JP2024083351A - Curable resin composition, cured film, laminate, method for producing cured film and semiconductor device - Google Patents

Abstract

To provide a curable resin composition having excellent resolution at the time of pattern formation, a cured film obtained by curing the curable resin composition, a laminate containing the cured film, a method for producing the cured film, and a semiconductor device including the cured film or the laminate.SOLUTION: There are provided: a curable resin composition which comprises at least one resin selected from the group consisting of a polyimide precursor containing at least one of a cyclic imide structure and a cyclic isoimide structure, a polybenzoxazole precursor containing a benzoxazole structure and a polyamideimide precursor containing at least one of a cyclic imide structure and a cyclic isoimide structure, and an organometallic complex, wherein a molar content of the cyclic imide structure, the cyclic isoimide structure or the benzoxazole structure is a specific content; a cured film obtained by curing the curable resin composition; a laminate containing the cured film; a method for producing the cured film; and a semiconductor device including the cured film or the laminate.SELECTED DRAWING: None

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.

Resins such as polyimide, polybenzoxazole, and polyamideimide are used in a variety of applications due to their excellent heat resistance and insulating properties. The applications are not particularly limited, but examples of applications include insulating films, sealing materials, and protective films for semiconductor devices for mounting. They are also used as base films and coverlays for flexible substrates.

For example, in the above-mentioned applications, resins such as polyimide, polybenzoxazole, and polyamideimide are used in the form of a curable resin composition containing at least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, and polyamideimide precursors.
Such a curable resin composition is applied to a substrate by, for example, coating to form a photosensitive film, and then, if necessary, exposure, development, heating, etc. are performed to form a cured product on the substrate.
The polyimide precursor, polybenzoxazole precursor, and polyamideimide precursor are cyclized, for example, by heating, and become polyimide, polybenzoxazole, and polyamideimide, respectively, in the cured product.
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, polyamideimide, 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 a negative photosensitive resin composition that contains 100 parts by mass of a polyimide precursor having a specific structure, 1 to 20 parts by mass of a photopolymerization initiator, and 0.01 to 10 parts by mass of a monocarboxylic acid compound having 2 to 30 carbon atoms and having one or more functional groups selected from the group consisting of a hydroxyl group, an ether group, and an ester group.

JP 2011-191749 A

Improved resolution is required when forming patterns from curable resin compositions.

The present invention aims to provide a curable resin composition that has excellent resolution during pattern formation, 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 having at least one of a cyclic imide structure and a cyclic isoimide structure, a polybenzoxazole precursor having a benzoxazole structure, and a polyamideimide precursor having at least one of a cyclic imide structure and a cyclic isoimide structure, and
Contains organometallic complexes,
the total molar content of the cyclic imide structure and the cyclic isoimide structure contained in 1 g of the polyimide precursor is 0.08 to 1.68 mmol/g;
the molar content of the benzoxazole structure contained in 1 g of the polybenzoxazole precursor is 0.22 to 3.97 mmol/g;
the total molar content of the cyclic imide structure and the cyclic isoimide structure contained in 1 g of the polyamideimide precursor is 0.062 to 1.186 mmol/g;
A curable resin composition.
<2> The curable resin composition according to <1>, further comprising a photopolymerization initiator.
<3> The curable resin composition according to <1> or <2>, wherein the photopolymerization initiator is an oxime compound.
<4> The curable resin composition according to any one of <1> to <3>, further comprising a crosslinking agent.
<5> The curable resin composition according to any one of <1> to <4>, wherein the organometallic complex is a metallocene compound.
<6> The curable resin composition according to any one of <1> to <5>, wherein the metal contained in the organometallic complex is at least one metal selected from the group consisting of titanium, zirconium, and hafnium.
<7> The curable resin composition according to any one of <1> to <6>, wherein the organometallic complex has a photoradical polymerization initiation ability.
<8> The curable resin composition according to any one of <1> to <7>, which is used for forming a photosensitive film to be subjected to negative development.
<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 <13>, wherein the exposure light used in the exposure contains light having a wavelength of 405 nm.
<15> The method for producing a cured film according to <13> or <14>, wherein the exposure is performed by a laser direct imaging method.
<16> A method for producing a cured film according to any one of <12> to <15>, comprising a heating step of heating the film at 50 to 450° C.
<17> A semiconductor device comprising the cured film according to <10> or the laminate according to <11>.

The present invention provides a curable resin composition that exhibits excellent resolution during pattern formation, 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.

Hereinafter, the main embodiments of the present invention will be described, 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 that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have substituents (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. Furthermore, 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 film, the direction from the substrate to the photosensitive film 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 comprises at least one resin selected from the group consisting of a polyimide precursor containing at least one of a cyclic imide structure and a cyclic isoimide structure, a polybenzoxazole precursor containing a benzoxazole structure, and a polyamideimide precursor containing at least one of a cyclic imide structure and a cyclic isoimide structure (hereinafter also referred to as a "specific resin"). In addition, the curable resin composition of the present invention comprises an organometallic complex, and the total molar content of the cyclic imide structure and the cyclic isoimide structure contained in 1 g of the polyimide precursor is 0.08 to 1.68 mmol/g, the molar content of the benzoxazole structure contained in 1 g of the polybenzoxazole precursor is 0.22 to 3.97 mmol/g, and the total molar content of the cyclic imide structure and the cyclic isoimide structure contained in 1 g of the polyamideimide precursor is 0.062 to 1.186 mmol/g.

The curable resin composition of the present invention is preferably used for forming a photosensitive film to be exposed to light and developed, and is preferably used for forming a film to be exposed to light and developed using a developer containing an organic solvent.
The curable resin composition of the present invention is preferably used for forming a photosensitive film to be subjected to negative development.
In the present invention, negative development refers to a development in which the non-exposed areas are removed by development during exposure and development, and positive development refers to a development in which the exposed areas are removed by development.
As the exposure method, the developer, and the development method, for example, the exposure method described in the exposure step and the developer and development method described in the development step in the description of the method for producing a cured film described later can be used.

The curable resin composition of the present invention is excellent in exposure sensitivity and in chemical resistance of the obtained pattern.
The mechanism by which the above effects are obtained is unclear, but is speculated to be as follows.

For example, as described in Patent Document 1, an organic titanium compound or the like is added to a curable resin composition in order to improve chemical resistance.
However, when a composition containing an organometallic complex is used for patterning, the organometallic complex may aggregate within the film, resulting in a decrease in resolution.
In the present invention, a resin containing a specific amount of a cyclic imide structure, a cyclic isoimide structure, or a benzoxazole structure is used as the resin in the resin composition. It is believed that the strong interaction between these structures and the organometallic complex causes the organometallic complex contained in the composition to be dispersed in a nearly uniform state within the film. As a result, it is presumed that the resin composition of the present invention has excellent resolution.

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 a polyimide precursor containing at least one of a cyclic imide structure and a cyclic isoimide structure, a polybenzoxazole precursor containing a benzoxazole structure, and a polyamideimide precursor containing at least one of a cyclic imide structure and a cyclic isoimide structure.
The curable resin composition of the present invention preferably contains, as the specific resin, a polyimide precursor containing at least one of a cyclic imide structure and a cyclic isoimide structure.
In addition, the specific resin preferably has a radical 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 photosensitive film 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 film or negative-type photosensitive film is formed.

