (S-1).

In formula (S-1), R represents a hydrogen atom or an organic group, R may bond to another structure to form a ring structure, and * each independently represents a bonding site to another structure.
The above R is preferably the same group as R ² in the following formula (S-2).
The compound having a sulfonamide structure may be a compound having two or more sulfonamide structures, but is preferably a compound having one sulfonamide structure.

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

In formula (S-2), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a monovalent organic group, and two or more of R ¹ , R ² and R ³ may be bonded to each other to form a ring structure.
It is preferable that R ¹ , R ² and R ³ each independently represent a monovalent organic group.
Examples of R ¹ , R ² , and R ³ include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxy group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a combination of two or more of these groups.
The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, and a 2-ethylhexyl group.
The cycloalkyl group is preferably a cycloalkyl group having 5 to 10 carbon atoms, and more preferably a cycloalkyl group having 6 to 10 carbon atoms. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, and more preferably an alkoxy group having 1 to 5 carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentoxy group.
The alkoxysilyl group is preferably an alkoxysilyl group having 1 to 10 carbon atoms, and more preferably an alkoxysilyl group having 1 to 4 carbon atoms. Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, and a butoxysilyl group.
The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. The aryl group may have a substituent such as an alkyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.
Examples of the heterocyclic group include groups in which one hydrogen atom has been removed from a heterocyclic structure such as a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimididine ring, a pyrazine ring, a piperidine ring, a piperazine ring, a morpholine ring, a dihydropyran ring, a tetrahydropyran group, or a triazine ring.

Among these, a compound in which R ¹ is an aryl group and R ² and R ³ are each independently a hydrogen atom or an alkyl group is preferred.

Examples of compounds having a sulfonamide structure include benzenesulfonamide, dimethylbenzenesulfonamide, N-butylbenzenesulfonamide, sulfanilamide, o-toluenesulfonamide, p-toluenesulfonamide, hydroxynaphthalenesulfonamide, naphthalene-1-sulfonamide, naphthalene-2-sulfonamide, m-nitrobenzenesulfonamide, p-chlorobenzenesulfonamide, methanesulfonamide, N,N-dimethylmethanesulfonamide, N,N-dimethylethanesulfonamide, N,N-diethylmethanesulfonamide, N-methoxymethanesulfonamide, N-dodecylmethanesulfonamide, N-cyclohexyl-1-butanesulfonamide, and 2-aminoethanesulfonamide.

[Compounds having a thiourea structure]
The thiourea structure is a structure represented by the following formula (T-1).

In formula (T-1), ^R4 and ^R5 each independently represent a hydrogen atom or a monovalent organic group, ^R4 and ^R5 may be bonded to form a ring structure, ^R4 may be bonded to another structure to which * is bonded to form a ring structure, ^R5 may be bonded to another structure to which * is bonded to form a ring structure, and * each independently represent a bonding site to another structure.

It is preferable that ^R4 and ^R5 each independently represent a hydrogen atom.
Examples of ^R4 and ^R5 include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxy group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a combination of two or more of these groups.
The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, and a 2-ethylhexyl group.
The cycloalkyl group is preferably a cycloalkyl group having 5 to 10 carbon atoms, and more preferably a cycloalkyl group having 6 to 10 carbon atoms. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, and more preferably an alkoxy group having 1 to 5 carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentoxy group.
The alkoxysilyl group is preferably an alkoxysilyl group having 1 to 10 carbon atoms, and more preferably an alkoxysilyl group having 1 to 4 carbon atoms. Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, and a butoxysilyl group.
The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. The aryl group may have a substituent such as an alkyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.
Examples of the heterocyclic group include a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimididine ring, a pyrazine ring, a piperidine ring, a piperazine ring, a morpholine ring, a dihydropyran ring, a tetrahydropyran group, and a group in which one hydrogen atom has been removed from a heterocyclic structure such as a triazine ring.
The compound having a thiourea structure may be a compound having two or more thiourea structures, but is preferably a compound having one thiourea structure.

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

In formula (T-2), R ⁴ to R ⁷ each independently represent a hydrogen atom or a monovalent organic group, and at least two of R ⁴ to R ⁷ may be bonded to each other to form a ring structure.

In formula (T-2), R ⁴ and R ⁵ have the same meanings as R ⁴ and R ⁵ in formula (T-1), and preferred embodiments are also the same.
In formula (T-2), it is preferable that R ⁶ and R ⁷ each independently represent a monovalent organic group.
In formula (T-2), the preferred embodiments of the monovalent organic group in R ⁶ and R ⁷ are the same as the preferred embodiments of the monovalent organic group in R ⁴ and R ⁵ in formula (T-1).

Examples of compounds having a thiourea structure include N-acetylthiourea, N-allylthiourea, N-allyl-N'-(2-hydroxyethyl)thiourea, 1-adamantylthiourea, N-benzoylthiourea, N,N'-diphenylthiourea, 1-benzyl-phenylthiourea, 1,3-dibutylthiourea, 1,3-diisopropylthiourea, 1,3-dicyclohexylthiourea, 1-(3-(trimethoxysilyl)propyl)-3-methylthiourea, trimethylthiourea, tetramethylthiourea, N,N-diphenylthiourea, ethylenethiourea (2-imidazolinethione), carbimazole, and 1,3-dimethyl-2-thiohydantoin.

〔Content〕
The total content of the compound having a sulfonamide structure and the compound having a thiourea structure relative to the total mass of the curable resin composition of the present invention is preferably 0.05 to 10 mass%, more preferably 0.1 to 5 mass%, and even more preferably 0.2 to 3 mass%.
The curable resin composition of the present invention may contain only one compound selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure, or may contain two or more compounds. When only one compound is contained, the content of the compound is preferably within the above range, and when two or more compounds are contained, the total amount is preferably within the above range.

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

Examples of polymerization inhibitors include hydroquinone, o-methoxyphenol, methoxyhydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol (t-butylcatechol), 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropanol), p-phenylamino)phenol, N-nitrosophenylhydroxyamine cerium salt, N-nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, N,N'-diphenyl-p-phenylenediamine, 2,4-di-tert-butylphenol, di-t-butylhydroxytoluene, 1,4-naphthoquinone, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethyl benzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenothiazine, 1,1-diphenyl-2-picrylhydrazyl, dibutyldithiocarbamate copper (II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. can be suitably used. In addition, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compounds described in paragraphs 0031 to 0046 of WO2015/125469 can also be used.

The following compounds can also be used (Me is a methyl group):

When the curable resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor may be 0.01 to 20.0 mass%, preferably 0.01 to 5 mass%, more preferably 0.02 to 3 mass%, and even more preferably 0.05 to 2.5 mass%, relative to the total solids content of the curable resin composition of the present invention.

The polymerization inhibitor may be one type or two or more types. When two or more types of polymerization inhibitors are used, it is preferable that the total amount is within the above range.

<Metal adhesion improver>
The curable resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used in electrodes, wiring and the like.
Examples of metal adhesion improvers include aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure, compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, amino compounds, and the like.

[Aluminum-based adhesion promoter]
Examples of aluminum-based adhesion promoters include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.
In addition, as the metal adhesion improver, the compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP-A-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 even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the specific resin. By making the content equal to or greater than the above lower limit, the adhesion between the pattern and the metal layer will be good, and by making the content equal to or less than the above upper limit, the heat resistance and mechanical properties of the pattern will be good. Only one type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, it is preferable that the total is within the above range.

<Other additives>
The curable resin composition of the present invention may contain various additives, such as a sensitizer, 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 anti-aggregation agent, etc., as necessary, within the range in which the effects of the present invention can be obtained. When these additives are added, the total amount of the additives is preferably 3 mass % or less of the solid content of the curable resin composition.

[Sensitizer]
The curable resin composition of the present invention may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes electronically excited. The sensitizer in the electronically excited state comes into contact with a thermal curing accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal curing accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo a chemical change and decompose, generating a radical, an acid, or a base.
Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylideneindanone, p-dimethylaminobenzylamine ... Dilidene indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbo Nyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2- Examples of such an alkyl ether compound include mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, and 3',4'-dimethylacetanilide.
As the sensitizer, a sensitizing dye may be used.
For details about the sensitizing dye, the description in paragraphs [0161] to [0163] of JP2016-027357A can be referred to, the contents of which are incorporated herein by reference.

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

[Chain transfer agent]
The curable resin composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pages 683-684. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. These can donate hydrogen to a low activity radical to generate a radical, or can generate a radical by being oxidized and then deprotonated. In particular, a thiol compound can be preferably used.

In addition, the chain transfer agent may be the compound described in paragraphs 0152 to 0153 of WO 2015/199219.

When the curable resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 1 to 5 parts by mass, relative to 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 type or two or more types. When two or more types of chain transfer agents are used, the total is preferably within the above range.

