WO2025205940A1 - Resin composition, cured product, laminate, production method for cured product, production method for laminate, production method for semiconductor device, semiconductor device, and resin - Google Patents

Abstract

Provided are: a resin composition for use in the formation of an insulating film, said resin composition containing a polymerization initiator and a resin that is selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles, and polybenzoxazole precursors and contains a polymerizable group and an alkenyl group in which a hydrogen atom is optionally substituted with a monovalent substituent group; a cured product obtained by curing the resin composition and a production method therefor; a laminate including the cured product and a production method therefor; a semiconductor device and a production method therefor; and a novel resin.

Description

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

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

BACKGROUND ART Nowadays, resin materials produced from resin compositions containing resins are being utilized in various fields.
For example, heterocycle-containing polymers such as polyimides have excellent heat resistance and insulating properties, and are therefore used in a variety of applications. Examples of such applications include, but are not limited to, insulating films, sealing materials, or protective films for semiconductor devices used for packaging. They are also used as base films or coverlays for flexible substrates.

For example, in the above-mentioned applications, heterocycle-containing polymers such as polyimides are used in the form of resin compositions containing polyimides or polyimide precursors.
Such a 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 carried out to form a cured product on the substrate.
Since the resin composition can be applied by a known coating method, etc., it can be said that the resin composition has excellent adaptability in manufacturing, for example, there is a high degree of freedom in designing the shape, size, application position, etc. of the applied resin composition when it is applied. In addition to the high performance of heterocycle-containing polymers such as polyimides, from the viewpoint of such excellent adaptability in manufacturing, industrial application development of the above-mentioned resin composition is expected to become increasingly widespread.

For example, Patent Document 1 describes a circuit board that includes a conductor that has been pre-formed to have a certain pattern, and a resin substrate that has been formed by transferring the conductor to the surface of a thermosetting resin and then curing the thermosetting resin, characterized in that the surface of the conductor and the surface of the resin substrate are flush with each other, and the thermosetting resin is in powder form.

International Publication No. 2008/044382

In cured products containing polyimide, as wiring patterns become finer, there is a demand to prevent defects by using resin-containing components that are less likely to expand.

The present invention aims to provide a resin composition that can give a cured product that has excellent adhesion to metals, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device that includes the method for producing the cured product, and a semiconductor device that includes the cured product.
Another object of the present invention is to provide a novel resin.

Examples of typical embodiments of the present invention are given below.
<1> A resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor, the resin having an alkynyl group in which a hydrogen atom may be substituted with a monovalent substituent, and a polymerizable group;
a polymerization initiator,
A resin composition used to form an insulating film.
<2> The resin composition according to <1>, wherein the alkynyl group is a group in which one hydrogen atom has been removed from an internal alkyne.
<3> The resin composition according to <1> or <2>, wherein the resin is selected from the group consisting of polyimide and polybenzoxazole.
<4> The resin composition according to any one of <1> to <3>, wherein the alkynyl group is present in a side chain or at a terminal of a main chain of the resin.
<5> The resin composition according to any one of <1> to <4>, wherein the resin has a group represented by the following formula (B-1) as the alkynyl group-containing group:
In formula (B-1), R ¹ represents a divalent linking group, Z ¹ represents a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms or a silicon atom, when Z ¹ is the alkylene group, n is 1, and R ² represents a hydrogen atom or a monovalent organic group, when Z ¹ is the silicon atom, n is 3, and each R ² independently represents a monovalent organic group, and * represents a bonding site to another structure.
<6> The resin composition according to any one of <1> to <5>, wherein the resin has an alkynyl group value of 0.01 to 1.0 mmol/g.
<7> The resin composition according to any one of <1> to <6>, wherein the resin has a polymerizable group value of 0.2 to 4.0 mmol/g.
<8> The resin composition according to any one of <1> to <7>, wherein when the resin composition is used to form a film-like cured product having a film thickness of 10 μm, the cured product has a transmittance of 15% or more at a wavelength of 365 nm.
<9> The resin composition according to any one of <1> to <8>, wherein the resin contains a repeating unit represented by the following formula (1-1):
In formula (1-1), ^X1 represents an organic group having 4 or more carbon atoms, ^Y1 represents an organic group having 4 or more carbon atoms, ^R1 each independently represents a structure represented by formula (R-1) below, m represents an integer of 0 to 4, n represents an integer of 0 or more, and n+m is an integer of 1 or more.
In formula (R-1), L ¹ represents a linking group having a valence of a1+1, A ¹ represents a polymerizable group, a1 represents an integer of 1 or more, and * represents a bonding site with X ¹ or Y ¹ in formula (1-1).
<10> The resin composition according to <9>, wherein at least one of A ¹ in formula (R-1) in formula (1-1) is a vinylphenyl group.
<11> The resin composition according to <9> or <10>, wherein ^X1 and ^Y1 in formula (1-1) each include a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of the following formulas (V-1) to (V-4):
In formula (V-2), R 1 and ^X1 each independently represent a hydrogen atom, an alkyl group or a halogenated alkyl group.
In formula (V-3), R 1 ^X2 and R ^{1 X3} each independently represent a hydrogen atom or a substituent, and R ^{1 X2} and R 1 ^X3 may be bonded to form a ring structure.
<12> The resin composition according to any one of <1> to <11>, wherein the resin has a radical polymerizable group value of 0.2 to 3.0 mmol/g.
<13> The resin composition according to any one of <1> to <12>, containing a metal or a salt thereof, or a metal complex.
<14> The resin composition according to any one of <1> to <13>, which contains a metal complex.
<15> The resin composition according to any one of <1> to <14>, further comprising a polymerizable compound having a melting point of 60°C or lower.
<16> The resin composition according to any one of <1> to <15>, further comprising an azole compound and a silane coupling agent.
<17> The resin composition according to any one of <1> to <16>, containing a solvent having a boiling point of 100 to 260°C at 1 atmosphere.
<18> The resin composition according to <17>, wherein the content of the solvent having a boiling point of 100 to 260°C is 40 mass% or more relative to the total mass of the composition.
<19> The resin composition according to <17> or <16>, comprising two or more solvents having a boiling point of 100 to 260°C.
<20> The resin composition according to any one of <1> to <19>, which is used for forming an interlayer insulating film for a rewiring layer.
<21> A cured product obtained by curing the resin composition according to any one of <1> to <20>.
<22> A laminate comprising two or more layers made of the cured product according to <21>, and a metal layer between any two adjacent layers made of the cured product.
<23> A method for producing a cured product, comprising a film-forming step of applying the resin composition according to any one of <1> to <20> onto a substrate to form a film.
<24> The method for producing a cured product according to <23>, comprising: an exposure step of selectively exposing the film to light; and a development step of developing the film with a developer to form a pattern.
<25> A method for producing a cured product according to <23> or <24>, comprising a heating step of heating the film at 50 to 450°C.
<26> A method for producing a laminate, comprising the method for producing a cured product according to any one of <23> to <25>.
<27> A method for producing a semiconductor device, comprising the method for producing a cured product according to any one of <23> to <25>.
<28> A semiconductor device comprising the cured product according to <21>.
<29> A copolymer having a repeating unit represented by formula (1-1) and a group represented by formula (B-1):
resin.
In formula (1-1), ^X1 represents an organic group having 4 or more carbon atoms, ^Y1 represents an organic group having 4 or more carbon atoms, ^R1 each independently represents a structure represented by formula (R-1) below, m represents an integer of 0 to 4, n represents an integer of 0 or more, and n+m is an integer of 1 or more.
In formula (R-1), L ¹ represents a linking group having a valence of a1+1, A ¹ represents a polymerizable group, a1 represents an integer of 1 or more, and * represents a bonding site with X ¹ or Y ¹ in formula (1-1).
In formula (B-1), R ¹ represents a divalent linking group, Z ¹ represents a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms or a silicon atom, when Z ¹ is the alkylene group, n is 1, and R ² represents a hydrogen atom or a monovalent organic group, when Z ¹ is the silicon atom, n is 3, and each R ² independently represents a monovalent organic group, and * represents a bonding site to another structure.