When the resin composition contains a polyimide precursor as the specific resin, from the viewpoint of resolution, the total molar content of the cyclic imide structure and the cyclic isoimide structure in 1 g of the polyimide precursor is 0.08 to 1.68 mmol/g, preferably 0.10 to 1.00 mmol/g, more preferably 0.12 to 0.80 mmol/g, and even more preferably 0.15 to 0.60 mmol/g.
The polyimide precursor preferably contains at least a cyclic imide structure.
The polyimide precursor may have at least one of a cyclic imide structure and a cyclic isoimide structure in a side chain, but preferably has it in the main chain.
In this specification, the main chain of a resin refers to the relatively longest molecular chain in the molecule.
When the resin composition contains a polybenzoxazole precursor as the specific resin, from the viewpoint of resolution, the molar amount of the benzoxazole structure in 1 g of the polybenzoxazole precursor is 0.22 to 3.97 mmol/g, preferably 0.25 to 3.00 mmol/g, more preferably 0.28 to 2.50 mmol/g, and even more preferably 0.30 to 2.00 mmol/g.
The polybenzoxazole precursor may have a benzoxazole structure in a side chain, but preferably has it in the main chain.
When the resin composition contains a polyamideimide precursor as the specific resin, from the viewpoint of resolution, the total molar content of the cyclic imide structure and the cyclic isoimide structure in 1 g of the polyamideimide precursor is 0.062 to 1.186 mmol/g, preferably 0.070 to 1.000 mmol/g, more preferably 0.080 to 0.800 mmol/g, and even more preferably 0.090 to 0.700 mmol/g.
In addition, the polyamide-imide precursor preferably contains at least a cyclic imide structure.
The polyamideimide precursor may have at least one of a cyclic imide structure and a cyclic isoimide structure in a side chain, but preferably has it in the main chain.

[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).

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, -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 )phenyl]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, acetoxyethyl Anamine, 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) 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 At least one diamine selected from 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(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.

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

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

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.

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

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-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride These include tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and their alkyl and alkoxy derivatives having 1 to 6 carbon atoms.

Furthermore, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 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 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 include those using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. as the diamine component.

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).

The polyimide precursor preferably contains, as a repeating unit having at least one of a cyclic imide structure and a cyclic isoimide structure, at least one repeating unit selected from the group consisting of repeating units represented by any of the following formulas (2-1) to (2-6), and more preferably contains at least one repeating unit selected from the group consisting of repeating units represented by the following formula (2-1), repeating units represented by the following formula (2-2), and repeating units represented by the following formula (2-3).

In formulas (2-1) to (2-6), R ¹¹¹ , R ¹¹³ , R ¹¹⁴ , R ¹¹⁵ , A ¹ and A ² have the same meanings as R ¹¹¹ , R ¹¹³ , R ¹¹⁴ , R ¹¹⁵ , A ¹ and A ² in formula (2) above, and preferred embodiments are also the same.

The total content of the repeating units represented by any one of formulas (2-1) to (2-6) may be an amount such that the total content of the cyclic imide structure and the cyclic isoimide structure in the polyimide precursor falls within the above-mentioned range.

One embodiment of the polyimide precursor of the present invention is one in which the total content of the repeating units represented by formula (2) and any of the repeating units represented by formulas (2-1) to (2-6) is 50 mol% or more of the total repeating units. The total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. There is no particular upper limit to the total content, and all of the repeating units in the polyimide precursor except for the terminals may be either the repeating units represented by formula (2) or any of the repeating units represented by formulas (2-1) to (2-6).

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.

[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).

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 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.

Furthermore, R ¹²¹ may be a structure derived from a dicarboxylic acid or dicarboxylic acid halide containing a benzoxazole structure. By making R ¹²¹ have the above structure, a benzoxazole structure is introduced into the benzoxazole precursor.
Examples of the above structure include the following structures: In the following structures, each * independently represents a bonding site with another structure.

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 R ₃ , 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 the production method of 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.
The polybenzoxazole precursor preferably contains, as a repeating unit having a benzoxazole structure, at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (3-1), a repeating unit represented by the following formula (3-2), and a repeating unit represented by the following formula (3-3):

In formulae (3-1) to (3-3), R ¹²¹ , R ¹²² , R ¹²³ and R ¹²⁴ have the same meanings as R ¹²¹ , R ¹²² , R ¹²³ and R ¹²⁴ in formula (3), respectively, and preferred embodiments are also the same.

The content of the repeating unit represented by formula (3-1), the repeating unit represented by formula (3-2), and the repeating unit represented by formula (3-3) may be set so that the content of the benzoxazole structure in the polybenzoxazole precursor falls within the above-mentioned range.

In addition, the polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating structural unit, in that this can suppress the occurrence of warping associated with ring closure.

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 after dehydration and ring closure of the polybenzoxazole precursor, 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.

[Polyamide-imide precursor]
The polyamideimide precursor preferably contains a repeating unit represented by the following formula (PAI-2).

In formula (PAI-2), R ¹¹⁷ represents a trivalent organic group, R ¹¹¹ represents a divalent organic group, A ² represents an oxygen atom or -NH-, and R ¹¹³ represents a hydrogen atom or a monovalent organic group.

In formula (PAI-2), R ¹¹⁷ is exemplified by a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, a heteroaromatic group, or a group in which two or more of these are linked by a single bond or a linking group. A linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined by a single bond or a linking group is preferred, and an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group is more preferred.
The above-mentioned linking group is preferably -O-, -S-, -C(=O)-, -S(=O) ₂ -, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these, and more preferably -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these.
The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
The halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and more preferably a halogenated alkylene group having 1 to 4 carbon atoms. In addition, examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. The halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms are substituted with halogen atoms. Examples of preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group.
The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and further preferably a 1,3-phenylene group or a 1,4-phenylene group.

Also, R ¹¹⁷ is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated. The halogenation is preferably chlorination.
In the present invention, a compound having three carboxy groups is called a tricarboxylic acid compound.
Of the three carboxy groups of the tricarboxylic acid compound, two carboxy groups may be converted into acid anhydrides.
The optionally halogenated tricarboxylic acid compound used in the production of the polyamideimide precursor includes branched aliphatic, cyclic aliphatic or aromatic tricarboxylic acid compounds.
These tricarboxylic acid compounds may be used alone or in combination of two or more.

Specifically, tricarboxylic acid compounds containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined via a single bond or a linking group are preferred, and tricarboxylic acid compounds containing an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined via a single bond or a linking group are more preferred.

Specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and compounds in which phthalic acid (or phthalic anhydride) and benzoic acid are linked via a single bond, -O-, _-CH2- , -C( _CH3 ) _2- , -C( _CF3 ) _2- , _-SO2- , or a phenylene group.
These compounds may be compounds in which two carboxy groups are anhydridized (e.g., trimellitic anhydride) or compounds in which at least one carboxy group is halogenated (e.g., trimellitic anhydride chloride).

In formula (PAI-2), R ¹¹¹ , A ² and R ¹¹³ have the same meanings as R ¹¹¹ , A ² and R ¹¹³ in formula (2) above, and preferred embodiments are also the same.

The polyamideimide precursor may further include other repeat units.
Examples of other repeating units include a repeating unit represented by the above formula (2), a repeating unit represented by any one of formulas (2-1) to (2-6), and a repeating unit represented by the following formula (PAI-1).

In formula (PAI-1), R ¹¹⁶ represents a divalent organic group, and R ¹¹¹ represents a divalent organic group.
In formula (PAI-1), R ¹¹⁶ is exemplified by a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, a heteroaromatic group, or a group in which two or more of these are linked by a single bond or a linking group. A linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined by a single bond or a linking group is preferred, and an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group is more preferred.
The above-mentioned linking group is preferably -O-, -S-, -C(=O)-, -S(=O) ₂ -, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these, and more preferably -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these.
The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
The halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and more preferably a halogenated alkylene group having 1 to 4 carbon atoms. In addition, examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. The halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms are substituted with halogen atoms. Examples of preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group.
The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and further preferably a 1,3-phenylene group or a 1,4-phenylene group.