[Surfactant]
A surfactant may be added to the curable resin composition of the present invention in order to further improve the coating property. As the surfactant, various types of surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used. The following surfactants are also preferred. In the following formula, the parentheses indicating the repeating unit of the main chain represent the content (mol%) of each repeating unit, and the parentheses indicating the repeating unit of the side chain represent the number of repeats of each repeating unit.

In addition, the surfactant may be the compound described in paragraphs 0159 to 0165 of WO 2015/199219.
The fluorine-containing surfactant may be a fluorine-containing polymer having an ethylenically unsaturated group in the side chain. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP-A-2010-164965, such as Megafac RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

The fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. Fluorine surfactants with a fluorine content within this range are effective in terms of uniformity of the coating film thickness and liquid saving, and also have good solubility in the composition.

Examples of silicone surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials, Inc.), KP341, KF6001, KF6002 (all manufactured by Shin-Etsu Silicone Co., Ltd.), BYK307, BYK323, BYK330 (all manufactured by BYK-Chemie Co., Ltd.), etc.

Examples of hydrocarbon surfactants include Paionin A-76, Newcalgen FS-3PG, Paionin B-709, Paionin B-811-N, Paionin D-1004, Paionin D-3104, Paionin D-3605, Paionin D-6112, Paionin D-2104-D, Paionin D-212, Paionin D-931, Paionin D-941, Paionin D-951, Paionin E-5310, Paionin P-1050-B, Paionin P-1028-P, Paionin P-4050-T, etc. (all manufactured by Takemoto Oil Co., Ltd.).

Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ether, Examples of such an agent include Stel, Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, and 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, and 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Co., Ltd.), NCW-101, NCW-1001, and NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), Paionin D-6112, D-6112-W, and D-6315 (manufactured by Takemoto Oil Co., Ltd.), Olfin E1010, and Surfynol 104, 400, and 440 (manufactured by Nissin Chemical Industry Co., Ltd.).

Specific examples of cationic surfactants include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 77, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), and W001 (manufactured by Yusho Co., Ltd.).

Specific examples of anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Industries, Ltd.), etc.

When the curable resin composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0 mass% relative to the total solid content of the curable resin composition of the present invention, and more preferably 0.005 to 1.0 mass%. The surfactant may be one type or two or more types. When two or more types of surfactants are used, the total is preferably within the above range.

[Higher fatty acid derivatives]
In order to prevent polymerization inhibition caused by oxygen, the curable resin composition of the present invention may contain a higher fatty acid derivative such as behenic acid or behenic acid amide, and the higher fatty acid derivative may be unevenly distributed on the surface of the curable resin composition during drying after application.

In addition, the higher fatty acid derivative may be the compound described in paragraph 0155 of International Publication No. 2015/199219.

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 mass% based on the total solid content of the curable resin composition of the present invention. The higher fatty acid derivative may be one type or two or more types. When there are two or more types of higher fatty acid derivatives, the total is preferably within the above range.

[Inorganic particles]
The resin composition of the present invention may contain inorganic particles, specifically, calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc.

The average particle size of the inorganic particles is preferably from 0.01 to 2.0 μm, more preferably from 0.02 to 1.5 μm, even more preferably from 0.03 to 1.0 μm, and particularly preferably from 0.04 to 0.5 μm.
By incorporating inorganic particles having the above average particle size, it is possible to achieve both good mechanical properties of the cured film and suppression of scattering of exposure light.

[Ultraviolet absorber]
The composition of the present invention may contain an ultraviolet absorbing agent. Examples of the ultraviolet absorbing agent that can be used include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbing agents.
Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-t-butylphenyl salicylate. Examples of benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octoxybenzophenone. Examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, and 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole.

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

In the present invention, the above-mentioned various ultraviolet absorbents may be used alone or in combination of two or more.
The composition of the present invention may or may not contain an ultraviolet absorber. When the composition of the present invention contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably from 0.001 mass % to 1 mass %, and more preferably from 0.01 mass % to 0.1 mass %, relative to the total solid content mass of the composition of the present invention.

[Organotitanium Compounds]
The resin composition of the present embodiment may contain an organotitanium compound. By containing an organotitanium compound in the resin composition, a resin layer having excellent chemical resistance can be formed even when cured at a low temperature.

Usable organotitanium compounds include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.
Specific examples of the organotitanium compound are shown below in I) to VII):
I) Titanium chelate compounds: Among these, titanium chelate compounds having two or more alkoxy groups are more preferred because they provide a negative photosensitive resin composition with good storage stability and a good cured pattern. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate, titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), and the like.
II) Tetraalkoxytitanium compounds: For example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], and the like.
III) Titanocene compounds: For example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like.
IV) Monoalkoxytitanium compounds: For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc.
V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, and the like.
VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate.
VII) Titanate coupling agents: for example, isopropyl tridodecylbenzenesulfonyl titanate.

Among them, the organic titanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, from the viewpoint of exhibiting better chemical resistance. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

When an organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the cyclized resin precursor. When the blending amount is 0.05 parts by mass or more, the obtained cured pattern exhibits good heat resistance and chemical resistance, while when the blending amount is 10 parts by mass or less, the composition has excellent storage stability.

〔Antioxidant〕
The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, it is possible to improve the elongation properties of the cured film and the adhesion to metal materials. Examples of the antioxidant include phenolic compounds, phosphite compounds, and thioether compounds. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. As a preferred phenolic compound, a hindered phenolic compound can be mentioned. A compound having a substituent at the site (ortho position) adjacent to the phenolic hydroxy group is preferred. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. In addition, the antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule. In addition, a phosphorus-based antioxidant can also be suitably used as the antioxidant. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl)oxy]ethyl]amine, and ethylbis(2,4-di-tert-butyl-6-methylphenyl)phosphite. Examples of commercially available antioxidants include ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-50F, ADK STAB AO-60, ADK STAB AO-60G, ADK STAB AO-80, and ADK STAB AO-330 (all manufactured by ADEKA CORPORATION). In addition, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used as the antioxidant. In addition, the composition of the present invention may contain a latent antioxidant as necessary. Examples of latent antioxidants include compounds in which a site functioning as an antioxidant is protected with a protecting group, and which function as an antioxidant when heated at 100 to 250° C. or heated at 80 to 200° C. in the presence of an acid/base catalyst, resulting in the elimination of the protecting group. Examples of the latent antioxidant include the compounds described in WO 2014/021023, WO 2017/030005, and JP 2017-008219 A. Examples of commercially available latent antioxidants include Adeka Arcles GPA-5001 (manufactured by ADEKA CORPORATION). Examples of preferred antioxidants include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, and a compound represented by the general formula (3).

In general formula (3), R5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms, and R6 represents an alkylene group having 2 or more carbon atoms. R7 represents a monovalent to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms, an O atom, and an N atom. k represents an integer from 1 to 4.

The compound represented by the general formula (3) inhibits the oxidative deterioration of the aliphatic groups and phenolic hydroxyl groups of the resin. In addition, the compound has a rust-preventing effect on metal materials, thereby inhibiting metal oxidation.

Since it can act simultaneously on resins and metal materials, k is preferably an integer between 2 and 4. Examples of R7 include alkyl groups, cycloalkyl groups, alkoxy groups, alkyl ether groups, alkylsilyl groups, alkoxysilyl groups, aryl groups, aryl ether groups, carboxyl groups, carbonyl groups, allyl groups, vinyl groups, heterocyclic groups, -O-, -NH-, -NHNH-, and combinations thereof, and may further have a substituent. Among these, it is preferable to have alkyl ether or -NH- from the viewpoints of solubility in the developer and metal adhesion, and -NH- is more preferable from the viewpoints of interaction with resins and metal adhesion due to metal complex formation.

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

The amount of antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to the resin. If the amount added is less than 0.1 part by mass, it is difficult to obtain the effect of improving the elongation properties after reliability and adhesion to metal materials, and if it is more than 10 parts by mass, there is a risk of a decrease in the sensitivity of the resin composition due to interaction with the photosensitizer. Only one type of antioxidant may be used, or two or more types may be used. If two or more types are used, it is preferable that the total amount is within the above range.

<Restrictions on other substances>
The water 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. Methods for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container.

From the viewpoint of insulation, the metal content of the curable resin composition of the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of metals include sodium, potassium, magnesium, calcium, iron, chromium, nickel, etc. When multiple metals are contained, it is preferable that the total of these metals is within the above range.

In addition, methods for reducing metal impurities unintentionally contained in the curable resin composition of the present invention include selecting raw materials having a low metal content as the raw materials constituting the curable resin composition of the present invention, filtering the raw materials constituting the curable resin composition of the present invention, and lining the inside of the apparatus with polytetrafluoroethylene or the like to perform distillation under conditions that minimize contamination as much as possible.