According to the present invention, there are provided a resin composition that can give a cured product that has excellent adhesion to metals, a cured product obtained by curing the resin composition, a laminate that includes the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device that includes the method for producing the cured product, and a semiconductor device that includes the cured product.
The present invention also provides a novel resin.

The main embodiments of the present invention will be described below, but 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 and upper limits, respectively.
In this specification, the term "step" includes not only an independent step but also a step that cannot be clearly distinguished from other steps, so long as the intended effect of the step can be achieved.
In the description of groups (atomic groups) in this specification, when a notation does not specify whether they are substituted or unsubstituted, it encompasses both groups (atomic groups) that have no substituents and groups (atomic groups) that have substituents. For example, the term "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 typified by excimer lasers, 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 term "total solids content" refers to the total mass of all components of the composition excluding the solvent, and the term "solids concentration" refers to the mass percentage of the components excluding the solvent relative to the total mass of the composition.
In this specification, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values measured using gel permeation chromatography (GPC) and are defined as polystyrene equivalent values. In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) can be determined, for example, using an 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 (all manufactured by Tosoh Corporation) connected in series. Unless otherwise specified, these molecular weights are measured using NMP (N-methyl-2-pyrrolidone) as the eluent. However, if NMP is not suitable as an eluent, such as when the solubility is low, THF (tetrahydrofuran) can also be used. Furthermore, unless otherwise specified, detection in GPC measurement is performed using a UV (ultraviolet) ray (ultraviolet) detector with a wavelength of 254 nm.
In this specification, when the positional relationship of each layer constituting a laminate is described as "up" or "down," it is sufficient that there is another layer above or below the reference layer among the multiple layers being considered. In other words, a third layer or element may be interposed between the reference layer and the other layer, and the reference layer and the other layer do not need to be in contact. Unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "up," or, if a resin composition layer is present, the direction from the substrate to the resin composition layer is referred to as "up," and the opposite direction is referred to as "down." Note that such vertical directions are defined for convenience in this specification, and in actual embodiments, the "up" direction in this specification may differ from the vertical upward direction.
In this specification, unless otherwise specified, a 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 atmospheric pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH.
As used herein, combinations of preferred embodiments are more preferred embodiments.

(Resin composition)
The resin composition of the present invention (hereinafter also simply referred to as "resin composition") is a resin composition used for forming an insulating film, which contains a resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor, and which has an alkynyl group in which a hydrogen atom may be substituted with a monovalent substituent and a polymerizable group, and a polymerization initiator.
Hereinafter, a resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor, which has an alkynyl group in which a hydrogen atom may be substituted with a monovalent substituent, and a polymerizable group, will also be simply referred to as a "specific resin."

The resin composition of the present invention is preferably used to form a photosensitive film that is subjected to exposure and development, and more preferably used to form a photosensitive film that is subjected to exposure and development using a developer containing an organic solvent.
The resin composition of the present invention can be used to form, for example, an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, etc., and is preferably used to form an interlayer insulating film for a rewiring layer.
The resin composition of the present invention is preferably used to form a photosensitive film to be subjected to negative development.
In the present invention, negative development refers to development in which the unexposed areas are removed by development, and positive development refers to 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 product described below can be used.

The resin composition of the present invention gives a cured product that has excellent adhesion to metals (preferably copper or copper-containing alloys).
The mechanism by which the above effects are obtained is unknown, but is speculated as follows.
The present inventors have found that when a cured product is formed using a resin composition so as to be in contact with metal (substrate, wiring, etc.), if moisture is contained in the cured product, the metal may be oxidized by the action of the moisture, and the adhesion between the cured product and the metal may be reduced.
Therefore, the present inventors conducted extensive research and found that the adhesion can be increased by using the above-mentioned specific resin having a polymerizable group and an alkynyl group whose hydrogen atom may be substituted with a monovalent substituent.
Although the mechanism by which the above-mentioned effect is obtained is unclear, it is presumed that the alkynyl group in which the hydrogen atom may be substituted with a monovalent substituent reacts with the moisture in the film, resulting in a decrease in moisture in the film, which in turn inhibits oxidation of the metal and increases adhesion.
Furthermore, it is believed that the specific resin having a polymerizable group improves the film Tg and heat resistance, thereby increasing adhesion.
Furthermore, since the specific resin has a polymerizable group, a crosslinked structure is formed between the specific resins themselves or between the specific resin and a polymerizable compound, etc., described later, which inhibits water penetration, and therefore, due to a synergistic effect with the above-mentioned alkynyl group, it is thought that metal oxidation can be further inhibited. Furthermore, it has been found that, due to the same mechanism as above, the amount of water in the film can be reduced when the cured product is used, and therefore the dielectric loss tangent of the cured product also decreases.
Furthermore, the action of moisture, halogen atoms, etc. in the cured product can accelerate decomposition of the resin main chain and corrosion of copper in the substrate, wiring, etc., resulting in the formation of voids between the metal and the cured product under high-temperature conditions, i.e., reduced insulation reliability.
The present inventors have found that when the resin has a polymerizable group and an alkynyl group, the resin has excellent insulation reliability.
Although the mechanism by which the above effect is obtained is unknown, it is presumed that the alkynyl groups react with halogen ions or halogen compounds and moisture in the film, reducing these and thereby improving insulation reliability.
In addition, it is believed that the occurrence of voids under high humidity conditions is also suppressed by the same mechanism as above.

Patent Document 1 does not describe any resin compositions containing resins that fall under the category of specific resins.

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

<Specific resin>
The resin composition of the present invention contains a resin (specific resin) selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor, which has an alkynyl group in which a hydrogen atom may be substituted with a monovalent substituent, and a polymerizable group.

The resin composition of the present invention preferably contains, as the specific resin, a resin selected from the group consisting of polyimide and polybenzoxazole, and more preferably contains polyimide from the viewpoint of suppressing shrinkage during curing, etc.
When the specific resin is a polyimide, the specific resin preferably has a repeating unit represented by the formula (1-1) described below.

In this specification, polyimide refers to a resin having a repeating unit containing an imide structure in the molecular chain, and is preferably a resin having a repeating unit containing an imide ring structure in the molecular chain.
Furthermore, when the polyimide is a linear resin, the polyimide is preferably a resin having a repeating unit containing an imide structure in the main chain, and more preferably a resin having a repeating unit containing an imide ring structure in the main chain.
In this specification, the term "main chain" refers to the relatively longest bonded chain in a resin molecule, and the term "side chain" refers to any other bonded chain.
In this specification, the imide structure refers to a structure represented by *-C(=O)N(-*)C(=O)-*, where * represents a bonding site to another structure, preferably a bonding site to a carbon atom, and more preferably a bonding site to a quaternary carbon atom.
In this specification, the imide ring structure refers to a ring structure containing two carbon atoms and all of the nitrogen atoms in the imide structure as ring members. The imide ring structure is preferably a five-membered ring.
The polyimide may be a so-called polyamideimide, which has an amide bond in the molecular chain in addition to the imide structure. In this specification, the amide bond refers to a structure represented by *-C(=O)N(-#)-*, where * represents a bonding site to another structure, preferably a bonding site to a carbon atom, and more preferably a bonding site to a quaternary carbon atom. Furthermore, # represents a bonding site to another structure, preferably a bonding site to a hydrogen atom or a carbon atom, and more preferably a bonding site to a hydrogen atom.

In the present invention, the polyimide precursor refers to a resin that changes its chemical structure in response to an external stimulus to become a polyimide. A resin that changes its chemical structure in response to heat to become a polyimide is preferred, and a resin that changes its chemical structure in response to heat to become a polyimide by forming a ring structure is more preferred.
The preferred embodiments of the polyimide to be formed are as described above.

In the present invention, polybenzoxazole refers to a resin having a repeating unit containing a benzoxazole structure in the molecular chain.
When the specific resin is polybenzoxazole, the specific resin preferably has a repeating unit represented by formula (X) described below.
When the polybenzoxazole is a linear resin, the polybenzoxazole is preferably a resin having a repeating unit containing a benzoxazole structure in the main chain.
In the present invention, the benzoxazole structure refers to a structure represented by the following formula (PBO-1).
In formula (PBO-1), * represents a bonding site to other structures.