Also, R ¹¹⁶ is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound.
In the present invention, a compound having two carboxy groups is called a dicarboxylic acid compound, and a compound having two halogenated carboxy groups is called a dicarboxylic acid dihalide compound.
The carboxy group in the dicarboxylic acid dihalide compound may be halogenated, but is preferably chlorinated, for example, i.e., the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.
Examples of the optionally halogenated dicarboxylic acid compound or dicarboxylic acid dihalide compound used in the production of the polyamideimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compound or dicarboxylic acid dihalide compound.
These dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used alone or in combination of two or more.

Specifically, the dicarboxylic acid compound or dicarboxylic acid dihalide compound is preferably a dicarboxylic acid compound or dicarboxylic acid dihalide compound that contains a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined by a single bond or a linking group, and more preferably a dicarboxylic acid compound or dicarboxylic acid dihalide compound that contains an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group.

Specific examples of dicarboxylic acid compounds 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, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, and hexadecafluorosuccinic acid. Examples of the fluorosebacic acid include fluorosebacic 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, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxydiphenyl ether, and benzophenone-4,4'-dicarboxylic acid.
Specific examples of the dicarboxylic acid dihalide compound include compounds having a structure in which two carboxy groups in the specific examples of the dicarboxylic acid compound are halogenated.

In formula (PAI-1), R ¹¹¹ has the same meaning as R ¹¹¹ in formula (2) above, and preferred embodiments are also the same.

The polyamideimide precursor preferably contains a repeating unit represented by either of the following formulas (PAI-3) and (PAI-4) as a repeating unit having at least one of a cyclic imide structure and a cyclic isoimide structure, and more preferably contains a repeating unit represented by the following formula (PAI-3).

In formula (PAI-3) or formula (PAI-4), R ¹¹¹ and R ¹¹⁷ have the same meanings as R ¹¹¹ and R ¹¹⁷ in formula (PAI-2), respectively, and preferred embodiments are also the same.

The content of the repeating units represented by either formula (PAI-3) or (PAI-4) may be an amount such that the total content of cyclic imide structures and cyclic isoimide structures in the polyamideimide precursor falls within the above-mentioned range.

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

In order to improve adhesion to the substrate, the polyamide-imide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specific examples include those using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. as the diamine component.

As an embodiment of the polyamideimide precursor in the present invention, the total content of the repeating unit represented by formula (PAI-2), the repeating unit represented by formula (PAI-1), the repeating unit represented by formula (PAI-3), the repeating unit represented by formula (PAI-4), the repeating unit represented by formula (2), and the repeating unit represented by any one of formulas (2-1) to (2-6) is 50 mol% or more of the total repeating units. The total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the polyamideimide precursor except for the terminals may be any one of the repeating units represented by formula (PAI-2), the repeating unit represented by formula (PAI-1), the repeating unit represented by any one of formulas (PAI-3) and (PAI-4), the repeating unit represented by formula (2), and the repeating unit represented by any one of formulas (2-1) to (2-6).
Another embodiment of the polyamideimide precursor of the present invention is one in which the total content of the repeating units represented by formula (PAI-2), the repeating units represented by formula (PAI-1), and the repeating units represented by any one of formulas (PAI-3) and (PAI-4) is 50 mol% or more of the total repeating units. The total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all of the repeating units in the polyamideimide precursor except for the terminals may be any of the repeating units represented by formula (PAI-2), the repeating units represented by formula (PAI-1), or the repeating units represented by any one of formulas (PAI-3) and (PAI-4).

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

The polydispersity of the molecular weight of the polyamideimide precursor is preferably 1.5 to 3.5, and more preferably 2 to 3.
In this specification, the dispersity of molecular weight refers to the value obtained by dividing the weight average molecular weight by the number average molecular weight (weight average molecular weight/number average molecular weight).

[Method for producing polyimide precursors, 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.

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 limitation, and examples of the non-halogenated catalyst include boroxine compounds, N-hydroxy compounds, tertiary amines, phosphoric esters, amine salts, urea compounds, and carbodiimide compounds. Examples of the carbodiimide compounds include N,N'-diisopropylcarbodiimide, N,N'-dicyclohexylcarbodiimide, and the like.
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.

In the synthesis of polyimides and the like, for example, the total molar content of the above-mentioned cyclic imide structure and cyclic isoimide structure, or the molar content of the above-mentioned benzoxazole structure can be adjusted by appropriately setting the reaction time, reaction temperature, and pH during the reaction when reacting a dicarboxylic acid or a dicarboxylic acid derivative (which may be halogenated with a halogenating agent, or may not be halogenated and a non-halogenated catalyst may be used) with a diamine.

-End-capping agent-
In the method for producing a polyimide precursor or the like, in order to further improve storage stability, 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 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-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-9-aminonaphthalene, 1-carboxy-10-aminonaphthalene, 1-carboxy-11-aminonaphthalene, 1-carboxy-12-aminonaphthalene, 1-carboxy-13-aminonaphthalene, 1-carboxy-14-aminonaphthalene, 1-carboxy-15-aminonaphthalene, 1-carboxy-16-aminonaphthalene, 1-carboxy-17-aminonaphthalene, 1-carboxy-18-aminonaphthalene, 1-carboxy-19 ... Examples of the amino acid include 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, and 4-aminothiophenol. 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.

It is also preferable that the curable resin composition of the present invention 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)).
When the curable resin composition of the present invention contains two or more kinds of polyimide precursors, it is sufficient that the total molar content of cyclic imide structures and cyclic isoimide structures contained in at least one polyimide precursor is within the above-mentioned range. It is preferable that the total molar content of cyclic imide structures and cyclic isoimide structures contained in all polyimide precursors is within the above-mentioned range when the total amount of all polyimide precursors is taken as 1 g, and it is more preferable that each of the polyimide precursors contained in the curable resin composition contains a cyclic imide structure and a cyclic isoimide structure in the above-mentioned range.
When the curable resin composition of the present invention contains two or more polybenzoxazole precursors, the molar content of the benzoxazole structure contained in at least one polybenzoxazole precursor may be within the above-mentioned range. When the total amount of all polybenzoxazole precursors is taken as 1 g, the total molar content of the benzoxazole structures contained in all polybenzoxazole precursors is preferably within the above-mentioned range, and it is more preferable that each of the polyimide precursors contained in the curable resin composition contains at least one of a cyclic imide structure and a cyclic isoimide structure within the above-mentioned range.
When the curable resin composition of the present invention contains two or more types of polyamideimide precursors, the total molar content of cyclic imide structures and cyclic isoimide structures contained in at least one polyamideimide precursor may be within the above-mentioned range, and it is preferable that the total molar content of cyclic imide structures and cyclic isoimide structures contained in all polyamideimide precursors relative to the total amount of all polyamideimide precursors being 1 g is within the above-mentioned range, and it is more preferable that each of the polyamideimide precursors contained in the curable resin composition contains at least one of a cyclic imide structure and a cyclic isoimide structure in the above-mentioned range.