Considering the use of the curable resin composition of the present invention as a semiconductor material, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm from the viewpoint of wiring corrosion. Among them, those present in the form of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferable that the total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above range.
A preferred method for adjusting the content of halogen atoms is ion exchange treatment.

A conventionally known container can be used as the container for the curable resin composition of the present invention. In addition, it is also preferable to use a multi-layer bottle whose inner wall is made of six types of six layers of resin, or a bottle with a seven-layer structure made of six types of resin, in order to prevent impurities from being mixed into the raw materials or the curable resin composition. Examples of such containers include the container described in JP 2015-123351 A.

<Uses of the curable resin composition>
The curable resin composition of the present invention is preferably used for forming an interlayer insulating film for a rewiring layer.
Furthermore, the present invention can also be used for forming an insulating film for a semiconductor device, a stress buffer film, or the like.

<Preparation of Curable Resin Composition>
The curable resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and can be a conventionally known method.

In addition, it is preferable to perform filtration using a filter in order to remove foreign matter such as dust and fine particles in the curable resin composition. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. On the other hand, from the viewpoint of productivity, it is preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon. The filter may be one that has been washed in advance with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or parallel. When multiple types of filters are used, filters with different pore sizes or materials may be used in combination. In addition, various materials may be filtered multiple times. When filtering multiple times, circulation filtration may be performed. In addition, filtering may be performed under pressure. When filtering under pressure, the pressure applied is preferably 0.05 MPa or more and 0.3 MPa or less. On the other hand, from the viewpoint of productivity, the pressure is preferably from 0.01 MPa to 1.0 MPa, more preferably from 0.03 MPa to 0.9 MPa, and even more preferably from 0.05 MPa to 0.7 MPa.
In addition to filtration using a filter, impurity removal treatment using an adsorbent may be performed. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent may be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon may be used.

(Resin film, cured film, laminate, semiconductor device, and manufacturing method thereof)
Next, a resin film, a cured film, a laminate, a semiconductor device, and methods for producing them will be described.

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

The cured film of the present invention may be laminated in two or more layers, or even three to seven layers, to form a laminate. The laminate of the present invention preferably includes two or more layers of the cured film and includes a metal layer between any of the cured films. For example, a laminate including at least a layer structure in which three layers, a first cured film, a metal layer, and a second cured film, are laminated in this order, is preferred. Both the first cured film and the second cured film are the cured films of the present invention, and for example, both the first cured film and the second cured film are films formed by curing the curable resin composition of the present invention. The curable resin composition of the present invention used to form the first cured film and the curable resin composition of the present invention used to form the second cured film may have the same composition or different compositions. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.

The fields in which the cured film of the present invention can be applied include insulating films for semiconductor devices, interlayer insulating films for rewiring layers, stress buffer films, etc. Other examples include etching patterns of sealing films, substrate materials (base films and coverlays for flexible printed circuit boards, interlayer insulating films), or insulating films for mounting applications such as those described above. For these applications, see, for example, Science & Technology Co., Ltd., "High-performance and Applied Technology of Polyimides," April 2008, edited by Masaaki Kakimoto, CMC Technical Library, "Basics and Development of Polyimide Materials," published in November 2011, and Japan Polyimide and Aromatic Polymer Research Association, "Latest Polyimides: Basics and Applications," NTS, August 2010.

The cured films of the present invention can also be used in the manufacture of printing plates such as offset printing plates or screen printing plates, for etching molded parts, and in the manufacture of protective lacquers and dielectric layers in electronics, especially microelectronics.

The method for producing a cured film of the present invention (hereinafter also simply referred to as the "production method of the present invention") preferably includes a film formation step of applying the curable resin composition of the present invention to a substrate to form a film (resin film).
The method for producing a cured film of the present invention preferably includes the film-forming step, an exposure step of exposing the film to light, and a development step of developing the film.
Moreover, the method for producing a cured film of the present invention includes the above-mentioned film forming step and, if necessary, the above-mentioned developing step, and more preferably includes a heating step of heating the film at 50 to 450°C.
Specifically, it is also preferable to include the following steps (a) to (d).
(a) a film-forming step of applying a curable resin composition to a substrate to form a film (curable resin composition layer), (b) an exposure step of exposing the film after the film-forming step, (c) a development step of developing the exposed film, and (d) a heating step of heating the developed film at 50 to 450° 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 base generator described above is decomposed, and sufficient curability is obtained.

A preferred embodiment of the present invention relates to a method for producing a laminate, which includes a method for producing a cured film of the present invention. In the method for producing a laminate of the present embodiment, after forming a cured film according to the above-mentioned method for producing a cured film, step (a) or steps (a) to (c) or steps (a) to (d) are performed again. In particular, it is preferable to perform each of the above steps in order multiple times, for example, 2 to 5 times (i.e., a total of 3 to 6 times). By stacking the cured films in this way, a laminate can be obtained. In the present invention, it is particularly preferable to provide a metal layer on the part where the cured film is provided, between the cured films, or on both. In addition, in the production of a laminate, it is not necessary to repeat all of the steps (a) to (d), and as described above, a laminate of cured films can be obtained by performing at least (a), preferably steps (a) to (c) or (a) to (d) multiple times.

<Film formation process (layer formation process)>
A production method according to a preferred embodiment of the present invention includes a film-forming step (layer-forming step) of applying a curable resin composition to a substrate to form a film (layer).

The type of substrate can be appropriately determined depending on the application, but is not particularly limited to semiconductor preparation substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, and plasma display panel (PDP) electrode plates. In addition, these substrates may have layers such as an adhesion layer and an oxide layer on the surface. In the present invention, semiconductor preparation substrates are particularly preferred, and silicon substrates, Cu substrates, and mold substrates are more preferred.
Furthermore, these substrates may have a layer such as an adhesion layer made of hexamethyldisilazane (HMDS) or an oxide layer provided on the surface.
As the base material, for example, a plate-shaped base material (substrate) is used.
The shape of the substrate is not particularly limited and may be circular or rectangular, but is preferably rectangular.
The size of the substrate is, for example, a diameter of 100 to 450 mm, preferably 200 to 450 mm, if circular, and, for example, a length of a short side of 100 to 1000 mm, preferably 200 to 700 mm, if rectangular.

In addition, when a curable resin composition layer is formed on the surface of a resin layer or a metal layer, the resin layer or metal layer becomes the substrate.

Coating is the preferred method for applying the curable resin composition to a substrate.

Specifically, examples of the means 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 inkjet method. From the viewpoint of uniformity of the thickness of the curable resin composition layer, more preferred are a spin coating method, a slit coating method, a spray coating method, and an inkjet method. By adjusting the solid content concentration and the coating conditions appropriately according to the method, a resin layer of a desired thickness can be obtained. In addition, the coating method can be appropriately selected depending on the shape of the substrate, and if the substrate is a circular substrate such as a wafer, a spin coating method, a spray coating method, an inkjet method, etc. are preferred, and if the substrate is a rectangular substrate, a slit coating method, a spray coating method, an inkjet method, etc. are preferred. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute.
Depending on the viscosity of the resin composition and the thickness of the film to be coated, it is also preferable to apply the film at a rotation speed of 300 to 3,500 rpm for 10 to 180 seconds. In order to obtain a uniform film thickness, a combination of multiple rotation speeds can be used for coating.
Alternatively, a coating film formed by applying the coating material to a temporary support in advance using the above-mentioned application method may be transferred onto the substrate.
Regarding the transfer method, the methods described in paragraphs 0023 and 0036 to 0051 of JP-A No. 2006-023696 and paragraphs 0096 to 0108 of JP-A No. 2006-047592 can be suitably used in the present invention.
Also, a process may be performed to remove excess film from the edge of the substrate, examples of which include edge bead rinse (EBR), air knife, back rinse, etc.
Furthermore, a pre-wetting step may be employed in which, before applying the resin composition to the substrate, the substrate is coated with various solvents to improve the wettability of the substrate, and then the resin composition is applied.

<Drying process>
The production method of the present invention may include a drying step to remove the solvent after the film-forming step (layer-forming step). The drying temperature is preferably 50 to 150° C., more preferably 70 to 130° C., and even more preferably 90 to 110° C. The drying time is, for example, 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 3 to 7 minutes.

<Exposure process>
The manufacturing method of the present invention may include an exposure step of exposing the film (curable resin composition layer). The amount of exposure is not particularly determined as long as the curable resin composition can be cured, but for example, it is preferable to irradiate with 100 to 10,000 mJ/ ^cm2 , and more preferably 200 to 8,000 mJ/ ^cm2 , calculated as exposure energy at a wavelength of 365 nm.

The exposure wavelength can be appropriately determined in the range of 190 to 1,000 nm, with 240 to 550 nm being preferred.