In the present invention, the polybenzoxazole precursor refers to a resin that undergoes a change in chemical structure in response to an external stimulus to become polybenzoxazole. A resin that undergoes a change in chemical structure in response to heat to become polybenzoxazole is preferred, and a resin that undergoes a ring-closing reaction in response to heat to form a ring structure to become polybenzoxazole is more preferred.
The preferred embodiments of the polybenzoxazole to be formed are as described above.

[Alkynyl group in which a hydrogen atom may be substituted with a monovalent substituent]
The specific resin contains an alkynyl group in which a hydrogen atom may be substituted with a monovalent substituent.
Examples of the substituent on the alkynyl group include a trialkylsilyl group.
The alkynyl group preferably has 2 to 20 carbon atoms (excluding carbon atoms contained in the substituent), and more preferably has 2 to 15 carbon atoms.
The alkynyl group may be linear, branched, cyclic, or a combination thereof, but is preferably linear.

The alkynyl group is preferably a group in which one hydrogen atom has been removed from an internal alkyne.
The internal alkyne refers to an alkyne in which both of the two carbon atoms forming the triple bond are bonded to groups other than hydrogen atoms, and is preferably an alkyne in which both of the two carbon atoms forming the triple bond are bonded to carbon atoms, or one of the carbon atoms is bonded to a silicon atom and the other is bonded to a carbon atom.
Specifically, the alkynyl group may be a group containing a structure represented by the following formula (AL-1) or a group containing a structure represented by the following formula (AL-2), but is preferably a group containing a structure represented by the following formula (AL-1):
In formula (AL-1), * represents a bonding site to another structure other than a hydrogen atom, and # represents a bonding site to a hydrogen atom or another structure.
In formula (AL-2), * represents a bonding site to another structure other than a hydrogen atom.

The alkynyl group is preferably present on a side chain or at the end of the main chain of the resin, and more preferably at the end of the main chain.
The presence of the alkynyl group in the side chain or at the end of the main chain further improves adhesion to metals. Because the side chain or the end of the main chain has higher mobility than the inside of the main chain, it is thought that the reactivity with water and halogen ions, which can cause corrosion of metals, is improved, making it easier to improve adhesion.

The specific resin preferably has a group represented by the following formula (B-1) as the alkynyl group-containing group.
The specific resin preferably has a group represented by the following formula (B-1) on a side chain or at a main chain terminal, more preferably at a main chain terminal.
In formula (B-1), R ¹ represents a divalent linking group, Z ¹ represents a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms or a silicon atom, when Z ¹ is the alkylene group, n is 1, and R ² represents a hydrogen atom or a monovalent organic group, when Z ¹ is the silicon atom, n is 3, and each R ² independently represents a monovalent organic group, and * represents a bonding site to another structure.

In formula (B-1), R ¹ is preferably a hydrocarbon group, more preferably an aromatic hydrocarbon group or an alkylene group.
The aromatic hydrocarbon group is preferably a phenylene group or a naphthylene group, more preferably a p-phenylene group or a 1,4-naphthylene group.
The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 6 carbon atoms. The alkylene group may be linear, branched, cyclic, or may have a structure represented by a combination of these, but is preferably linear.

In formula (B-1), ^Z1 is preferably an alkylene group having 1 to 25 carbon atoms or a silicon atom, and more preferably an alkylene group having 2 to 20 carbon atoms or a silicon atom. The alkyl group in ^Z1 may be substituted with a known substituent such as a halogen atom or an aryl group.

In formula (B-1), when Z ¹ is a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, R ² is preferably a hydrogen atom, an alkoxy group, an aryl group or an aryloxy group, more preferably a hydrogen atom.
In formula (B-1), when ^Z1 is a silicon atom, ^R2 is preferably an alkyl group, an alkoxy group, an aryl group, or an aryloxy group, more preferably an alkyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.

In formula (B-1), * preferably represents a bonding site with an oxygen atom or a nitrogen atom.

Specific examples of the group represented by formula (B-1) are shown below, but the present invention is not limited to these.

The content of the alkynyl group (alkynyl group value) relative to the total mass of the specific resin is preferably 0.01 to 1.0 mmol/g, more preferably 0.02 to 0.8 mmol/g, and even more preferably 0.05 to 0.6 mmol/g.
The alkynyl group value can be calculated by, for example, using tetramethylsilane as a standard substance, from the ratio of the integrated intensity of the peak at around 0.1 ppm or around 1.7 to 3.3 ppm attributable to the alkynyl group in ^{a 1} H-NMR chart to the integrated intensity of the peak attributable to the standard substance, the amount of the standard substance, and the amount of the specific resin, and from the molar amount of the alkynyl group in the specific resin.
The molar amounts of other structures can also be determined by calculating the integrated intensity of the peaks corresponding to each structure.

[Polymerizable group]
The specific resin preferably has a polymerizable group.
Examples of the polymerizable group include a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, and a benzoxazolyl group, with a group having an ethylenically unsaturated bond being preferred.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group.
Among these, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group is preferred, and a (meth)acryloyl group is more preferred from the viewpoint of reactivity. Furthermore, a vinylphenyl group or a maleimide group is preferred from the viewpoint of reducing the dielectric loss tangent.
From the viewpoint of adhesiveness, a hydrophobic vinylphenyl group is preferred.

The content of the polymerizable group relative to the total mass of the specific resin (polymerizable group value) is preferably from 0.2 to 4.0 mmol/g, more preferably from 0.3 to 3.5 mmol/g, and even more preferably from 0.4 to 3.0 mmol/g.
In particular, the content of the radically polymerizable group relative to the total mass of the specific resin (radical polymerizable group value) is preferably 0.2 to 3.0 mmol/g, more preferably 0.3 to 2.8 mmol/g, and even more preferably 0.4 to 2.6 mmol/g.
For example, the content of vinylphenyl groups in the resin in the composition can be calculated by the following method: The calculation method is similar for other polymerizable groups and radically polymerizable groups.
1 g of the composition is added to 50 g of methanol or water to cause crystallization, and the specific resin is precipitated and filtered. The residue is recovered and dissolved in 3.0 g of THF (tetrahydrofuran), and this is added to 50 g of methanol or water to cause crystallization, filtered, and dried at 40°C for 20 hours.
0.1 g of the specific resin dried above is dissolved in 0.9 g of deuterated dimethyl sulfoxide, and then measured by ¹ H-NMR to calculate the amount of vinylphenyl groups. The number of ¹ H-NMR measurements is set to 640.
For example, using tetramethylsilane as a reference substance, the molar amount of vinylphenyl groups in the specific resin can be calculated from the ratio of the integrated intensity of the peak at around 5.0 to 7.0 ppm derived from the vinylphenyl group in ^{the 1H} -NMR chart to the integrated intensity of the peak derived from the reference substance, the amount of the reference substance, and the amount of the specific resin.
The molar amounts of other structures can also be determined by calculating the integrated intensity of the peaks corresponding to each structure.

[Repeating unit represented by formula (1-1)]
The specific resin preferably has a repeating unit represented by formula (1-1).
In formula (1-1), ^X1 represents an organic group having 4 or more carbon atoms, ^Y1 represents an organic group having 4 or more carbon atoms, ^R1 each independently represents a structure represented by formula (R-1) below, m represents an integer of 0 to 4, n represents an integer of 0 or more, and n+m is an integer of 1 or more.
In formula (R-1), L ¹ represents a linking group having a valence of a1+1, A ¹ represents a polymerizable group, a1 represents an integer of 1 or more, and * represents a bonding site with X ¹ or Y ¹ in formula (1-1).