<Organometallic Complex>
The curable resin composition of the present invention contains an organometallic complex.
The organometallic complex may be an organic complex compound containing a metal atom, but is preferably a complex compound containing a metal atom and an organic group, more preferably a compound in which an organic group is coordinated to a metal atom, and further preferably a metallocene compound.
In the present invention, the metallocene compound refers to an organometallic complex having two cyclopentadienyl anion derivatives, which may have a substituent, as η5-ligands.
The organic group is not particularly limited, but is preferably a hydrocarbon group or a group consisting of a combination of a hydrocarbon group and a heteroatom, preferably an oxygen atom, a sulfur atom, or a nitrogen atom.
In the present invention, it is preferred that at least one of the organic groups is a cyclic group, and more preferred that at least two of the organic groups are cyclic groups.
The cyclic group is preferably selected from a 5-membered cyclic group and a 6-membered cyclic group, and more preferably a 5-membered cyclic group.
The cyclic group may be a hydrocarbon ring or a heterocyclic ring, with a hydrocarbon ring being preferred.
The five-membered cyclic group is preferably a cyclopentadienyl group.
The organometallic complex used in the present invention preferably contains 2 to 4 cyclic groups in one molecule.

The metal contained in the organometallic complex is not particularly limited, but is preferably a metal belonging to Group 4 elements, more preferably at least one metal selected from the group consisting of titanium, zirconium, and hafnium, even more preferably at least one metal selected from the group consisting of titanium and zirconium, and particularly preferably titanium.

The organometallic complex may contain two or more metal atoms or only one metal atom, but preferably contains only one metal atom. When the organometallic complex contains two or more metal atoms, it may contain only one type of metal atom, or it may contain two or more types of metal atoms.

The organometallic complex is preferably a ferrocene compound, a titanocene compound, a zirconocene compound, or a hafnocene compound, more preferably a titanocene compound, a zirconocene compound, or a hafnocene compound, even more preferably a titanocene compound or a zirconocene compound, and particularly preferably a titanocene compound.

An embodiment in which the organometallic complex has a photoradical polymerization initiation ability is also one of the preferred embodiments of the present invention.
According to the present invention, it is believed that the use of a specific resin allows the organometallic complex to be dispersed in a nearly uniform state in the film.
Therefore, when the organometallic complex has photoradical polymerization initiation ability, it is considered that local aggregation of the radical polymerization initiator due to aggregation of the organometallic complex is suppressed.
It is believed that the degree of polymerization of the specific resin or crosslinking agent is likely to be uniform in the film by suppressing the aggregation of the radical polymerization initiator, which makes it less likely that development residues or breaks in the pattern will occur, and improves the resolution.
In the present invention, having photoradical polymerization initiation ability means that it is possible to generate free radicals that can initiate radical polymerization by irradiation with light. For example, when a composition containing a radical crosslinking agent and an organometallic complex is irradiated with light in a wavelength range in which the organometallic complex absorbs light and the radical crosslinking agent does not absorb light, the presence or absence of photoradical polymerization initiation ability can be confirmed by checking whether or not the radical crosslinking agent disappears. To check whether or not the radical crosslinking agent disappears, an appropriate method can be selected depending on the type of radical crosslinking agent, and for example, it may be confirmed by IR measurement (infrared spectroscopy measurement) or HPLC measurement (high performance liquid chromatography).
When the organometallic complex has photoradical polymerization initiation ability, the organometallic complex is preferably a metallocene compound, more preferably a titanocene compound, a zirconocene compound or a hafnocene compound, further preferably a titanocene compound or a zirconocene compound, and particularly preferably a titanocene compound.
When the organometallic complex does not have photoradical polymerization initiation ability, the organometallic complex is preferably at least one compound selected from the group consisting of titanocene compounds, tetraalkoxytitanium compounds, titanium acylate compounds, titanium chelate compounds, zirconocene compounds, and hafnocene compounds, more preferably at least one compound selected from the group consisting of titanocene compounds, zirconocene compounds, and hafnocene compounds, even more preferably at least one compound selected from the group consisting of titanocene compounds and zirconocene compounds, and particularly preferably a titanocene compound.

The molecular weight of the organometallic complex is preferably 50 to 2,000, and more preferably 100 to 1,000.

Preferred examples of the organometallic complex include compounds represented by the following formula (P).

In formula (P), M is a metal atom, and each R is independently a substituent.
It is preferable that each R is independently selected from an aromatic group, an alkyl group, a halogen atom, and an alkylsulfonyloxy group.

In formula (P), the metal atom represented by M is preferably an iron atom, a titanium atom, a zirconium atom or a hafnium atom, more preferably a titanium atom, a zirconium atom or a hafnium atom, still more preferably a titanium atom or a zirconium atom, and particularly preferably a titanium atom.
The aromatic group for R in formula (P) includes aromatic groups having 6 to 20 carbon atoms, and is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, such as a phenyl group, a 1-naphthyl group, or a 2-naphthyl group.
The alkyl group for R in formula (P) is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a t-butyl group, an isopentyl group, a 2-ethylhexyl group, a 2-methylhexyl group, and a cyclopentyl group.
The halogen atom in R includes F, Cl, Br and I.
The alkyl group constituting the alkylsulfonyloxy group in R is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a t-butyl group, an isopentyl group, a 2-ethylhexyl group, a 2-methylhexyl group, and a cyclopentyl group.
The R may further have a substituent. Examples of the substituent include a halogen atom (F, Cl, Br, I), a hydroxy group, a carboxy group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a monoalkylamino group, a dialkylamino group, a monoarylamino group, and a diarylamino group.

Specific examples of the organometallic complex include, but are not limited to, tetraisopropoxytitanium, tetrakis(2-ethylhexyloxy)titanium, diisopropoxybis(ethylacetoacetate)titanium, diisopropoxybis(acetylacetonato)titanium, bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, and the following compounds.

Other compounds described in paragraphs 0078 to 0088 of WO 2018/025738 can also be used, but are not limited to these.

The content of the organometallic complex is preferably 0.1 to 30 mass% based on the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 1.0 mass% or more, further preferably 1.5 mass% or more, and particularly preferably 3.0 mass% or more. The upper limit is more preferably 25 mass% or less.
The organometallic complexes 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.

<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 high polymerizable group value and a weight-average molecular weight of 20,000 or less to the composition in place of or in addition to the crosslinking agent 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.

<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 ... Suitable examples of 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, ethyl 2-ethoxy-2-methylpropionate, etc.), 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 examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

Suitable examples of cyclic hydrocarbons include 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.

Preferred examples of 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.

From the viewpoint of improving the properties of the coating surface, it is also preferable to mix two or more types of solvents.

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 of them, is preferred. A combination 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.

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 content of the solvent 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 the above-mentioned organometallic complex, but does not include a compound having photoradical polymerization initiation ability.
The composition of the present invention preferably contains 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. Alternatively, it may be an activator that generates active radicals by reacting with a photoexcited sensitizer.

In the present invention, compounds that fall under the category of organometallic complexes are not considered to fall under the category of photosensitizers or photoradical polymerization initiators.

When the organometallic complex has photoradical polymerization initiation ability, it is also preferable that the composition of the present invention is substantially free of radical polymerization initiators other than the organometallic complex. Substantially free of radical polymerization initiators other than the organometallic complex means that the content of radical polymerization initiators other than the organometallic complex in the composition of the present invention is 5% by mass or less, preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably 0.1% by mass, based on the total mass of the organometallic complex.
In addition, when the composition of the present invention contains an organometallic complex having radical polymerization initiation ability, it is also preferable that the composition of the present invention contains the organometallic complex and a photoradical polymerization initiator. According to such an embodiment, the generation of development residues and breakage of patterns can be suppressed as described above, and the exposure sensitivity can be improved.
When the composition of the present invention contains an organometallic complex that does not have photoradical polymerization initiation ability, the composition of the present invention preferably contains a photoradical polymerization initiator. Since the composition of the present invention contains a specific resin, it is considered that the aggregation of the organometallic complex is suppressed. It is presumed that the aggregation of the organometallic complex that does not have photoradical polymerization initiation ability is suppressed, and the increase in local film plasticity due to aggregation is suppressed, and the increase in local polymerization degree at the aggregation site is also suppressed. As a result, it is presumed that the occurrence of sensitivity variation depending on the part of the film is suppressed, and the resolution is improved.
When the composition of the present invention contains an organometallic complex and a photoradical polymerization initiator, the content of the organometallic complex relative to the total content of the organometallic complex and the photoradical polymerization initiator is preferably 20 to 80 mass%, and more preferably 30 to 70 mass%.
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, organic boron compounds, 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 photoradical polymerization initiators. 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 Corporation) can be used.