In terms of the light source, the exposure wavelength may be, in particular, (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, and i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, and the like. For the curable resin composition of the present invention, exposure by a high pressure mercury lamp is particularly preferred, and among these, exposure by i-line is preferred. This allows for particularly high exposure sensitivity to be obtained.
From the viewpoint of ease of handling and productivity, a broad (three wavelengths of g, h, and i lines) light source such as a high-pressure mercury lamp or a semiconductor laser with a wavelength of 405 nm is also suitable.

<Developing process>
The manufacturing method of the present invention may include a development step in which the exposed film (curable resin composition layer) is developed (the film is developed). By performing development, the unexposed part (non-exposed part) is removed in the case of a negative type, and the exposed part is removed in the case of a positive type. The development method is not particularly limited as long as it can form a desired pattern, and examples thereof include discharging the developer from a nozzle, spraying, and immersing the substrate in the developer, and the like, and the discharge from a nozzle is preferably used. The development step can include a step in which the developer is continuously supplied to the substrate, a step in which the developer is kept substantially stationary on the substrate, a step in which the developer is vibrated by ultrasonic waves or the like, and a combination of these steps.

Development is carried out using a developer.
The developer is not particularly limited and any known developer can be used, but a developer containing an organic solvent or an aqueous alkaline solution can be used.

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 calculated by inputting the structural formula in ChemBioDraw.

When the developer contains an organic solvent, the organic solvent may be, for example, esters such as 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 alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionic acid alkyl esters (e.g., 3-alkyloxypropionic acid alkyl esters ... Methyl cypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionic acid alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyloxy-2-methylpropionic acid Methyl and ethyl 2-alkyloxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., and ethers such as 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, Preferred examples of the organic solvents include ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and the like; cyclic hydrocarbons such as toluene, xylene, anisole, limonene, and the like; and sulfoxides such as dimethyl sulfoxide. Also preferred examples of the organic solvents include mixtures of these.

When the developer contains an organic solvent, in the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred. When the developer contains an organic solvent, the organic solvent may be used alone or in combination of two or more.

When the developer contains an organic solvent, the developer preferably contains 50% by weight or more of the organic solvent, more preferably 70% by weight or more of the organic solvent, and even more preferably 90% by weight or more of the organic solvent. The developer may also contain 100% by weight of the organic solvent.

The developer may further comprise other components.
Examples of other components include known surfactants and known defoamers.

When the developer is an alkaline aqueous solution, examples of basic compounds that the alkaline aqueous solution may contain include TMAH (tetramethylammonium hydroxide), KOH (potassium hydroxide), sodium carbonate, etc., and preferably TMAH. When TMAH is used, the content of the basic compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass, based on the total mass of the developer.

[Method of Supplying Developer]
The method of supplying the developer is not particularly limited as long as the desired pattern can be formed, and includes a method of immersing the substrate in the developer, a method of supplying the developer onto the substrate using a nozzle for paddle development, and a method of continuously supplying the developer. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
From the viewpoints of the permeability of the developer, the removability of non-image areas, and production efficiency, a method of supplying the developer through a straight nozzle or a method of continuously supplying the developer through a spray nozzle is preferred, and from the viewpoint of the permeability of the developer into the image areas, a method of supplying the developer through a spray nozzle is more preferred.
Alternatively, a process may be adopted in which the developer is continuously supplied through a straight nozzle, the substrate is spun to remove the developer from the substrate, and after spin drying, the developer is continuously supplied again through a straight nozzle, and the substrate is spun to remove the developer from the substrate. This process may be repeated multiple times.
As a method for supplying the developer in the development process, a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept substantially stationary on the substrate, a process in which the developer is vibrated on the substrate by ultrasonic waves or the like, or a combination of these processes can be used.

The development time is preferably 5 seconds to 10 minutes, more preferably 10 seconds to 5 minutes. The temperature of the developer during development is not particularly specified, but is usually 10 to 45°C, preferably 20 to 40°C.

After the treatment using the developer, rinsing may be further performed. Alternatively, a method of supplying a rinsing liquid before the developer in contact with the pattern is completely dried may be adopted. Rinsing is preferably performed with a solvent different from the developer. For example, rinsing can be performed with a solvent contained in the curable resin composition.
When the developer contains an organic solvent, the rinse liquid may be PGMEA (propylene glycol monoethyl ether acetate), IPA (isopropanol), etc., and is preferably PGMEA. In addition, the rinse liquid for development using a developer containing an alkaline aqueous solution is preferably water.
The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes, and even more preferably 5 seconds to 1 minute. The temperature of the rinsing liquid during rinsing is not particularly limited, but is preferably 10 to 45° C., and more preferably 18 to 30° C.

When the rinse solution contains an organic solvent, examples of the organic solvent include esters such as 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 alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., 3-methyl methyl 2-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionic acid alkyl esters (e.g. methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g. methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g. methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.) ethyl, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., and ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate. , propylene glycol monopropyl ether acetate, etc.; ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc.; aromatic hydrocarbons such as toluene, xylene, anisole, limonene, etc.; sulfoxides such as dimethyl sulfoxide; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, triethylene glycol, etc.; and amides such as N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. are preferably exemplified.

When the rinse solution contains an organic solvent, the organic solvent may be used alone or in combination of two or more. In the present invention, cyclopentanone, γ-butyrolactone, dimethylsulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, with cyclopentanone, γ-butyrolactone, dimethylsulfoxide, PGMEA, and PGME being more preferred, and cyclohexanone and PGMEA being even more preferred.

When the rinse solution contains an organic solvent, the rinse solution preferably contains 50% by mass or more of the organic solvent, more preferably 70% by mass or more of the organic solvent, and even more preferably 90% by mass or more of the organic solvent. In addition, the rinse solution may contain 100% by mass of the organic solvent.

The rinse solution may further contain other ingredients.
Examples of other components include known surfactants and known defoamers.

[Method of Supplying Rinse Liquid]
The method of supplying the rinse liquid is not particularly limited as long as it can form a desired pattern, and examples of the method include a method of immersing the substrate in the rinse liquid, a method of supplying the rinse liquid onto the substrate by puddling, a method of supplying the rinse liquid onto the substrate by showering, and a method of continuously supplying the rinse liquid onto the substrate by means of a straight nozzle or the like.
From the viewpoints of the permeability of the rinse liquid, the removability of non-image areas, and production efficiency, the rinse liquid may be supplied using a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuously supplying the rinse liquid using a spray nozzle is preferred, while from the viewpoint of the permeability of the rinse liquid into the image areas, the method of supplying the rinse liquid using a spray nozzle is more preferred. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, a spray nozzle, etc.
That is, the rinsing step is preferably a step of supplying a rinsing liquid to the exposed film through a straight nozzle or continuously supplying the rinsing liquid to the exposed film, and more preferably a step of supplying the rinsing liquid through a spray nozzle.
As a method of supplying the rinsing liquid in the rinsing step, a step in which the rinsing liquid is continuously supplied to the substrate, a step in which the rinsing liquid is kept substantially stationary on the substrate, a step in which the rinsing liquid is vibrated on the substrate by ultrasonic waves or the like, or a combination of these steps can be used.

<Heating process>
The manufacturing method of the present invention preferably includes a step of heating the developed film at 50 to 450° C. (heating step).
The heating step is preferably included after the film forming step (layer forming step), the drying step, and the developing step. In the heating step, for example, the above-mentioned thermal base generator is decomposed to generate a base, and the cyclization reaction of the precursor of the specific resin proceeds. In addition, the curable resin composition of the present invention may contain a radical polymerizable compound other than the precursor of the specific resin, but the curing of the radical polymerizable compound other than the unreacted precursor of the specific resin can also proceed in this step. The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50° C. or higher, more preferably 80° C. or higher, even more preferably 140° C. or higher, even more preferably 150° C. or higher, even more preferably 160° C. or higher, and even more preferably 170° C. or higher. The upper limit is preferably 500° C. or lower, more preferably 450° C. or lower, even more preferably 350° C. or lower, even more preferably 250° C. or lower, and even more preferably 220° C. or lower.

Heating is preferably performed at a heating rate of 1 to 12°C/min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min. By setting the heating rate at 1°C/min or more, it is possible to prevent excessive volatilization of the amine while ensuring productivity, and by setting the heating rate at 12°C/min or less, it is possible to alleviate the residual stress of the cured film. In addition, in the case of an oven capable of rapid heating, it is preferable to perform heating from the temperature at the start of heating to the maximum heating temperature at a heating rate of 1 to 8°C/sec, more preferably 2 to 7°C/sec, and even more preferably 3 to 6°C/sec.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature begins. For example, when a curable resin composition is applied to a substrate and then dried, it is the temperature of the film (layer) after drying, and it is preferable to gradually increase the temperature from a temperature that is 30 to 200°C 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 even more preferably 30 to 240 minutes.

In particular, when forming a multi-layer laminate, from the viewpoint of interlayer adhesion of the cured film, the heating temperature is preferably 180°C to 320°C, and more preferably 180°C to 260°C. The reason for this is unclear, but it is thought that by heating at this temperature, a crosslinking reaction occurs between the ethynyl groups of the specific resin between the layers.