-X ¹ -
^X1 has 4 or more carbon atoms, preferably 4 to 50 carbon atoms, and more preferably 4 to 40 carbon atoms.
In formula (1-1), ^X1 preferably represents an organic group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-1) to (V-10) below.
When X ¹ is an organic group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-1) to (V-10), the chemical resistance and flatness of the cured product are improved.
Furthermore, when ^X1 is an organic group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-1) to (V-5), effects such as suppression of development residues, lowering of the dielectric constant of the cured product, and reduction of the thermal expansion coefficient can be obtained.
The organic group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-6) to (V-10) provides the following effects: the pattern of the cured product is less likely to become tapered due to improved ultraviolet light transmittance; and the tolerance for the exposure dose is wide.
In formula (V-2), R 1 and ^X1 each independently represent a hydrogen atom, an alkyl group or a halogenated alkyl group.
In formula (V-3), R 1 ^X2 and R ^{1 X3} each independently represent a hydrogen atom or a substituent, and R ^{1 X2} and R 1 ^X3 may be bonded to form a ring structure.
In formula (V-8), R ^{1 and X5} each independently represent a hydrogen atom, an alkyl group or a halogenated alkyl group.

In formula (V-2), R and ^X1 are each independently preferably an alkyl group or a halogenated alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group or a trifluoromethyl group. A halogenated alkyl group refers to an alkyl group in which at least one hydrogen atom has been substituted with a halogen atom. The halogen atom is preferably F or Cl, and more preferably F.
In formula (V-3), it is preferable that R ^X2 and R ^X3 each independently represent a hydrogen atom. When R ^X2 and R ^X3 combine to form a ring structure, the structure formed by combining R ^X2 and R ^X3 is preferably a single bond, -O-, or -C(R) ₂ -, more preferably -O- or -C(R) ₂ -, and even more preferably -O-. R represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom.
In formula (V-8), R and ^X5 are each independently preferably an alkyl group or a halogenated alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group or a trifluoromethyl group. A halogenated alkyl group refers to an alkyl group in which at least one hydrogen atom has been substituted with a halogen atom. The halogen atom is preferably F or Cl, and more preferably F.

When X ¹ is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-1), X ¹ is preferably a group represented by the following formula (V-1-1). In the following formula, * represents the bonding site to which X ¹ in formula (1-1) bonds with the four carbonyl groups, and n1 represents an integer of 0 to 5, and is also preferably an integer of 1 to 5. Furthermore, the hydrogen atom in the following structure may be further substituted by R ¹ in formula (1-1) or a known substituent such as a hydrocarbon group.

When ^X1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-2), ^X1 is preferably a group represented by formula (V-2-1) or formula (V-2-2) below, and from the viewpoint of lowering the amine value in the resin, a group represented by formula (V-2-2) is preferred. In this specification, a bond crossing a side of a ring structure means substituting one of the hydrogen atoms in the ring structure. In the following formulas, L ^X1 represents a single bond or —O—, and * represents the bonding site with the four carbonyl groups to which ^X1 in formula (1-1) is bonded. The definition and preferred embodiments of R ^X1 are as described above. The hydrogen atoms in these structures may be further substituted with R ¹ in formula (1-1) or a known substituent such as a hydrocarbon group.

When X ¹ is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-3), X ¹ is preferably a group represented by formula (V-3-1) or formula (V-3-2) below, and from the viewpoint of reducing the dielectric constant of the cured product, a group represented by formula (V-3-2) is preferred. In the following formulas, * represents the bonding site to the four carbonyl groups to which X ¹ in formula (1-1) is bonded. The definitions and preferred embodiments of R ^X2 and R ^X3 are as described above. The hydrogen atoms in these structures may be further substituted with R ¹ in formula (1-1) or a known substituent such as a hydrocarbon group.

When X ¹ is a group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by formula (V-4), X ¹ is preferably a group represented by the following formula (V-4-1).
In the following formula (V-4-1), * represents the bonding site of ^X1 in formula (1-1) with the four carbonyl groups, and n1 represents an integer of 0 to 5. Furthermore, the hydrogen atoms in formula (V-4-1) may be further substituted with ^R1 in formula (1-1) or known substituents such as hydrocarbon groups. Examples of known substituents include alkyl groups, halogenated alkyl groups, and halogen atoms. However, it is also preferable that none of the hydrogen atoms in the structure represented by (V-4-1) are substituted.

When X ¹ is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-5), X ¹ is preferably a group represented by the following formula (V-5-1). In the following formula, * represents the bonding site to which X ¹ in formula (1-1) bonds with the four carbonyl groups. In addition, the hydrogen atom in formula (V-5-1) may be further substituted with R ¹ in formula (1-1) or a known substituent such as a hydrocarbon group. Examples of the known substituent include an alkyl group, a halogenated alkyl group, and a halogen atom. However, it is also preferable that none of the hydrogen atoms in the structure represented by (V-5-1) are substituted.

When X ¹ is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-6), X ¹ is preferably a group represented by the following formula (V-6-1). In the following formula, * represents the bonding site to which X ¹ in formula (1-1) bonds with the four carbonyl groups. In addition, the hydrogen atoms in the following structure may be further substituted by R ¹ in formula (1-1) or a known substituent such as a hydrocarbon group.

When X ¹ is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-7), X ¹ is preferably a group represented by the following formula (V-7-1). In the following formula, * represents the bonding site to which X ¹ in formula (1-1) bonds with the four carbonyl groups. In addition, the hydrogen atoms in the following structure may be further substituted by R ¹ in formula (1-1) or a known substituent such as a hydrocarbon group.

When X ¹ is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-8), X ¹ is preferably a group represented by the following formula (V-8-1). In the following formula, * represents the bonding site to the four carbonyl groups to which X ¹ in formula (1-1) is bonded. The definition and preferred embodiments of R ^X5 are as described above. In addition, the hydrogen atom in the following structure may be further substituted by R ¹ in formula (1-1) or a known substituent such as a hydrocarbon group.

When X ¹ is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-9), X ¹ is preferably a group represented by the following formula (V-9-1). In the following formula, * represents the bonding site to which X ¹ in formula (1-1) bonds with the four carbonyl groups. In addition, the hydrogen atoms in the following structure may be further substituted by R ¹ in formula (1-1) or a known substituent such as a hydrocarbon group.

When X ¹ is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-10), X ¹ is preferably a group represented by the following formula (V-10-1). In the following formula, * represents the bonding site to which X ¹ in formula (1-1) bonds with the four carbonyl groups. In addition, the hydrogen atoms in the following structure may be further substituted with R ¹ in formula (1-1), known substituents such as hydrocarbon groups, etc.

Alternatively, X ¹ may be a tetracarboxylic acid residue remaining after removal of the anhydride groups from the tetracarboxylic acid dianhydride described in paragraphs 0055 to 0057 of JP-A No. 2023-003421.

Furthermore, it is preferable that ^X1 does not contain an imide structure in its structure.
Furthermore, it is preferable that ^X1 does not contain a urethane bond, a urea bond, or an amide bond in the structure.
In the present invention, the urethane bond is a bond represented by *-O-C(=O)-NR ^N -*, where R ^N represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom. R ^N is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom.
In the present invention, the urea bond is a bond represented by *-NR ^N -C(=O)-NR ^N -*, where each R ^N independently represents a hydrogen atom or a monovalent organic group, and each * represents a bonding site with a carbon atom. Preferred aspects of R ^N are as described above.
Furthermore, it is preferable that ^X1 does not contain an ester bond in the structure.
In the present invention, the ester bond is a bond represented by *--O--C(.dbd.O)--*.
Among these, it is preferable that X ¹ does not contain an imide structure, a urethane bond, a urea bond, or an amide bond, and it is more preferable that X 1 does not contain an imide structure, a urethane bond, a urea bond, an amide bond, or an ester bond.

Furthermore, ^X1 may be a structure represented by the following formula (X-2), or a structure in which the hydrogen atom of the group represented by ^X2 or the hydrogen atom of the group represented by ^L3 in the structure represented by formula (X-2) is substituted with a group represented by ^R1 in formula (1-1).
In formula (X-2), ^X2 's each independently represent a trivalent linking group, ^L3 's represents a divalent linking group, and * represents a bonding site to another structure.

In formula (X-2), ^X2 is exemplified by a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic 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 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 even more preferably a halogenated alkylene group having 1 to 4 carbon atoms. Examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred. The halogenated alkylene group may contain hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms be 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 even more preferably a 1,3-phenylene group or a 1,4-phenylene group.