As an aminoacetophenone initiator, the compounds described in JP 2009-191179 A, which have a maximum absorption 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.

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 Japanese Patent No. 6636081.

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 thioaryl groups 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 metallocene compounds or oxime compounds being even more preferred, and oxime compounds being even more preferred.

As the photoradical polymerization initiator, benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone 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, benzyl derivatives such as benzyl dimethyl ketal, etc. can also be used. 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).

The photoradical polymerization initiator may also 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 solid 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 areas of the photosensitive film, which increases the solubility of the exposed areas in a developer (e.g., an alkaline aqueous solution), thereby obtaining a positive pattern in which the exposed areas are removed by the developer.
In addition, by containing a photoacid generator and a crosslinking agent other than the radical crosslinking agent described later, for example, the crosslinking reaction of the crosslinking agent is promoted by the acid generated in the exposed area, and the exposed area is more difficult to remove by 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 sulfonates.

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 total 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 the oxime sulfonate compound 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, the following 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, an s-triazine derivative having at least one mono-, di-, or trihalogen-substituted methyl group bonded to the s-triazine ring is used, 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, azine, 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) 2-(4-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 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 the selenonium salt described in Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979), the arsonium salt described in C. S. Wen et al., Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct. (1988), and the 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), Ar ₁₁ 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), Ar ₂₁ and Ar ₂₂ 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. Z ₂₁ ^- 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), R ₃₁ , R ₃₂ , and R ₃₃ 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 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, 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 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.

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 solid 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, the total content is preferably 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, 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 JP 2012-093746 A, the compounds described in paragraphs 0022 to 0069 of JP 2013-194205 A, the compounds described in paragraphs 0026 to 0074 of JP 2013-204019 A, and the compounds described in paragraph 0052 of WO 2010/064631 A.

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.), etc.

When a photobase generator is included, its content is preferably 0.1 to 30 mass % relative to the total solid 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 crosslinking agent 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 mass% based on the total solid content of the composition of the present invention, more preferably 0.1 to 20 mass%, and even more preferably 0.5 to 15 mass%. 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 JP2013-072935A.

Among these, from the viewpoint of having little residue in the organic film and being 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 preferable, 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. nium, trifluoromethanesulfonate (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, 3-(5-(((propylsulfonyl)oxy)imino)thiophene-2(5H)-ylidene)-2-(o-tolyl)propanenitrile, and 2,2-bis(3-(methanesulfonylamino)-4-hydroxyphenyl)hexafluoropropane are preferred as thermal acid generators.

The compounds described in paragraph 0059 of JP2013-167742A are also preferred as thermal acid generators.

The content of the thermal acid generator is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more, per 100 parts by mass of the specific resin. By containing 0.01 parts by mass or more, the crosslinking reaction is promoted, and 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, the content 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.

Specific examples of compounds among the above-mentioned onium salts that are thermal base generators, or specific examples of thermal base generators other than the above-mentioned onium salts, include the following compounds.

The content of the other thermal base generator 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, 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, 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 the film strength of the obtained pattern, 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. Specific examples can be found in paragraphs 0113 to 0122 of JP 2016-027357 A, the contents of which 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 compound include polyfunctional acrylates and methacrylates such as 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. Other examples include polyfunctional (meth)acrylates 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.

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-2010-160418, JP-A-2010-129825, Japanese Patent No. 4364216, etc., 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, compounds 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, difunctional 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 Examples include Oligomer UAS-10, UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, 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 during production and excellent developability. In addition, the agent 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.

From the viewpoints 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. These can be used in a mixture of two or more kinds as required. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a formula weight of about 200 for the polyethylene glycol chain.
From the viewpoint of suppressing warpage associated with controlling the elastic modulus of the pattern, 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, the total amount is preferably 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 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, TriML-35XL, Examples include 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, and Nikalac MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.).

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

[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 curing the curable resin composition at low temperatures and suppressing warpage.

The epoxy compound preferably contains a polyethylene oxide group. This further reduces the elastic modulus and suppresses warping. The polyethylene oxide group refers to a group having 2 or more repeating ethylene oxide units, and the number of repeating units is preferably 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.), etc.

[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 B-a type benzoxazine, B-m type benzoxazine, P-d type benzoxazine, F-a type benzoxazine (all trade names, manufactured by Shikoku Kasei Corporation), 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 solid 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, the total is preferably 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 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 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.
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), 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.

<Migration Inhibitor>
The curable resin composition of the present invention preferably further contains a migration inhibitor. By containing the migration inhibitor, it is possible to effectively suppress the migration of metal ions derived from the metal layer (metal wiring) into the photosensitive film.

The migration inhibitor is not particularly limited, but examples thereof include compounds having a heterocycle (pyrrole ring, furan ring, thiophene ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), thioureas and compounds having a sulfanyl group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole and benzotriazole, and tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

Alternatively, an ion trapping agent that captures anions such as halogen ions can be used.

Other migration inhibitors that can be used include the rust inhibitors described in paragraph 0094 of JP 2013-015701 A, the compounds described in paragraphs 0073 to 0076 of JP 2009-283711 A, the compounds described in paragraph 0052 of JP 2011-059656 A, the compounds described in paragraphs 0114, 0116, and 0118 of JP 2012-194520 A, and the compounds described in paragraph 0166 of WO 2015/199219.

Specific examples of migration inhibitors include the following compounds:

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

The migration inhibitor may be one type or two or more types. When two or more types of migration inhibitors are used, it is preferable that the total is 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-nitrophenol, 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-sulfopropionyl) (4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-ol, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione ... Xyl free radical, phenothiazine, 1,1-diphenyl-2-picrylhydrazyl, dibutyldithiocarbonate copper (II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt N,N'-diphenyl-p-phenylenediamine, 2,4-di-tert-butylphenol, di-t-butylhydroxytoluene, 1,4-naphthoquinone, etc. can be suitably used. In addition, the polymerization inhibitor described in paragraph 0060 of JP2015-127817A and the compounds described in paragraphs 0031 to 0046 of WO2015/125469A can also be used.

The following compounds can also be used:

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% by mass, preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, and even more preferably 0.05 to 2.5% by mass, based on the total solid content of the curable resin composition of the present invention.

The polymerization inhibitor may be one 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, etc. Examples of the metal adhesion improver include silane coupling agents, 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.

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

Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyl Examples of the silane include pyrrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[Aluminum-based adhesion promoter]
Examples of aluminum-based adhesion promoters include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

As metal adhesion improvers, 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 also 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.

<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, etc. 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 also 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, per 100 parts by mass of the heterocycle-containing polymer precursor. By making the content equal to or greater than the above lower limit, the adhesion between the pattern and the metal layer after the heating step is good, and by making the content equal to or less than the above upper limit, the heat resistance and mechanical properties of the cured product after the heating step are 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 mass %, more preferably 0.1 to 15 mass %, and even more preferably 0.5 to 10 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 kinds.

[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.

The chain transfer agent may also be the compound described in paragraphs 0152 to 0153 of WO 2015/199219.

When the curable resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, and 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, Newkalgen 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 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, and W017 (manufactured by Yusho Co., Ltd.), and Sandet BL (manufactured by Sanyo Chemical Industries, Ltd.).

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.