Heating may be performed in stages. For example, a pretreatment step may be performed in which the temperature is increased from 25°C to 180°C at 3°C/min, held at 180°C for 60 minutes, increased from 180°C to 200°C at 2°C/min, and held at 200°C for 120 minutes. The heating temperature for the pretreatment step is preferably 100 to 200°C, more preferably 110 to 190°C, and even more preferably 120 to 185°C. In this pretreatment step, it is also preferable to treat while irradiating with ultraviolet light as described in U.S. Pat. No. 9,159,547. Such a pretreatment step can improve the properties of the film. The pretreatment step is preferably performed for a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps. For example, pretreatment step 1 may be performed in the range of 100 to 150°C, and then pretreatment step 2 may be performed in the range of 150 to 200°C.

Furthermore, after heating, the material may be cooled, in which case the cooling rate is preferably 1 to 5°C/min.

The heating step is preferably carried out in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, argon, etc., in order to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
The heating means is not particularly limited, but examples thereof include a hot plate, an infrared oven, an electric heating oven, and a hot air oven.

<Metal Layer Forming Process>
The production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the developed film (curable resin composition layer).

As the metal layer, any existing metal species can be used without any particular limitation, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten. Copper, aluminum and alloys containing these metals are more preferred, and copper is even more preferred.

The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in JP 2007-157879 A, JP 2001-521288 A, JP 2004-214501 A, and JP 2004-101850 A can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and combinations of these methods can be considered. More specifically, examples include a patterning method that combines sputtering, photolithography, and etching, and a patterning method that combines photolithography and electrolytic plating.

The thickness of the metal layer at its thickest part is preferably 0.01 to 100 μm, more preferably 0.1 to 50 μm, and even more preferably 1 to 10 μm.

<Lamination process>
The manufacturing method of the present invention preferably further includes a lamination step.

The lamination process is a series of processes including (a) a film formation process (layer formation process), (b) an exposure process, (c) a development process, and (d) a heating process, which are carried out again on the surface of the cured film (resin layer) or metal layer in this order. However, it is also possible to repeat only the film formation process (a). In addition, the heating process (d) may be carried out all at once at the end or in the middle of the lamination. In other words, it is also possible to carry out the processes (a) to (c) a predetermined number of times, and then carry out heating (d), thereby curing the laminated curable resin composition layers all at once. In addition, after the development process (c), the metal layer formation process (e) may be included, and heating (d) may be carried out each time, or heating (d) may be carried out all at once after lamination a predetermined number of times. It goes without saying that the lamination process may further include the above-mentioned drying process, heating process, etc. as appropriate.

If a further lamination step is performed after the lamination step, a surface activation treatment step may be performed after the heating step, the exposure step, or the metal layer formation step. An example of the surface activation treatment is a plasma treatment.

The lamination step is preferably carried out 2 to 20 times, more preferably 2 to 5 times, and even more preferably 3 to 5 times.
Moreover, the layers in the lamination step may be layers having the same composition, shape, film thickness, etc., or may be layers having different compositions.

For example, a configuration of 3 to 7 resin layers, such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, is preferred, and a configuration of 3 to 5 resin layers is even more preferred.

In the present invention, it is particularly preferable to form a cured film (resin layer) of the curable resin composition so as to cover the metal layer after providing the metal layer. Specifically, the steps may be repeated in the order of (a) film formation, (b) exposure, (c) development, (e) metal layer formation, and (d) heating, or the steps may be repeated in the order of (a) film formation, (b) exposure, (c) development, and (e) metal layer formation, with (d) heating at the end or in the middle. The curable resin composition layer (resin layer) and the metal layer can be alternately laminated by alternately performing the lamination step of laminating the curable resin composition layer (resin layer) and the metal layer formation step.

(Surface activation treatment process)
The method for producing a laminate of the present invention may include a surface activation treatment step of subjecting at least a part of the metal layer and the photosensitive resin composition layer to a surface activation treatment.
The surface activation treatment step is usually carried out after the metal layer formation step, but after the exposure and development step, the photosensitive resin composition layer may be subjected to the surface activation treatment step before the metal layer formation step.
The surface activation treatment may be performed on at least a part of the metal layer, or on at least a part of the photosensitive resin composition layer after exposure, or on at least a part of both the metal layer and the photosensitive resin composition layer after exposure. The surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on a part or all of the area of the metal layer on which the photosensitive resin composition layer is formed. In this way, by performing the surface activation treatment on the surface of the metal layer, the adhesion with the resin layer provided on the surface can be improved.
In addition, the surface activation treatment is preferably performed on a part or the whole of the photosensitive resin composition layer (resin layer) after exposure. By performing the surface activation treatment on the surface of the photosensitive resin composition layer in this manner, the adhesion between the surface-activated layer and a metal layer or a resin layer provided on the surface can be improved.
Specifically, the surface activation treatment is selected from plasma treatment with various raw gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, etching treatment with CF ₄ /O ₂ , NF ₃ /O ₂ , SF ₆ , NF ₃ , NF ₃ /O ₂ , surface treatment by ultraviolet (UV) ozone method, immersion treatment in an organic surface treatment agent containing a compound having at least one amino group and thiol group after immersion in an aqueous hydrochloric acid solution to remove the oxide film, and mechanical roughening treatment using a brush, and plasma treatment is preferred, and oxygen plasma treatment using oxygen as the raw gas is particularly preferred. In the case of corona discharge treatment, the energy is preferably 500 to 200,000 J/m ² , more preferably 1000 to 100,000 J/m ² , and most preferably 10,000 to 50,000 J/m ² .

The present invention also discloses a semiconductor device comprising the cured film or laminate of the present invention. Specific examples of semiconductor devices using the curable resin composition of the present invention for forming an interlayer insulating film for a rewiring layer can be seen in paragraphs 0213 to 0218 and FIG. 1 of JP 2016-027357 A, the contents of which are incorporated herein by reference.

The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing contents, processing procedures, etc. shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. "Parts" and "%" are by weight unless otherwise specified.

<Synthesis Example MP-1: Synthesis of Compound MP-1>
In a flask equipped with a stirrer and a condenser, 7.25 g (105 mmol) of 1,2,4-triazole (manufactured by Tokyo Chemical Industry Co., Ltd.), 15.52 g (100 mmol) of Karenz MOI (manufactured by Showa Denko K.K.), and 0.01 g of Neostan U-600 (manufactured by Nitto Kasei K.K.) were dissolved in 70 mL of tetrahydrofuran (manufactured by Tokyo Chemical Industry Co., Ltd.) and stirred at 25° C. for 1 hour. Then, after stirring at 45° C. for 2 hours, the mixture was dissolved in 600 mL of ethyl acetate and transferred to a separatory funnel. Then, the mixture was washed twice with 100 mL of water and twice with 150 mL of saturated saline, and dried over sodium sulfate. The mixture was transferred to a one-neck flask while being filtered through filter paper, and the solvent was removed with an evaporator to obtain 18 g of MP-1. The structure of MP-1 is presumed to be a structure represented by the following formula (MP-1).

<Synthesis Example MP-2: Synthesis of Compound MP-2>
In a flask equipped with a stirrer and a condenser, 15.2 g (0.22 mol) of triazole was mixed with 150 mL of methylene chloride and cooled to 10 ° C. or less. Subsequently, 10.5 g (0.1 mol) of methacrylic acid chloride was dropped over 1 hour, and the temperature was raised to 20-25 ° C. After stirring at 20-25 ° C. for 3 hours, 200 mL of methylene chloride was added, the generated salt was filtered with filter paper, and the filtrate was collected. The filtrate was transferred to a separatory funnel, washed twice with 50 mL of water and twice with 150 mL of saturated saline, and dried with sodium sulfate. This was transferred to a one-neck flask while filtering with filter paper, and the solvent was removed with an evaporator to obtain 20 g of MP-2. The structure of MP-2 is estimated to be a structure represented by the following formula (MP-2).

<Synthesis Example MC-1: Synthesis of Compound MC-1>
In a flask equipped with a stirrer and a condenser, 10.5 g (0.105 mol) of succinic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed with 200 mL of tetrahydrofuran and cooled to 10 ° C. or less. Subsequently, 13. g (0.1 mol) of 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour, and the temperature was raised to 20 to 25 ° C. After stirring at 20 to 25 ° C. for 3 hours, 500 mL of methylene chloride was added, transferred to a separatory funnel, washed twice with 100 mL of water and twice with 150 mL of saturated saline, and dried with sodium sulfate. This was transferred to a one-neck flask while filtering with filter paper, and the solvent was removed with an evaporator to obtain 18 g of MC-1. The structure of MC-1 is presumed to be a structure represented by the following formula (MC-1).