^X2 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.
Two of the three carboxy groups of the tricarboxylic acid compound may be converted into acid anhydrides.
Examples of the tricarboxylic acid compound which may be halogenated include branched aliphatic, cyclic aliphatic, and aromatic tricarboxylic acid compounds.
These tricarboxylic acid compounds may be used alone or in combination of two or more.

It is preferable that ^X2 does not contain an imide structure in its structure.
Furthermore, it is preferable that ^X2 does not contain a urethane bond, a urea bond, or an amide bond in the structure.
Furthermore, it is preferable that ^X2 does not contain an ester bond in the structure.
Among these, ^X2 preferably does not contain an imide structure, a urethane bond, a urea bond, or an amide bond, and more preferably does not contain an imide structure, a urethane bond, a urea bond, an amide bond, or an ester bond.

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 combining two or more of these groups 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 combining two or more aromatic groups having 6 to 20 carbon atoms 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—, —CH ₂ —, —C(CH ₃ ) ₂ —, —C(CF ₃ ) ₂ —, —SO ₂ —, or a phenylene group.
These compounds may be compounds in which two carboxy groups are anhydrides (e.g., trimellitic anhydride), or may be compounds in which at least one carboxy group is halogenated (e.g., trimellitic anhydride chloride).

In formula (X-2), ^L3 is exemplified by a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, or a group in which two or more of these are linked by a single bond or a linking group, and is preferably a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined by a single bond or a linking group, and more preferably 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.
The 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 even more preferably a halogenated alkylene group having 1 to 4 carbon atoms. Examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred. The halogenated alkylene group may contain hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms be 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 even more preferably a 1,3-phenylene group or a 1,4-phenylene group.

Furthermore, ^X1 may be a structure represented by the following formula (X-3), or a structure in which the hydrogen atom of the group represented by ^X2 or the hydrogen atom of the group represented by ^L3 in the structure represented by formula (X-3) is substituted with a group represented by ^R1 in formula (1-1).
In formula (X-3), ^X2 's each independently represent a trivalent linking group, ^L3 represents a divalent linking group, and * represents a bonding site to another structure.
In formula (X-3), the preferred embodiments of ^X2 and ^L3 are the same as the preferred embodiments of ^X2 and ^L3 in formula (X-2).

^-Y1-
Y ¹ has 4 or more carbon atoms, preferably 4 to 50 carbon atoms, and more preferably 4 to 40 carbon atoms.
In formula (1-1), Y ¹ may be a group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-1) to (V-10) above.
The organic group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-1) to (V-10) improves the chemical resistance and flatness of the cured product.

When Y ¹ is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-1), Y ¹ is preferably a group represented by the following formula (V-1-2): In the following formula, * represents the bonding site to the two nitrogen atoms to which Y ¹ in formula (1-1) is bonded, and n1 represents an integer of 1 to 5. Furthermore, the hydrogen atoms in the following structure may be further substituted by R ¹ in formula (1-1) or a known substituent such as a hydrocarbon group.

When Y ¹ is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-2), Y ¹ is preferably a group represented by formula (V-2-3) or formula (V-2-4) below, and from the viewpoint of reducing the dielectric constant of the cured product, a group represented by formula (V-2-4) is preferred. In the following formulas, L ^X1 represents a single bond or —O—, and * represents the bonding site with the two nitrogen atoms to which Y ¹ is bonded in formula (1-1). In addition, preferred aspects of R ^X1 are as described above. In addition, the hydrogen atoms in these structures may be further substituted with R ¹ in formula (1-1) or a known substituent such as a hydrocarbon group.

When Y ¹ is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-3), Y ¹ is preferably a group represented by formula (V-3-3) or formula (V-3-4) below, and from the viewpoint of reducing the dielectric constant of the cured product, a group represented by formula (V-3-3) is preferred. In the following formulas, * represents the bonding site with the two nitrogen atoms to which Y ¹ in formula (1-1) is bonded. In addition, preferred aspects of R ^X2 and R ^X3 are as described above. In addition, the hydrogen atoms in these structures may be further substituted with R ¹ in formula (1-1) or a known substituent such as a hydrocarbon group.

When Y ¹ is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-4), Y ¹ is preferably a group represented by formula (V-4-2) or formula (V-4-3) below. In the formulas below, * represents the bonding site with the two nitrogen atoms to which Y ¹ in formula (1-1) is bonded, and n1 represents an integer of 0 to 5. An embodiment in which n1 is 0 is also one of the preferred embodiments of the present invention. Furthermore, the hydrogen atom in the structure below may be further substituted with R ¹ in formula (1-1) or a known substituent such as a hydrocarbon group. Examples of known substituents include an alkyl group, a halogenated alkyl group, and a halogen atom.

When Y ¹ is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-5), Y ¹ is preferably a group represented by formula (V-5-2) below. In the following formula, * represents the bonding site with the two nitrogen atoms to which Y ¹ in formula (1-1) is bonded. Furthermore, the hydrogen atom in formula (V-5-2) may be further substituted with R ¹ in formula (1-1) or a known substituent such as a hydrocarbon group. Examples of the known substituent include an alkyl group, a halogenated alkyl group, and a halogen atom. However, it is also preferable that none of the hydrogen atoms in the structure represented by (V-5-2) is substituted.

When Y ¹ is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-6), Y ¹ is preferably a group represented by the following formula (V-6-2). In the following formula, * represents the bonding site with the two nitrogen atoms to which Y ¹ is bonded in formula (1-1). In addition, the hydrogen atom in the following structure may be further substituted with R ¹ in formula (1-1) or a known substituent such as a hydrocarbon group.

When Y ¹ is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-7), Y ¹ is preferably a group represented by the following formula (V-7-2). In the following formula, * represents the bonding site with the two nitrogen atoms to which Y ¹ is bonded in formula (1-1). In addition, the hydrogen atoms in the following structure may be further substituted with R ¹ in formula (1-1) or a known substituent such as a hydrocarbon group.

When Y ¹ is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-8), Y ¹ is preferably a group represented by the following formula (V-8-2). In the following formula, * represents the bonding site with the two nitrogen atoms to which Y ¹ is bonded in formula (1-1). In addition, the hydrogen atom in the following structure may be further substituted with R ¹ in formula (1-1) or a known substituent such as a hydrocarbon group.

When Y ¹ is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-9), Y ¹ is preferably a group represented by the following formula (V-9-2). In the following formula, * represents the bonding site with the two nitrogen atoms to which Y ¹ is bonded in formula (1-1). In addition, preferred aspects of R ^X5 are as described above. In addition, the hydrogen atom in the following structure may be further substituted with R ¹ in formula (1-1) or a known substituent such as a hydrocarbon group.

When Y ¹ is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-10), Y ¹ is preferably a group represented by the following formula (V-10-2). In the following formula, * represents the bonding site with the two nitrogen atoms to which Y ¹ is bonded in formula (1-1). In addition, the hydrogen atom in the following structure may be further substituted with R ¹ in formula (1-1) or a known substituent such as a hydrocarbon group.

Additionally, Y ¹ may be a group described in paragraphs 0042 to 0053 of JP-A No. 2023-003421.
It is also preferable that ^Y1 does not contain an imide structure in its structure.
It is also preferred that ^Y1 does not contain a urethane bond, a urea bond or an amide bond in the structure.
Furthermore, it is preferable that ^Y1 does not contain an ester bond in the structure.
Among these, ^Y1 preferably does not contain an imide structure, a urethane bond, a urea bond, or an amide bond, and more preferably does not contain an imide structure, a urethane bond, a urea bond, an amide bond, or an ester bond.

Among these, it is preferable that ^X1 and ^Y1 in formula (1-1) both contain a ring structure, and each is more preferably an organic group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by any one of formulas (V-1) to (V-10) above, and even more preferably an organic group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by any one of formulas (V-1) to (V-4) above. Preferred aspects of these groups are as described above.