The higher fatty acid derivative may also be the compound described in paragraph 0155 of WO 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. Only one type of higher fatty acid derivative may be used, or two or more types may be used. When two or more types of higher fatty acid derivatives are used, 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.
When the inorganic particles have a large average particle size, the mechanical properties of the cured film may deteriorate. When the inorganic particles have an average particle size of more than 2.0 μm, the resolution may decrease due to scattering of the 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; 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 organic titanium 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 storage stability of the composition is excellent.

〔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. 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 formula (3), ^R5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms, ^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, and k represents an integer of 1 to 4.

The compound represented by 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, which inhibits metal oxidation.

K is preferably an integer between 2 and 4, since it can act simultaneously on resin and metal materials. R7 may be an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkyl silyl group, an alkoxy silyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, -O-, -NH-, -NHNH-, or a combination thereof, and may further have a substituent. Among these, it is preferable to have an 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 the resin 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. When 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, and nickel. When multiple metals are contained, it is preferable that the total of these metals is within the above range.

Methods for reducing metal impurities unintentionally contained in the curable resin composition of the present invention include selecting raw materials with 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, lining the inside of the apparatus with polytetrafluoroethylene or the like and performing distillation under conditions that suppress 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 containers 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 in 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 to be 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.

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

The cured film of the present invention is a cured film obtained by curing the resin composition of the present invention. The cured film is preferably a patterned cured film. 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, a preferred embodiment includes an embodiment in which both the first cured film and the second cured film are films formed by curing the resin composition of the present invention. The resin composition of the present invention used to form the first cured film and the 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 sealing films, substrate materials (base films and coverlays for flexible printed circuit boards, interlayer insulating films), and the etching of patterns for insulating films for mounting applications such as those mentioned above. For these applications, reference can be made to, for example, "High-performance and Applied Technology of Polyimides" published by Science & Technology Co., Ltd. in April 2008, edited by Masaaki Kakimoto, CMC Technical Library "Basics and Development of Polyimide Materials" published in November 2011, and "Latest Polyimides: Basics and Applications" edited by the Japan Polyimide and Aromatic Polymer Research Association, 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 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. A pattern of the cured film is obtained by the exposure step and the development step.
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 resin composition to a substrate to form a film (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.

The method for producing a laminate according to a preferred embodiment of the present invention includes the method for producing a cured film according to the present invention. In the method for producing a laminate according to 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., 3 to 6 times in total). 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 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.

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

The preferred method for applying the resin composition to the substrate is coating.

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 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 photosensitive resin composition and the film thickness to be set, it is also preferable to apply the composition 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 also 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 (resin composition layer) to light. The amount of exposure is not particularly determined as long as the 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 within the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.
The exposure light preferably contains light having a wavelength of 365 nm or 405 nm, and more preferably contains light having a wavelength of 405 nm.

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 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.

The exposure method is not particularly limited as long as it is a method in which at least a part of a film (photosensitive film) made of a curable resin composition is exposed, and examples of the exposure method include exposure using a photomask and exposure by a laser direct imaging method.
In the present invention, an embodiment in which the exposure in the exposure step is performed by a laser direct imaging method is also one of the preferred embodiments.

<Developing process>
The manufacturing method of the present invention may include a development step in which the exposed film (resin composition layer) is developed (the film is developed). By performing development, the unexposed portion (non-exposed portion) is removed. The development method is not particularly limited as long as the desired pattern can be formed, 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 may 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.

The development is carried out using a developer. There are no particular limitations on the developer that can be used as long as it can remove the unexposed portions.
As the developer, a developer containing an organic solvent or an alkaline aqueous solution can be used.

In the present invention, the developer preferably contains an organic solvent with a ClogP value of -1 to 5, and more preferably contains an organic solvent with 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, Suitable examples of organic solvents include ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and cyclic hydrocarbons such as toluene, xylene, anisole, and limonene. Suitable examples of sulfoxides include dimethyl sulfoxide. Mixtures of these organic solvents are also suitable.

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

When the developer contains an organic solvent, the developer 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. The developer may also contain 100% by mass 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 the basic compound that the alkaline aqueous solution may contain include TMAH (tetramethylammonium hydroxide), KOH (potassium hydroxide), and sodium carbonate, with TMAH being preferred. 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, and 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 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 from 10 seconds to 10 minutes, more preferably from 20 seconds to 5 minutes, and even more preferably from 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, Suitable examples of the ketones include propylene glycol monopropyl ether acetate, ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene, anisole, and limonene, sulfoxides such as dimethyl sulfoxide, alcohols such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol, and amides such as N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide are given below.

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 by a paddle above the substrate, a method of supplying the rinse liquid to the substrate by a shower, and a method of continuously supplying the rinse liquid by means of a straight nozzle or the like above the substrate.
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 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 precursor of the unreacted 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. As the upper limit, it 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.

The 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 reduce the residual stress of the cured film. In addition, in the case of an oven capable of rapid heating, it is preferable to perform the 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 resin composition is applied to a substrate and then dried, this is the temperature of the film (layer) after drying, and it is preferable to gradually increase the temperature from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the 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 in 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 perform the treatment while irradiating with ultraviolet rays 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, and more preferably for 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 (resin composition layer).

The metal layer can be made of any existing metal species without any particular limitations, and examples 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 point 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) to cure the laminated 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 structure with 2 to 20 resin layers, such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, is preferred, a structure with 3 to 7 layers is more preferred, and a structure with 3 to 5 layers is even more preferred.

In the present invention, a particularly preferred embodiment is one in which, after the metal layer is provided, a cured film (resin layer) of the resin composition is further formed to cover the metal layer. Specifically, the steps may be repeated in the order of (a) film formation step, (b) exposure step, (c) development step, (e) metal layer formation step, and (d) heating step, or the steps may be repeated in the order of (a) film formation step, (b) exposure step, (c) development step, and (e) metal layer formation step, with (d) heating step provided at the end or in the middle. By alternately performing the lamination step of laminating the resin composition layer (resin layer) and the metal layer formation step, the resin composition layer (resin layer) and the metal layer can be laminated alternately.

(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 may be 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 in an aqueous hydrochloric acid solution to remove the oxide film, and then immersion in an organic surface treatment agent containing a compound having at least one amino group and thiol group, and mechanical roughening treatment using a brush, with plasma treatment being preferred, and oxygen plasma treatment using oxygen as the raw gas being 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 including the cured film or laminate of the present invention. Specific examples of semiconductor devices using the resin composition of the present invention to form an interlayer insulating film for a rewiring layer can be seen in paragraphs 0213 to 0218 and FIG. 1 of JP2016-027357A, 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 changed 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 based on mass unless otherwise specified.