<Synthesis Example PC-1: Synthesis of Compound PC-1>
20 g of propylene glycol monomethyl ether was added to a flask (flask 1), and the mixture was heated to 80° C. while flowing nitrogen, and stirred.
Next, 23.2 g (80 mmol) of 3-(triethoxysilyl)propyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.72 g (20 mmol) of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.46 g of polymerization initiator V-601 (manufactured by Fujifilm Wako Co., Ltd.) were added to another flask (flask 2), dissolved in 38.1 g of propylene glycol monomethyl ether, and added dropwise to flask 1 over 3 hours. Next, the temperature was raised to 85° C., and after stirring for 3 hours, the mixture was cooled to room temperature to obtain a PC-1 solution. The structure of PC-1 is presumed to be a structure represented by the following formula (PC-1). In the following formula, the subscripts in parentheses represent the content ratio (molar ratio) of each repeating unit.
The weight average molecular weight (Mw) was measured to be 23,100.

<Synthesis Examples PC-2 to PC-5: Synthesis of Compounds PC-2 to PC-5>
Compounds PC-2 to PC-5 were synthesized in the same manner as in Synthesis Example PC-1.
The presumed structures of PC-2 to PC-5 are shown in the following formulae (PC-2) to (PC-5), respectively. In the following formulae, the subscripts in parentheses represent the content ratio (molar ratio) of each repeating unit.
The weight average molecular weight (Mw) of PC-2 was 17,500, that of PC-3 was 8,900, that of PC-4 was 12,000, and that of PC-5 was 33,800.

<Synthesis Example PB-1: Synthesis of Compound PB-1>
7.5 g of propylene glycol monomethyl ether was added to a flask (flask 1), and the mixture was heated to 80° C. while flowing nitrogen, and stirred.
Next, 7.78 g (70 mmol) of 2-isopropyl-2-oxazoline (manufactured by Aldrich Co., Ltd.), 2.74 g (20 mmol) of MP-2 (the above synthetic product), 1.26 g (10 mmol) of allyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.55 g of a polymerization initiator V-601 (manufactured by Fujifilm Wako Co., Ltd.) were added to another flask (flask 2), dissolved in 20 g of propylene glycol monomethyl ether, and added dropwise to flask 1 over 3 hours. Next, the temperature was raised to 85° C., and the mixture was stirred for 3 hours, and then cooled to room temperature to obtain a PB-1 solution.
The structure of PB-1 is presumed to be a structure represented by the following formula (PB-1): In the following formula, the subscripts in parentheses represent the content ratio (molar ratio) of each repeating unit.
The weight average molecular weight (Mw) was measured and found to be 16,900.

<Synthesis Examples PB-2 to PB-3, PB-5 to PB-6: Synthesis of Compounds PB-2 to PB-3, PB-5 to PB-6>
Compounds PB-2 to PB-3 and PB-5 to PB-6 were synthesized in the same manner as in Synthesis Example PB-1.
The Mw of PB-2 was 9,800, the Mw of PB-3 was 12,500, the Mw of PB-5 was 25,800, and the Mw of PB-6 was 18,700.

<Synthesis Example C-1: Synthesis of Compound C-1>
In a flask, 9.81 g (100 mmol) of maleic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 80 g of tetrahydrofuran, and the solution was cooled to 0°C to 10°C.
Next, 22.1 g (100 mmol) of 3-aminopropyltriethoxysilane (Tokyo Chemical Industry Co., Ltd.) was added dropwise to the flask over 1 hour. The temperature was then raised to 25° C. and the mixture was stirred for 3 hours. The solution was transferred to a single-neck flask, and the solvent was removed with an evaporator to obtain 30 g of compound C-1.

<Synthesis Examples C-2 to C-3: Synthesis of Compounds C-2 to C-3>
Compounds C-2 and C-3 were synthesized in the same manner as for compound C-1.
In addition, in compound C-2, phthalic anhydride was used instead of maleic anhydride.
Compound C-3 used succinic anhydride instead of maleic anhydride.

<Synthesis Example C-4: Synthesis of Compound C-4>
In a flask, 13.7 g (100 mmol) of p-aminobenzoic acid (Tokyo Chemical Industry Co., Ltd.) was dissolved in 140 g of tetrahydrofuran, and the solution was cooled to 0°C to 10°C.
Next, 24.7 g (100 mmol) of 3-(triethoxysilyl)propyl isocyanate (Tokyo Chemical Industry Co., Ltd.) was added dropwise to the flask over 1 hour. The temperature was then raised to 25° C. and the mixture was stirred for 3 hours. The solution was transferred to a single-neck flask, and the solvent was removed with an evaporator to obtain 37 g of compound C-4.

<Synthesis Example C-5: Synthesis of Compound C-5>
In a flask, 15.2 g (100 mmol) of 4-hydroxymethylbenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.1 g of Neostan U-600 (manufactured by Nitto Chemical Industry Co., Ltd.) were dissolved in 150 g of tetrahydrofuran.
Next, 24.7 g (100 mmol) of 3-(triethoxysilyl)propyl isocyanate (Tokyo Chemical Industry Co., Ltd.) was added dropwise to the flask over 1 hour. The temperature was then raised to 40° C. and stirred for 5 hours. The solution was transferred to a separatory funnel and diluted with 800 mL of ethyl acetate. This was washed with 100 mL of water and 100 mL of saturated saline, then dried over magnesium sulfate, and transferred to a one-neck flask while filtering with filter paper. The solvent was removed with an evaporator to obtain 30 g of compound C-5.

<Synthesis Example C-6: Synthesis of Compound C-6>
46.0 g of N-methyl-2-pyrrolidone (NMP), 4.84 g (15 mmol) of 3,3',4,4'-benzophenonetetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), and 6.64 g (30 mmol) of 3-aminopropyltriethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were placed in a flask and stirred at 25°C for 5 hours to obtain a 20% by mass solution of C-6 in NMP.

<Synthesis Example A-1: Synthesis of polybenzoxazole precursor A-1 from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 4,4'-oxydibenzoyl chloride>
28.0 g (76.4 mmol) of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was dissolved in 200 g of N-methylpyrrolidone with stirring. Then, 12.1 g (153 mmol) of pyridine was added, and a solution of 20.7 g (70.1 mmol) of 4,4'-oxydibenzoyl chloride dissolved in 75 g of N-methylpyrrolidone was added dropwise over 1 hour while maintaining the temperature at -10 to 0°C. After stirring for 30 minutes, 1.00 g (12.7 mmol) of acetyl chloride was added and stirred for an additional 60 minutes. The polybenzoxazole precursor resin was then precipitated in 6 liters of water, and the water-polybenzoxazole precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes. The polybenzoxazole precursor resin was filtered off, stirred again in 6 liters of water for 30 minutes, and filtered again. The resulting polybenzoxazole precursor resin was then dried under reduced pressure at 45° C. for 3 days to obtain polybenzoxazole precursor A-1. This polybenzoxazole precursor A-1 had Mw=21500 and Mn=9500. The carboxy group content in A-1 was 0.002 mmol/g.
The structure of the polybenzoxazole precursor A-1 is presumed to be a structure represented by the following formula (A-1).

<Synthesis Example A-2: Synthesis of polyimide precursor from pyromellitic dianhydride, 4,4′-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate (A-2: polyimide precursor having radical polymerizable group)>
14.06g (64.5mmol) of pyromellitic dianhydride (dried at 140°C for 12 hours), 16.8g (129mmol) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 20.4g (258mmol) of pyridine, and 100g of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at a temperature of 60°C for 18 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. The resulting diester was then chlorinated with SOCl ₂ , and converted into a polyimide precursor with 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example A-5, to obtain a polyimide precursor A-2 in the same manner as in Synthesis Example A-5. The weight average molecular weight of this polyimide precursor A-2 was 21,000. The content of carboxy groups in A-2 was 0.35mmol/g.
The structure of the polyimide precursor A-2 is presumed to be a structure represented by the following formula (A-2).

<Synthesis Example A-3: Synthesis of polyimide precursor from 4,4'-oxydiphthalic dianhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate (A-3: polyimide precursor having radical polymerizable group)>
20.0 g (64.5 mmol) of 4,4'-oxydiphthalic dianhydride (dried at 140 ° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine, and 100 g of diglyme were mixed and stirred at a temperature of 60 ° C. for 18 hours to produce a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Next, the obtained diester was chlorinated with SOCl ₂ , and then converted into a polyimide precursor with 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example A-5, and a polyimide precursor A-3 was obtained in the same manner as in Synthesis Example A-5. The weight average molecular weight of this polyimide precursor A-3 was 19,600. The content of carboxy groups in A-3 was 0.25 mmol / g.
The structure of the polyimide precursor A-3 is presumed to be a structure represented by the following formula (A-3).