-R ¹ -
R ¹ in formula (1-1) is a group represented by formula (R-1).
In formula (R-1), ^L1 is preferably a group represented by the following formula (L-2).
In formula (L-2), ^Z2 represents -O-, -NR ^N -, -C(=O)O- or -C(=O)NR ^N -, R ^N represents a hydrogen atom or a monovalent organic group, when a1 is 1, L ^x represents a single bond or a divalent linking group, when a1 is 2 or more, L ^x represents an a1+1-valent linking group, a1 represents an integer of 1 or more, * represents a bonding site to another structure in ^X1 or ^Y1 in formula (1-1), and # represents a bonding site to ^A1 in formula (R-1).

In formula (L-2), ^Z2 is preferably —O— or —C(═O)O—. When ^Z2 is —NR ^N — or —C(═O)NR ^N —, R ^N is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or a phenyl group, and still more preferably a hydrogen atom.
In formula (L-2), when a1 is 1, ^Lx is preferably an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, still more preferably an alkylene group having 1 to 4 carbon atoms, and particularly preferably a methylene group.
In formula (L-2), when a1 is 2 or more, ^Lx is preferably a hydrocarbon group, a heterocyclic group, or a group represented by a combination thereof, more preferably a saturated aliphatic hydrocarbon group having 2 to 20 carbon atoms, and even more preferably a saturated aliphatic hydrocarbon group having 3 to 15 carbon atoms.
In formula (L-2), a1 has the same meaning as a1 in formula (R-1).

In formula (R-1), A ¹ represents a polymerizable group. Preferred embodiments of the polymerizable group are the same as the preferred embodiments of the polymerizable group contained in the specific resin described above.

Among these, ^A1 is preferably a vinylphenyl group, a (meth)acryloxy group, a vinyl ether group, a maleimide group, an allyl group, or a group containing these, and more preferably a maleimide group, a (meth)acryloxy group, a (meth)acrylamide group, or a vinylphenyl group. In particular, a (meth)acryloxy group is preferred from the viewpoint of reactivity. Furthermore, a maleimide group or a vinylphenyl group is preferred from the viewpoint of reducing the dielectric loss tangent of the cured product.
In particular, at least one of A ¹ in formula (R-1) included in formula (1-1) is preferably a vinylphenyl group, a (meth)acryloxy group, a vinyl ether group, a maleimide group, an allyl group, an epoxy group, or a group containing any of these, more preferably a maleimide group, a (meth)acryloxy group, a (meth)acrylamide group, or a vinylphenyl group, and even more preferably a vinylphenyl group.

Among these, it is preferable that A ¹ in formula (R-1) is a vinylphenyl group and L ¹ is a group represented by formula (L-2-1).
In formula (L-2-1), L and ^X2 represent a hydrocarbon group, and a1 represents an integer of 1 or more.
In formula (L-2-1), L and ^X2 are preferably saturated aliphatic hydrocarbon groups.
When a1 is 1, L ^X2 is preferably an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, still more preferably an alkylene group having 1 to 4 carbon atoms, and particularly preferably a methylene group.
In formula (L-2-1), a1 has the same meaning as a1 in formula (R-1).

It is also preferred that A ¹ in formula (R-1) is a maleimide group, L ¹ is a group represented by formula (L-2), and L ^X in formula (L-2) is an aromatic group or an aliphatic saturated hydrocarbon group having 4 or more carbon atoms.
The aromatic group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, with an aromatic hydrocarbon group being preferred.
The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and more preferably an aromatic hydrocarbon group having 6 carbon atoms.
Examples of heteroatoms in the aromatic heterocyclic group include oxygen atoms, nitrogen atoms, and sulfur atoms. The number of heteroatoms in the aromatic heterocyclic group is preferably 1 or 2. The aromatic heterocyclic group is preferably a 5- or 6-membered ring containing the heteroatom. Furthermore, the aromatic heterocyclic group may be condensed with another aromatic heterocyclic group or another aromatic hydrocarbon ring group.
The aliphatic saturated hydrocarbon group having 4 or more carbon atoms may have any of a linear, branched, or cyclic structure, or a structure represented by a combination thereof.
The aliphatic saturated hydrocarbon group having 4 or more carbon atoms preferably has 4 to 20 carbon atoms, and more preferably has 5 to 10 carbon atoms.

In formula (R-1), a1 is preferably an integer of 1 to 4, and more preferably an integer of 1 or 2. An embodiment in which a1 is 1 is also a preferred embodiment of the present invention.

Furthermore, the number of ester bonds contained in formula (R-1) is preferably 1 or 0.

-n and m-
In formula (1-1), m is preferably an integer of 0 to 2, and more preferably 0 or 1. An embodiment in which m is 0 is also one of the preferred embodiments of the present invention.
In formula (1-1), n is preferably 1 or more, more preferably 1 or 2, and even more preferably 2.

[Repeating unit represented by formula (1-2)]
The specific resin may have a repeating unit represented by formula (1-2).
In formula (1-2), X ²¹ represents an organic group having 4 or more carbon atoms, Y ²¹ represents an organic group having 4 or more carbon atoms, R ²¹ each independently represents a group containing a group represented by formula (B-1) above, m represents an integer of 0 to 4, n represents an integer of 0 or more, and n+m is an integer of 1 or more.

In formula (1-2), preferred embodiments of ^X21 are the same as preferred embodiments of ^X1 in formula (1-1) above, except that the description of "the bonding site to ^R1 " in the description of ^X1 should be read as "the bonding site to ^R21 ".
In formula (1-2), preferred embodiments of Y ²¹ are the same as preferred embodiments of Y ¹ in formula (1-1) above, except that the description of "the bonding site to R ¹ " in the description of X ¹ should be read as "the bonding site to R ²¹ ".

R ²¹ is preferably a group represented by the following formula (B-2).
In formula (B-2), Z ^B1 represents —O—, —NR ^N —, —C(═O)O— or —C(═O)NR ^N —; R ^N represents a hydrogen atom or a monovalent organic group; R ^B1 represents a group represented by formula (B-1) above; and * represents a bonding site to the structure of X ²¹ or Y ²¹ in formula (1-2).

In formula (B-2), Z ^B1 is preferably —O—. When Z ^B1 is —NR ^N — or —C(═O)NR ^N —, R ^N is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or a phenyl group, and still more preferably a hydrogen atom.
In formula (B-2), preferred embodiments of R ^B1 are the same as the preferred embodiments of the group represented by formula (B-1) above.

In formula (1-2), m is preferably an integer of 0 to 2, and more preferably 0 or 1. An embodiment in which m is 0 is also one of the preferred embodiments of the present invention.
In formula (1-2), n is preferably 1 or more, more preferably 1 or 2, and even more preferably 2.

[Repeating unit represented by formula (4)]
The specific resin may contain a repeating unit represented by formula (4).
A repeating unit corresponding to the repeating unit represented by formula (1-1) or formula (1-2) does not correspond to the repeating unit represented by formula (4).
In formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group.

R ¹³¹ represents a divalent organic group. Examples of R ¹³¹ include groups described in paragraphs 0042 to 0053 of JP-A No. 2023-003421. These descriptions are incorporated herein by reference.

R ¹³² represents a tetravalent organic group. Examples of R ¹³² include groups described in paragraphs 0055 to 0057 of JP-A No. 2023-003421. These descriptions are incorporated herein by reference.

When the specific resin is a polyimide, the content of the repeating unit represented by formula (1-1) relative to the total mass of the specific resin is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more. The upper limit of the content is not particularly limited, and may be 100% by mass.
Furthermore, when the specific resin is a polyimide, the total content of the repeating unit represented by formula (1-1), the repeating unit represented by formula (1-2), and the repeating unit represented by formula (4) relative to the total mass of the specific resin is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. The upper limit of this content is not particularly limited, and may be 100% by mass.
Furthermore, when the specific resin contains a repeating unit represented by formula (1-1), it may contain two or more repeating units represented by formula (1-1) with different structures. In that case, it is preferable that the total amount is within the above range.
When the specific resin contains a repeating unit represented by formula (1-2), it may contain two or more repeating units represented by formula (1-2) with different structures. In that case, it is preferable that the total amount is within the above range.
When the specific resin contains a repeating unit represented by formula (4), it may contain two or more repeating units represented by formula (4) having different structures. In that case, it is preferable that the total amount is within the above range.