Synthesis Example 1: Synthesis of Polymer A-1
23.48 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 22.27 g of 4,4'-biphthalic dianhydride (BPDA) were placed in a separable flask, 39.69 g of 2-hydroxyethyl methacrylate (HEMA) and 136.83 g of γ-butyrolactone were added, and the mixture was stirred at room temperature, and 24.66 g of pyridine was added while stirring 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 left at room temperature for 16 hours.
Next, under ice cooling, a solution of 62.46 g of dicyclohexylcarbodiimide (DCC) dissolved in 61.57 g of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring, followed by the addition of a suspension of 27.42 g of 4,4'-diaminodiphenyl ether (DADPE) in 119.73 g of γ-butyrolactone over 60 minutes while stirring. After further stirring at room temperature for a certain period of time, 7.17 g of ethyl alcohol was added and stirred for 1 hour, and then 136.83 g of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.
By lengthening the certain time, the total molar content of the cyclic imide structure and the cyclic isoimide structure in the polyimide precursor can be increased, and by shortening the certain time, the total molar content can be decreased. For example, by setting the certain time to 30 minutes, a resin having a total molar content of the cyclic imide structure and the cyclic isoimide structure in 1 g of the polyimide precursor of 0.083 mmol/g was obtained.
In the present examples and comparative examples, the above-mentioned certain time was appropriately adjusted to perform experiments using a plurality of polyimide precursors in which the total molar content of the cyclic imide structure and the cyclic isoimide structure in the polyimide precursor was changed. In each example and comparative example, the total molar content of the cyclic imide structure and the cyclic isoimide structure is shown in the "Specific structure mmol/g" column in the table.
The obtained reaction solution was added to 716.21 g of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was filtered off and dissolved in 403.49 g of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 8470.26 g of water to precipitate the polymer, and the resulting precipitate was filtered off and then vacuum dried to obtain a powdered polymer (polyimide precursor) A-1. The molecular weight of polymer A-1 was measured by gel permeation chromatography (standard polystyrene equivalent) to find that the weight average molecular weight (Mw) was 20,000.

Synthesis Example 2: Synthesis of Polymer A-2
Except for changing 23.48 g of ODPA and 22.27 g of BPDA to 46.96 g of ODPA, polymer A-2 was synthesized in the same manner as in Synthesis Example 1. In the examples, the total molar content of the cyclic imide structure and cyclic isoimide structure is shown in the column of "Specific structure mmol/g" in the table.

Synthesis Example 3: Synthesis of Polymer A-3
Except for changing 23.48 g of ODPA and 22.27 g of BPDA to 46.96 g of ODPA and changing 39.69 g of HEMA to 19.85 g of HEMA and 18.32 g of diethylene glycol monomethyl ether, polymer A-3 was synthesized in the same manner as in Synthesis Example 1. In the examples, the total molar content of the cyclic imide structure and cyclic isoimide structure is shown in the column of "Specific structure mmol/g" in the table.

Synthesis Example 4: Synthesis of Polymer A-4
In a dry reactor equipped with a stirrer, a condenser, and a flat-bottom joint with an internal thermometer, 10.65 g (50 mmol) of 4,6-dihydroxy-1,3-phenylenediamine dihydrochloride was dissolved in 85.8 g of N-methylpyrrolidone (NMP) while removing moisture. Then, 9.74 g (48 mmol) of terephthalic acid chloride dissolved in 55.0 g of NMP was added dropwise over 1 hour and stirred at 25° C. for a certain period of time.
By lengthening the above-mentioned certain time, the molar content of the benzoxazole structure in the polybenzoxazole precursor can be increased, and by shortening the time, the molar content of the benzoxazole structure in the polybenzoxazole precursor can be decreased. For example, by setting the time to 15 minutes, the molar content of the benzoxazole structure can be set to 0.373 mmol/g.
After stirring, the mixture was precipitated in 2 liters of water/methanol = 75/25 (volume ratio) and stirred at a speed of 2,000 rpm for 30 minutes. The precipitated polybenzoxazole precursor resin was removed by filtration and washed with 1.5 liters of water. The obtained resin was dried under reduced pressure at 40 ° C for 1 day to obtain A-4.

Synthesis Example 5: Synthesis of Polymer A-5
29.08 g of trimellitic anhydride was placed in a separable flask, 19.85 g of 2-hydroxyethyl methacrylate (HEMA) and 136.83 g of γ-butyrolactone were added, and the mixture was stirred at room temperature, and 24.66 g of pyridine was added while stirring 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 left at room temperature for 16 hours.
Next, under ice cooling, a solution of 62.46 g of dicyclohexylcarbodiimide (DCC) dissolved in 61.57 g of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring, followed by the addition of a suspension of 27.42 g of 4,4'-diaminodiphenyl ether (DADPE) in 119.73 g of γ-butyrolactone over 60 minutes while stirring. After further stirring at room temperature for a certain period of time, 7.17 g of ethyl alcohol was added and stirred for 1 hour, and then 136.83 g of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.
By lengthening the above-mentioned certain time, the total molar content of the cyclic imide structure and the cyclic isoimide structure in the polyamideimide precursor can be increased, and by shortening the time, the total molar content can be decreased. For example, by setting the time to 15 minutes, the molar content of the benzoxazole structure can be set to 0.104 mmol/g.
The resulting reaction solution was added to 716.21 g of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was filtered off and dissolved in 403.49 g of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 8470.26 g of water to precipitate the polymer, and the resulting precipitate was filtered off and then vacuum dried to obtain a powdered polymer (polyamideimide precursor) A-5.

<Synthesis Example 6: Synthesis of Polymer A-6>
Except for changing 23.48 g of ODPA and 22.27 g of BPDA to 44.54 g, polymer A-6 was synthesized in the same manner as in Synthesis Example 1. In the examples, the total molar content of the cyclic imide structure and cyclic isoimide structure is shown in the column of "Specific structure mmol/g" in the table.

<Synthesis Example 7: Synthesis of Polymer A-7>
Polymer A-7 was synthesized in the same manner as in Synthesis Example 1, except that 23.48 g of ODPA and 22.27 g of BPDA were changed to 46.96 g of ODPA and 39.69 g of HEMA were changed to 52.52 g of a compound represented by the following formula (7-1). In the examples, the total molar content of the cyclic imide structure and the cyclic isoimide structure is shown in the column of "Specific structure mmol/g" in the table.

<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 content of each component shown in Tables 1 to 5 is the amount (parts by mass) shown in parentheses in each column of Tables 1 to 5.
The obtained curable resin composition and comparative composition were pressure filtered using a polytetrafluoroethylene filter having a pore width of 0.8 μm.
In addition, in Tables 1 to 5, the notation "-" indicates that the composition does not contain the corresponding component.

Details of each component listed in Tables 1 to 5 are as follows:

〔resin〕
A-1 to A-7: Polymers A-1 to A-7 obtained by the above synthesis examples

[Photosensitizer (photoradical polymerization initiator)]
B-1 to B-3: Compounds having the following structure

[Organometallic Complexes]
X-1: bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium; X-2: pentamethylcyclopentadienyltitanium trimethoxide; X-3: bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluorophenyl)titanium; X-4: tetraisopropoxytitanium (manufactured by Matsumoto Fine Chemical Co., Ltd.)
X-5: Diisopropoxybis(acetylacetonato)titanium (manufactured by Matsumoto Fine Chemical Co., Ltd.)
X-6 to X-8: Compounds having the following structures:

The above X-1 and X-3 are compounds having photoradical polymerization initiation ability.

[Crosslinking Agent (Radical Crosslinking Agent)]
C-1 to C-2: Compounds having the following structures

[Polymerization inhibitors, migration suppressants]
D-1 to D-7: Compounds having the following structures

〔Additive〕
E-1 to E-6: Compounds having the following structure

[Metal adhesion improver]
F-1 to F-6: Compounds having the following structure

In the above structural formula, Me represents a methyl group and Et represents an ethyl group.

[Solvent (solvent)]
NMP: N-methyl-2-pyrrolidone EL: Ethyl lactate DMSO: Dimethyl sulfoxide

<Evaluation>
[Measurement of molar amount of cyclic structure]
For the resins used in each Example, the total molar content of cyclic imide structures and cyclic isoimide structures contained in 1 g of polyimide precursor, the molar content of benzoxazole structures contained in 1 g of polybenzoxazole precursor, and the total molar content of cyclic imide structures and cyclic isoimide structures contained in 1 g of polyamideimide precursor were measured. The measurement results are shown in the column of "specific structure mmol/g" in the table.
Specifically, 0.1 g of the polymer was dissolved in 0.9 g of deuterated DMSO and the measurement was performed using NMR. For the polyimide precursor or polyamideimide precursor, the amount of cyclic imide structure was determined from the ratio of the peak area at about 7.15 ppm to the peak area of the aromatic ring.
Similarly, the amount of cyclic isoimide structures in the polyimide precursor or polyamideimide precursor, and the amount of benzoxazole structures in the polybenzoxazole precursor were specified.