<Synthesis Example A-4: Synthesis of polyimide precursor from 4,4'-oxydiphthalic dianhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (orthotolidine) and 2-hydroxyethyl methacrylate (A-4: polyimide precursor having radical polymerizable group)>
20.0 g (64.5 mmol) of 4,4'-oxydiphthalic dianhydride (dried at 140 ° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine, and 100 g of diglyme were mixed and stirred at a temperature of 60 ° C. for 18 hours to produce a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The diester obtained was then chlorinated with SOCl ₂ , and converted into a polyimide precursor with 4,4'-diamino-2,2'-dimethylbiphenyl in the same manner as in Synthesis Example A-5, to obtain a polyimide precursor A-4 in the same manner as in Synthesis Example A-5. The weight average molecular weight of this polyimide precursor A-4 was 23,500. The carboxyl group content in A-4 was 0.21 mmol/g.
The structure of the polyimide precursor A-4 is presumed to be a structure represented by the following formula (A-4).

<Synthesis Example A-5: Synthesis of Polyimide Precursor Resin A-5 from Oxydiphthalic Dianhydride, 4,4'-Biphthalic Anhydride, 2-Hydroxyethyl Methacrylate, and 4,4'-Diaminodiphenyl Ether>
9.49 g (32.25 mmol) of 4,4'-biphthalic anhydride and 10.0 g (32.25 mmol) of oxydiphthalic dianhydride were suspended in 140 mL of diglyme while removing moisture in a dry reactor equipped with a stirrer, a condenser and an internal thermometer. 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 0.05 g of pure water and 10.7 g (135 mmol) of pyridine were added successively and stirred at a temperature of 60°C for 18 hours. The mixture was then cooled to -20°C, after which 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. The mixture was then warmed to room temperature and stirred for 2 hours, after which 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to obtain a clear solution. 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was then added dropwise over 1 hour to the obtained clear solution. 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were then added and the mixture was stirred for 2 hours. The polyimide precursor resin was then precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes. The polyimide precursor resin was collected by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. The obtained polyimide precursor resin was then dried under reduced pressure at 45°C for 3 days to obtain polyimide precursor A-5. The resulting polyimide precursor A-5 had a weight average molecular weight of 23,800 and a number average molecular weight of 10,400. The carboxy group content in A-5 was 0.19 mmol/g.
The structure of the polyimide precursor A-5 is presumed to be a structure represented by the following formula (A-5).

<Synthesis Example A-6: Synthesis of Polyimide Precursor A-6 from 4,4'-oxydiphthalic dianhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate>
155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a separable flask, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added. 79.1 g of pyridine was added with stirring at room temperature to obtain a reaction mixture. After the heat generation due to the reaction had ceased, the mixture was allowed to cool to room temperature and was left to stand for a further 16 hours.
Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Then, a suspension of 93.0 g of 4,4'-diaminodiphenyl ether suspended in 350 ml of γ-butyrolactone was added over 60 minutes while stirring. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and stirred for 1 hour. Then, 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.
The obtained reaction solution was added to 3 liters of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was filtered and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 liters of water to precipitate the polymer, and the resulting precipitate was filtered and then vacuum dried to obtain a powdered polyimide precursor A-6. The weight average molecular weight (Mw) of this polyimide precursor A-6 was measured and found to be 24,000. The carboxy group content in A-6 was 0.11 mmol/g.

<Synthesis Example A-7: Synthesis of Polyimide Precursor A-7 from 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate>
Polymer A-7 was obtained by carrying out a reaction in the same manner as in Synthesis Example 6, except that 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride was used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride in Synthesis Example 6. The weight average molecular weight (Mw) of this polymer A-7 was measured and found to be 22,900. The carboxy group content in A-7 was 0.15 mmol/g.

<Synthesis Example PBI-1: Synthesis of Polyimide PBI-1>
In a flask equipped with a condenser and a stirrer, 22.2 g (50 mmol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 0.02 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were dissolved in 100.0 g of N-methylpyrrolidone (NMP) while removing moisture. Next, 11.9 g (45 mmol) of diamine (AA-1) described later was added, and the mixture was stirred at 25°C for 3 hours, and further stirred at 45°C for 3 hours. Next, 15.8 g (200 mmol) of pyridine, 12.8 g (125 mmol) of acetic anhydride, and 50 g of N-methylpyrrolidone (NMP) were added, and the mixture was stirred at 80°C for 3 hours, and 50 g of N-methylpyrrolidone (NMP) was added to dilute the mixture.
The reaction solution was precipitated in 1 liter of methanol and stirred at 3000 rpm for 15 minutes. The resin was filtered off, stirred again in 1 liter of methanol for 30 minutes, and filtered again. The resulting resin was dried under reduced pressure at 40°C for one day to obtain polyimide PBI-1. The molecular weight of PBI-1 was Mw=19,000 and Mn=8,100.
The structure of polyimide PBI-1 is presumed to be a structure represented by the following formula (PBI-1): The content of carboxy groups in PBI-1 was 0.21 mmol/g.

<Synthesis Example AA-1: Synthesis of diamine AA-1>
In a flask equipped with a condenser and a stirrer, 26.0 g (0.2 mol) of 2-hydroxyethyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) and 17.4 g (0.22 mol) of dehydrated pyridine (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) were dissolved in 78 g of ethyl acetate and cooled to 5° C. or lower. Next, 48.4 g (0.21 mol) of 3,5-dinitrobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 145 g of ethyl acetate, and this solution was dropped into the flask using a dropping funnel over 1 hour. After the dropwise addition was completed, the mixture was stirred at 10° C. or lower for 30 minutes, heated to 25° C., and stirred for 3 hours. Next, the reaction solution was diluted with 600 mL of ethyl acetate (CH ₃ COOEt), transferred to a separatory funnel, and washed in order with 300 mL of water, 300 mL of saturated sodium bicarbonate water, 300 mL of dilute hydrochloric acid, and 300 mL of saturated saline. After separation and washing, the mixture was dried over 30 g of magnesium sulfate, concentrated using an evaporator, and dried in vacuum to obtain 61.0 g of dinitro compound (A-1).
Into a flask equipped with a condenser and a stirrer, 27.9 g (500 mmol) of reduced iron (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 5.9 g (110 mmol) of ammonium chloride (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 3.0 g (50 mmol) of acetic acid (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), and 0.03 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were weighed out, and 200 mL of isopropyl alcohol (IPA) and 30 mL of pure water were added and stirred.
Next, 16.2 g of the dinitro body (A-1) was added in small portions over 1 hour, and stirred for 30 minutes. Next, the external temperature was raised to 85°C, stirred for 2 hours, cooled to 25°C or less, and then filtered using Celite (registered trademark). The filtrate was concentrated with a rotary evaporator and dissolved in 800 mL of ethyl acetate. This was transferred to a separatory funnel, washed twice with 300 mL of saturated sodium bicarbonate water, washed with 300 mL of water, and washed with 300 mL of saturated saline in that order. After separation and washing, the mixture was dried with 30 g of magnesium sulfate, concentrated using an evaporator, and dried in vacuum to obtain 11.0 g of diamine (AA-1).

<Examples and Comparative Examples>
In each of the examples, the components shown in the following table were mixed to obtain a curable resin composition. In each of the comparative examples, the components shown in the following table were mixed to obtain a comparative composition.
Specifically, the contents of the components other than the solvent shown in the table were the amounts (parts by mass) shown in the "Amount added" column of the table.
The obtained curable resin composition and comparative composition were pressure filtered through a polytetrafluoroethylene filter having a pore width of 0.8 μm.
In the table, "-" indicates that the composition does not contain the corresponding component.

Details of each ingredient listed in the table are as follows:

〔resin〕
A-1 to A-7, PBI-1: Polybenzoxazole precursor A-1, polyimide precursors A-2 to A-7, and polyimide PBI-1 synthesized in the above synthesis examples

[Compounds having an oxazoline group]
B-1 to B-6: Compounds having the following structures: B-1, B-2, B-4, and B-5 are manufactured by Tokyo Chemical Industry Co., Ltd., and B-3 and B-6 are manufactured by Aldrich.
PB-1 to PB-3, PB-5 to PB-6: PB-1 to PB-3, PB-5 to PB-6 synthesized in the above synthesis examples
PB-4: EPOCROS RPS-1005 (manufactured by Nippon Shokubai Co., Ltd.)
PB-1 to PB-6 are resins having a repeating unit containing an oxazoline group.

[Compounds Having an Acid Group and an Alkoxysilyl Group]
C-1 to C-6: C-1 to C-6 synthesized in the above synthesis examples
PC-1 to PC-5: PC-1 to PC-5 synthesized in the above synthesis examples
PC-1 to PC-5 are resins having a repeating unit containing an acid group and a repeating unit containing an alkoxysilyl group.
The structures of C-1 to C-6 are presumed to be structures represented by the following formulas (C-1) to (C-6).
In the formulae (PC-1) to (PC-5), the subscripts in the parentheses indicate the content ratio (molar ratio) of the repeating units.