When the specific resin is a polyimide, the weight average molecular weight (Mw) of the specific resin is preferably 3,000 to 100,000.
The lower limit of the Mw is preferably 5,000 or more, more preferably 8,000 or more, and even more preferably 10,000 or more.
The upper limit of the Mw is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less.
By setting the weight-average molecular weight to 3,000 or more, the break resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties (e.g., breaking elongation), the weight-average molecular weight is particularly preferably 5,000 or more.
When the specific resin is a polyimide, the number average molecular weight (Mn) of the specific resin is preferably from 1,000 to 40,000, more preferably from 2,000 to 30,000, and even more preferably from 5,000 to 20,000.
When the specific resin is a polyimide, the molecular weight dispersity of the specific resin is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyimide is not particularly specified, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, even more preferably 6.0 or less, still more preferably 4.5 or less, and particularly preferably 3.0 or less.
In this specification, the molecular weight dispersity is a value calculated by dividing the weight average molecular weight by the number average molecular weight.
When the resin composition contains multiple polyimides as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one of the resins are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated by treating the multiple resins as one resin are each within the above-mentioned ranges.

When the specific resin is a polyimide, the imidization rate (also referred to as "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, from the viewpoint of the film strength, insulating properties, etc. of the resulting organic film. The upper limit of the imidization rate is not particularly limited, and it is sufficient if it is 100% or less.
When the specific resin is a polyimide, the content of the imide structure in the specific resin is preferably 3 mmol/g or less, more preferably 2.5 mmol/g or less. The lower limit of the content is not particularly limited, but can be, for example, 0.5 mmol/g or more.
The imidization rate is measured, for example, by the following method.
The infrared absorption spectrum of the specific resin is measured, and the peak intensity P1 near 1377 cm ⁻¹ , which is an absorption peak derived from the imide structure, is determined. Next, the specific resin is heat-treated at 350°C for 1 hour, and then the infrared absorption spectrum is measured again, and the peak intensity P2 near 1377 cm ⁻¹ is determined. Using the obtained peak intensities P1 and P2, the imidization rate of the specific resin can be calculated based on the following formula.
Imidization rate (%) = (peak intensity P1/peak intensity P2) × 100

[Repeating unit represented by formula (2)]
The resin composition of the present invention preferably contains a resin having a repeating unit represented by formula (2) as the specific resin.
In formula (2), ^A1 and ^A2 each independently represent an oxygen atom or ^-NRz- , ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group, and ^Rz represents a hydrogen atom or a monovalent organic group.

In formula (2), A ¹ and A ² each independently represent an oxygen atom or —NR ^z —, and preferably an oxygen atom.
^Rz represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom.

In formula (2), preferred embodiments of R ¹¹¹ and R ¹¹⁵ are the same as the preferred embodiments of Y ¹ and X ¹ in formula (1-1) above, respectively, except that R ¹¹¹ and R ¹¹⁵ may not have a bonding site with R ¹ in formula (1-1), or may have a bonding site with the same group as R ²¹ in formula (1-2).

In formula (2), R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. It is also preferable that at least one of R ¹¹³ and R ¹¹⁴ contains a polymerizable group, and more preferably that both contain polymerizable groups. It is also preferable that at least one of ^{R 113} and R ¹¹⁴ contains two or more polymerizable groups. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, radicals, or the like, 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, and an amino group. The radically polymerizable group contained in the polyimide precursor is preferably a group having an ethylenically unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III), and the group represented by the following formula (III) is preferred.

In formula (III), R ²⁰⁰ represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and is preferably a hydrogen atom or a methyl group.
In formula (III), * represents a bonding site to another structure.
In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, —CH ₂ CH(OH)CH ₂ —, a cycloalkylene group, or a polyalkyleneoxy group.
Suitable examples of R ²⁰¹ include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, 1,2-butanediyl, 1,3-butanediyl, —CH ₂ CH(OH)CH ₂ —, and polyalkyleneoxy groups, of which alkylene groups such as ethylene and propylene, —CH ₂ CH(OH)CH ₂ —, cyclohexyl, and polyalkyleneoxy groups are more preferred, and alkylene groups such as ethylene and propylene, or polyalkyleneoxy groups are even more preferred.
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 in the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 6, still more preferably 2 to 5, still more preferably 2 to 4, still more preferably 2 or 3, and particularly 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 to 20, more preferably 2 to 10, and even more preferably 2 to 6.
As the polyalkyleneoxy group, from the viewpoint of solvent solubility and solvent resistance, a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded is preferred, a polyethyleneoxy group or a polypropyleneoxy group is more preferred, and a polyethyleneoxy group is even more preferred. In the group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in a pattern such as alternating. The preferred embodiments of the number of repetitions of the ethyleneoxy groups etc. in these groups are as described above.

At least one of R ¹¹³ and R ¹¹⁴ may be a group represented by the above formula (B-1). Preferred embodiments of the group represented by formula (B-1) are as described above.

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. Examples of such a tertiary amine compound having an ethylenically unsaturated bond include N,N-dimethylaminopropyl methacrylate.

When the specific resin is a polyimide precursor, the content of the repeating unit represented by formula (2) relative to the total mass of the specific resin is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more. The upper limit of the content is not particularly limited, and may be 100% by mass.
Furthermore, when the specific resin is a polyimide precursor, the total content of the repeating unit represented by formula (2) and the repeating unit represented by formula (4) relative to the total mass of the specific resin is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. The upper limit of this content is not particularly limited, and may be 100% by mass.
Furthermore, when the specific resin contains a repeating unit represented by formula (2), it may contain two or more repeating units represented by formula (2) having different structures. In that case, it is preferable that the total amount is within the above range.
Furthermore, when the specific resin contains a repeating unit represented by formula (4), it may contain two or more repeating units represented by formula (4) having different structures. In that case, it is preferable that the total amount is within the above range.

When the specific resin is a polyimide precursor, the weight average molecular weight (Mw) of the specific resin is preferably 3,000 to 100,000.
The lower limit of the Mw is preferably 5,000 or more, more preferably 8,000 or more, and even more preferably 10,000 or more.
The upper limit of the Mw is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less.
By setting the weight-average molecular weight to 3,000 or more, the break resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties (e.g., breaking elongation), the weight-average molecular weight is particularly preferably 5,000 or more.
When the specific resin is a polyimide precursor, the number average molecular weight (Mn) of the specific resin is preferably 1,000 to 40,000, more preferably 2,000 to 30,000, and even more preferably 5,000 to 20,000.
When the specific resin is a polyimide precursor, the molecular weight dispersity of the specific resin is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyimide is not particularly specified, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, even more preferably 6.0 or less, still more preferably 4.5 or less, and particularly preferably 3.0 or less.
When the resin composition contains multiple polyimide precursors as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one of the resins are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated by treating the multiple resins as one resin are each within the above-mentioned ranges.

When the specific resin is a polyimide precursor, the imidization rate (also referred to as "ring closure rate") of the polyimide precursor is preferably less than 70%, more preferably 50% or less, and even more preferably 30% or less, from the viewpoint of the film strength, insulating properties, etc. of the resulting organic film. The lower limit of the imidization rate is not particularly limited, and may be 0% or more.
The imidization rate is measured by the method described above.

[Repeating unit represented by formula (X)]
The specific resin is preferably a resin having a repeating unit represented by the following formula (X), and more preferably a resin having a repeating unit represented by the following formula (X) and a polymerizable group. Preferred embodiments of the polymerizable group are as described above.
In formula (X), R ¹³³ represents a divalent organic group, and R ¹³⁴ represents a tetravalent organic group.
When the compound has a polymerizable group, the polymerizable group may be located at at least one of R ¹³³ and R ¹³⁴ , or may be located at the end of the polybenzoxazole as shown in the following formula (X-1) or formula (X-2).
Formula (X-1)
In formula (X-1), at least one of R ¹³⁵ and R ¹³⁶ is a polymerizable group, and if it is not a polymerizable group, it is an organic group, and the other groups have the same meanings as in formula (X).
Formula (X-2)
In formula (X-2), R ¹³⁷ is a polymerizable group, and the other groups have the same meanings as in formula (X).