[Resolution evaluation]
In each of the Examples and Comparative Examples, the prepared curable resin composition or comparative composition was applied onto a silicon wafer by spin coating. The silicon wafer was dried on a hot plate at 100° C. for 5 minutes to form a curable resin composition layer having a uniform thickness of 20 μm on the silicon wafer.
In the examples in which the exposure condition is marked "M", the curable resin composition layer on the silicon wafer was exposed using a stepper. Exposure was performed using light having a wavelength shown in the "Exposure wavelength nm" column in the table, using a fuse box photomask with 1 μm intervals from 5 μm to 25 μm. The exposure amount was set to the amount that minimized the minimum line width described below.
In the examples in which the exposure condition is marked "D", exposure was performed using a direct exposure device (ADTECH DE-6UH III). Exposure was performed by laser direct imaging exposure at a wavelength of 405 nm such that the exposed portion became a line portion in a line and space pattern with 1 μm intervals from 5 μm to 25 μm. The exposure amount was set to the amount that minimized the minimum line width described below.
The exposed curable resin composition layer was developed with cyclopentanone for 60 seconds, and then rinsed with PGMEA (propylene glycol monomethyl ether acetate).
In the pattern obtained after development, the line width of the line pattern with the smallest line width among the line patterns where the silicon wafer is exposed between the line patterns was defined as the "minimum line width" and evaluated according to the following evaluation criteria. The smaller the line width, the better the resolution, which indicates that, for example, the width of the metal wiring formed in the subsequent plating process can be made finer, and therefore is a preferable result. The measurement limit is 5 μm. The evaluation results are shown in the "resolution" column in the table.
-Evaluation criteria-
A: The minimum line width was 5 μm or more and less than 8 μm.
B: The minimum line width was 8 μm or more and less than 10 μm.
C: The minimum line width was 10 μm or more and less than 12 μm.
D: The minimum line width was 12 μm or more.

[Exposure Sensitivity Evaluation]
A curable resin composition layer having a uniform thickness of 20 μm was formed on a silicon wafer by the same method as in the above-mentioned resolution evaluation.
In the examples in which the exposure condition is marked "M", the curable resin composition layer on the silicon wafer was exposed by a stepper using a photomask having a masked portion (examples marked "negative" in the development condition column in the table) or a non-masked portion (examples marked "positive" in the current condition column in the table) with a diameter of 15.0 μm. The exposure wavelength is shown in the table as "Exposure wavelength nm". The exposure dose was changed in increments of 50 mJ/ ^cm2 in the range of 50 to 500 mJ/ ^cm2 .
In the examples in which the exposure condition is marked "D", laser direct imaging exposure was performed using a direct exposure device (ADTECH DE-6UH III). The exposure wavelength was 405 nm, and exposure was performed so as to form a non-exposed portion having a diameter of 15.0 μm. The exposure dose was changed in ^increments of 50 mJ/cm2 within the range of 50 to 500 mJ/ ^cm2 .
The sensitivity was evaluated according to the following evaluation criteria from the minimum exposure dose at which a hole pattern with a bottom diameter of 15.0 μm was formed. The smaller the minimum exposure dose (the higher the sensitivity), the more preferable it is, and the better the exposure sensitivity is. The evaluation results are shown in the "Sensitivity" column in the table.
-Evaluation criteria-
A: The minimum exposure amount was less than 100 mJ/cm ² .
B: The minimum exposure amount was 100 mJ/cm ² or more and less than 150 mJ/cm ² .
C: The minimum exposure amount was 150 mJ/cm ² or more.

From the above results, it is apparent that the curable resin composition of the present invention has excellent resolution.
The polyimide precursors contained in the comparative compositions according to Comparative Examples 1 to 4 have a total molar content of cyclic imide structures and cyclic isoimide structures contained in 1 g of the polyimide precursor of less than 0.08 mmol/g.
The polyimide precursor contained in the comparative composition according to Comparative Example 5 has a total molar content of cyclic imide structures and cyclic isoimide structures contained in 1 g of the polyimide precursor exceeding 1.68 mmol/g.
The polybenzoxazole precursor contained in the comparative composition according to Comparative Example 6 has a molar content of the benzoxazole structure contained in 1 g of the polybenzoxazole precursor of less than 0.22 mmol/g.
The polybenzoxazole precursor contained in the comparative composition according to Comparative Example 7 has a molar content of the benzoxazole structure contained in 1 g of the polybenzoxazole precursor exceeding 3.97 mmol/g.
The polyamideimide precursor contained in the comparative composition according to Comparative Example 8 has a total molar content of cyclic imide structures and cyclic isoimide structures contained in 1 g of the polyimide precursor exceeding 1.186 mmol/g.
The polyamideimide precursor contained in the comparative composition according to Comparative Example 9 has a total molar content of cyclic imide structures and cyclic isoimide structures contained in 1 g of the polyamideimide precursor of less than 0.062 mmol/g.
It can be seen that when these comparative compositions are used, the resolution is poor.

<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 photosensitive film 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 film was heated at 100°C for 4 minutes. After the heating, the film 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 120 minutes 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 having at least one of a cyclic imide structure and a cyclic isoimide structure, a polybenzoxazole precursor having a benzoxazole structure, and a polyamideimide precursor having at least one of a cyclic imide structure and a cyclic isoimide structure, and
Contains organometallic complexes,
the total molar content of the cyclic imide structure and the cyclic isoimide structure contained in 1 g of the polyimide precursor is 0.08 to 1.68 mmol/g;
the molar amount of the benzoxazole structure contained in 1 g of the polybenzoxazole precursor is 0.22 to 3.97 mmol/g;
the total molar content of the cyclic imide structure and the cyclic isoimide structure contained in 1 g of the polyamideimide precursor is 0.062 to 1.186 mmol/g;
A curable resin composition. The curable resin composition according to claim 1, further comprising a photopolymerization initiator. The curable resin composition according to claim 1 or 2, wherein the photopolymerization initiator is an oxime compound. The curable resin composition according to any one of claims 1 to 3, further comprising a crosslinking agent. The curable resin composition according to any one of claims 1 to 4, wherein the organometallic complex is a metallocene compound. The curable resin composition according to any one of claims 1 to 5, wherein the metal contained in the organometallic complex is at least one metal selected from the group consisting of titanium, zirconium, and hafnium. The curable resin composition according to any one of claims 1 to 6, wherein the organometallic complex has photoradical polymerization initiation ability. The curable resin composition according to any one of claims 1 to 7, which is used to form a photosensitive film to be subjected to negative development. The curable resin composition according to any one of claims 1 to 8, which is used to form an interlayer insulating film for a rewiring layer. A cured film obtained by curing the curable resin composition according to any one of claims 1 to 9. A laminate comprising two or more layers of the cured film according to claim 10, 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 9 to a substrate to form a film. The method for producing the cured film according to claim 12, comprising an exposure step of exposing the film to light and a development step of developing the film. The method for producing a cured film according to claim 13, wherein the exposure light used for the exposure contains light having a wavelength of 405 nm. The method for producing a cured film according to claim 13 or 14, wherein the exposure is by a laser direct imaging method. The method for producing the cured film according to any one of claims 12 to 15, comprising a heating step of heating the film at 50 to 450°C. A semiconductor device comprising the cured film according to claim 10 or the laminate according to claim 11.