[Base Generator]
D-1 to D-3: Compounds having the following structure D-4: WPBG-27 (FUJIFILM Wako Pure Chemical Industries, Ltd.)

[Photopolymerization initiators (all trade names)]
OXE-01: IRGACURE OXE 01 (manufactured by BASF)
OXE-02: IRGACURE OXE 02 (manufactured by BASF)

[Polymerizable compounds (all trade names)]
SR-209: SR-209 (manufactured by Sartomer)
SR-231: SR-231 (manufactured by Sartomer)
SR-239: SR-239 (manufactured by Sartomer)
A-DPH: Dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[Polymerization inhibitor]
G-1: 1,4-benzoquinone G-2: 4-methoxyphenol G-3: 1,4-dihydroxybenzene G-4: Compound of the following structure

[Compounds Having an Azole Group (Other Compounds Having an Azole Group)]
H-1 to H-3: Compounds having the following structures

[Other additives]
I-1: N-phenyldiethanolamine (Tokyo Chemical Industry Co., Ltd.)

〔solvent〕
DMSO: dimethylsulfoxide; GBL: γ-butyrolactone; NMP: N-methylpyrrolidone. In the table, "DMSO/GBL" indicates that a mixture of DMSO and GBL in a mixing ratio (mass ratio) of 80:20 was used.

<Evaluation>
[Evaluation of copper adhesion]
Each of the curable resin compositions or comparative compositions after the filtration was applied in a layer form on a copper substrate by spin coating to form a curable resin composition layer. The obtained copper substrate to which the curable resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes to form a uniform curable resin composition layer having a thickness of 20 μm on the copper substrate. The curable resin composition layer on the copper substrate was exposed to light using a stepper (Nikon NSR 2005 i9C) with an exposure energy of 500 mJ/cm ² using a 100 μm square photomask, and then developed with cyclopentanone for 60 seconds to obtain a 100 μm square resin layer. Furthermore, the temperature was increased at a rate of 10° C./min under a nitrogen atmosphere, and after reaching the temperature described in the “Curing temperature (° C.)” column in the table, this temperature was maintained for 3 hours to obtain a resin film 2.
However, in the example in which I-4 was used as the base generator, after the temperature described in the above "Curing temperature (°C)" column was reached, i-line exposure was performed on the entire surface of the pattern with an exposure dose of 500 mJ/ ^cm2 while heating for 3 hours.
The shear force of a 100 μm square resin film 2 on a copper substrate was measured using a bond tester (CondorSigma, manufactured by XYZTEC) under an environment of 25° C. and 65% relative humidity (RH). The greater the shear force, the greater the adhesion, which means that the adhesion between the metal and the cured film is excellent, resulting in a favorable result.
The evaluation was carried out according to the following evaluation criteria, and the evaluation results are shown in the "copper adhesion" column in the table.
-Evaluation criteria-
A: Shear force exceeds 40 gf B: Shear force exceeds 35 gf and is equal to or less than 40 gf C: Shear force exceeds 30 gf and is equal to or less than 35 gf D: Shear force exceeds 25 gf and is equal to or less than 30 gf E: Shear force is equal to or less than 25 gf 1 gf is 9.80665×10 ^-3 N.

[Evaluation of chemical resistance (film change rate)]
In each of the examples and comparative examples, the curable resin composition or the comparative composition was applied to a silicon wafer by spin coating to form 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° C. for 5 minutes to form a curable resin composition layer of a uniform thickness of 15 μm on the silicon wafer. The curable resin composition layer on the silicon wafer was exposed to i-line light with an exposure energy of 500 mJ/cm ² using a stepper (Nikon NSR 2005 i9C), and the exposed curable resin composition layer (resin layer) was heated at a heating rate of 10° C./min under a nitrogen atmosphere and heated for 3 hours at the temperature listed in the “Curing temperature (° C.)” column in the table to obtain a cured layer (resin layer) of the curable resin composition layer.
The obtained resin layer was immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated.
Chemical solution: 90:10 (mass ratio) mixture of dimethyl sulfoxide (DMSO) and 25% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) Evaluation conditions: The resin layer was immersed in the above chemical solution at 75°C for 15 minutes, and the film thickness was compared before and after the immersion, and the dissolution rate (nm/min) was calculated. The film thickness was measured at 10 points on the coating surface using an ellipsometer (KT-22 manufactured by Foothill Corporation) and calculated as the arithmetic average value.
The evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in the column "Chemical resistance" in the table. It can be said that the smaller the dissolution rate value, the more excellent the chemical resistance of the obtained cured film (resin layer).
-Evaluation criteria-
A: The dissolution rate was less than 200 nm/min.
B: The dissolution rate was 200 nm/min or more and less than 300 nm/min.
C: The dissolution rate was 300 nm/min or more and less than 400 nm/min.
D: The dissolution rate was 400 nm/min or more.

From the above results, it is evident that the curable resin composition of the present invention can provide a cured film having excellent metal adhesion (copper adhesion).
The comparative compositions according to Comparative Examples 1 to 3 do not contain a compound having an oxazoline group, and it is clear that such comparative compositions have poor metal adhesion (copper adhesion).

<Example 101>
The curable resin composition used in Example 1 was applied in a layer form by spin coating on the surface of the copper thin layer of the resin substrate on which the copper thin layer was formed, and dried at 100°C for 4 minutes to form a curable resin composition layer with a thickness of 20 μm, and then exposed using a stepper (Nikon Corporation, NSR1505 i6). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line and space pattern and a line width of 10 μm). After exposure, the substrate was heated at 100°C for 4 minutes. After the heating, the substrate was developed with cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern.
Next, the temperature was increased at a rate of 10° C./min in a nitrogen atmosphere, and after reaching 230° C., the temperature was maintained at 230° C. for 3 hours to form an interlayer insulating film for a rewiring layer. This interlayer insulating film for a rewiring layer had excellent insulating properties.
Furthermore, when semiconductor devices were manufactured using these interlayer insulating films for redistribution layers, it was confirmed that they operated without any problems.

Claims (17)

at least one resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, a polyimide, and a polybenzoxazole;
A compound having an oxazoline group, which is not included in the above-mentioned resin , and
A compound not corresponding to the resin or the compound having an oxazoline group, including a compound having an acid group and an alkoxysilyl group,
The compound containing an acid group and an alkoxysilyl group is a resin.
A curable resin composition. at least one resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, a polyimide, and a polybenzoxazole;
A compound having an oxazoline group, which is not included in the above-mentioned resin , and
A compound not corresponding to the resin or the compound having an oxazoline group, including a compound having an acid group and an alkoxysilyl group,
the compound containing an acid group and an alkoxysilyl group is a resin containing an azole group ;
A curable resin composition. at least one resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, a polyimide, and a polybenzoxazole;
A compound having an oxazoline group, which is not included in the above-mentioned resin , and
A compound not corresponding to the resin or the compound having an oxazoline group, including a compound having an acid group and an alkoxysilyl group,
the compound having an oxazoline group contains at least one selected from the group consisting of an alkoxysilyl group, a radical polymerizable group, and an azole group,
The compound having an oxazoline group is a resin.
A curable resin composition. The curable resin composition according to any one of claims 1 to 3, wherein the content of carboxy groups in the resin is 1.0 mmol/g or less. The curable resin composition according to any one of claims 1 to 4, wherein the compound having an oxazoline group is a compound containing two or more oxazoline groups in its structure. The curable resin composition according to claim 1 or 2, wherein the compound having an oxazoline group contains at least one selected from the group consisting of an alkoxysilyl group, a radically polymerizable group, and an azole group. The curable resin composition according to claim 1, 2 or 6, wherein the compound having an oxazoline group is a resin. The curable resin composition according to claim 2 or 3, wherein the compound containing an acid group and an alkoxysilyl group is a resin. The curable resin composition according to claim 1 or 3, wherein the compound containing an acid group and an alkoxysilyl group contains at least one group selected from the group consisting of a radical polymerizable group and an azole group. The curable resin composition according to any one of claims 1 to 9, comprising at least one compound selected from the group consisting of a thermal base generator, a photobase generator, and an onium salt. The curable resin composition according to any one of claims 1 to 10, which is used to form an interlayer insulating film for a redistribution layer. A cured film obtained by curing the curable resin composition according to any one of claims 1 to 11. A laminate comprising two or more layers of the cured film according to claim 12, and including a metal layer between any of the cured films. A method for producing a cured film, comprising a film formation step of applying the curable resin composition according to any one of claims 1 to 11 to a substrate to form a film. The method for producing the cured film according to claim 14, comprising an exposure step of exposing the film to light and a development step of developing the film. The method for producing the cured film according to claim 14 or 15, comprising a heating step of heating the film at 50 to 450°C. A semiconductor device comprising the cured film according to claim 12 or the laminate according to claim 13.