Preferred embodiments of the polymerizable group are as described above.

R ¹³³ represents a divalent organic group. Examples of the divalent organic group include an aliphatic group and an aromatic group. Specifically, R ¹³³ may be the same group as R ¹³¹ in the following formula (R133-1) or formula (4).
In formula (R133-1), Y ¹ represents an organic group having 4 or more carbon atoms, each R ¹ independently represents a structure represented by formula (R-1) above, n represents an integer of 1 or more, and * represents a bonding site to another structure.
In formula (R133-1), preferred embodiments of Y ¹ , R ¹ and n are the same as the preferred embodiments of Y ¹ , R ¹ and n shown in formula (1-1) above.

R ¹³⁴ represents a tetravalent organic group. Examples of the tetravalent organic group include an aliphatic group and an aromatic group. Specifically, R ¹³⁴ may be the same group as R ¹³² in the following formula (R134-1) or formula (4).
In formula (R134-1), ^X1 represents an organic group having 4 or more carbon atoms, each ^R1 independently represents a structure represented by formula (R-1) above, m represents an integer of 0 to 4 or more, and * represents a bonding site to another structure.
In formula (R134-1), preferred embodiments of X ¹ , R ¹ and m are the same as the preferred embodiments of X ¹ , R ¹ and m shown in formula (1-1) above.

When the specific resin is polybenzoxazole, the weight-average molecular weight (Mw) is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By adjusting the weight-average molecular weight to 5,000 or more, the fold resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties, the weight-average molecular weight is particularly preferably 20,000 or more. When two or more types of polybenzoxazoles are contained, it is preferable that the weight-average molecular weight of at least one type of polybenzoxazole be within the above range.
When the specific resin is polybenzoxazole, the number average molecular weight (Mn) is preferably from 7,200 to 14,000, more preferably from 8,000 to 12,000, and even more preferably from 9,200 to 11,200.
When the specific resin is polybenzoxazole, the molecular weight dispersity is 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 polybenzoxazole 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.
When the resin composition contains multiple polybenzoxazoles as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polybenzoxazole are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated by treating the multiple polybenzoxazoles as a single resin are within the above-mentioned ranges.

When the specific resin is polybenzoxazole, the polybenzoxazole preferably has an oxazolization rate of 85% or more, more preferably 90% or more. The upper limit is not particularly limited, and may be 100%. When the oxazolization rate is 85% or more, film shrinkage due to ring closure that occurs when oxazolized by heating is reduced, and warpage can be more effectively suppressed.
The oxazole ratio is measured, for example, by the following method.
The infrared absorption spectrum of the polybenzoxazole is measured, and the peak intensity Q1 near 1650 cm ⁻¹ , which is an absorption peak derived from the amide structure of the precursor, is determined. This is then normalized by the absorption intensity of the aromatic ring observed near 1490 cm ⁻¹ . After heat treating the polybenzoxazole at 350°C for 1 hour, the infrared absorption spectrum is measured again, and the peak intensity Q2 near 1650 cm ⁻¹ is determined and normalized by the absorption intensity of the aromatic ring observed near 1490 cm ⁻¹ . The normalized values of the peak intensities Q1 and Q2 obtained can be used to calculate the oxazolization rate of the polybenzoxazole based on the following formula:
Oxazolization rate (%) = (normalized value of peak intensity Q1/normalized value of peak intensity Q2) × 100

The polybenzoxazole may contain repeating units of the above formula (X) in which the combination of R ¹³³ and R ¹³⁴ is the same, or may contain repeating units of the above formula (X) containing two or more different combinations of R ¹³³ and R ^134. Furthermore, the polybenzoxazole may contain other types of repeating units in addition to the repeating units of the above formula (X).

[Repeating unit represented by formula (3)]
The specific resin is preferably a resin having a repeating unit represented by the following formula (3), and more preferably a resin having a repeating unit represented by the following formula (3) and a polymerizable group. Preferred embodiments of the polymerizable group are as described above.
In formula (3), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group.

In formula (3), R ¹²³ and R ¹²⁴ each have the same definition as R ¹¹³ in formula (2), and the preferred range is also the same. That is, it is preferable that at least one of them is a polymerizable group.
In formula (3), preferred embodiments of R ¹²¹ are the same as preferred embodiments of R ¹²¹ in formula (3) described in paragraphs 0074 to 0079 of WO 2022/145355.
In formula (3), preferred embodiments of R ¹²² are the same as preferred embodiments of R ¹²² in formula (3) described in paragraphs 0080 to 0090 of WO 2022/145355.

When the specific resin is a polybenzoxazole precursor, the weight-average molecular weight (Mw) is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By adjusting the weight-average molecular weight to 5,000 or more, the fold resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties, the weight-average molecular weight is particularly preferably 20,000 or more. When two or more polybenzoxazole precursors are contained, it is preferable that the weight-average molecular weight of at least one polybenzoxazole precursor be within the above range.
When the specific resin is a polybenzoxazole precursor, the number average molecular weight (Mn) is preferably from 7,200 to 14,000, more preferably from 8,000 to 12,000, and even more preferably from 9,200 to 11,200.
When the specific resin is a polybenzoxazole precursor, the molecular weight dispersity is 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 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.
When the resin composition contains multiple polybenzoxazole precursors as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polybenzoxazole precursor be within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated by treating the multiple polybenzoxazole precursors as a single resin be within the above-mentioned ranges.

When the specific resin is a polybenzoxazole precursor, the polybenzoxazole precursor preferably has an oxazole ratio of 15% or less, more preferably 10% or less. The lower limit is not particularly limited, and may be 0%.
The oxazole conversion rate is measured, for example, by the method described above.

The polybenzoxazole precursor may contain repeating units of the above formula (3) in which the combinations of R ¹²¹ to R ¹²⁴ are the same, or may contain repeating units of the above formula (3) in which two or more types of combinations of R ¹²¹ to R ¹²⁴ are different in part or in whole. Furthermore, the polybenzoxazole precursor may contain other types of repeating units in addition to the repeating units of the above formula (3).

[Method for producing specific resin]
The specific resin can be synthesized by, for example, the method described in paragraphs 0134 to 0136 of WO 2022/145355 or by reference to this method. The above description is incorporated herein by reference. Alternatively, the specific resin may be synthesized by reference to other known methods.

Examples of a method for introducing a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms into a specific resin include a method using a compound having the alkylene group as an end-capping agent, and a method using a compound having the alkylene group as a raw material for the resin, such as a carboxylic acid dianhydride or a derivative thereof (e.g., a diester) or a diamine.
For details of these synthesis methods, please refer to the description of the resin synthesis methods in the Examples below.
Examples of the end-capping agent include compounds represented by the following formula (TM-1).
In formula (TM-1), ^R1 represents a divalent linking group, ^Z1 represents a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms or a silicon atom, and when ^Z1 is the alkylene group, n is 1, and ^R2 represents a hydrogen atom or a monovalent organic group, and when ^Z1 is the silicon atom, n is 3, and each ^R2 independently represents a monovalent organic group, and ^R3 represents a group bonding to a resin terminal.

In formula (TM-1), preferred embodiments of R ¹ , Z ¹ , n, and R ² are the same as the preferred embodiments of R ¹ , Z ¹ , n, and R ² in formula (B-1) above.
In formula (TM-1), R ³ may be an amino group, a hydroxy group, a carboxy group, a carboxylic acid halide group, or the like, and is preferably an amino group.

[Content]
The content of the specific resin in the resin composition of the present invention is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and even more preferably 30% by mass or more, based on the total solid content of the resin composition. Also, the content of the resin in the resin composition of the present invention is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on the total solid content of the resin composition.
The resin composition of the present invention may contain only one specific resin or two or more specific resins. When two or more specific resins are contained, the total amount is preferably within the above range.

<Other resins>
The resin composition of the present invention may contain other resins (hereinafter simply referred to as "other resins") different from the specific resins described above.
Examples of other resins are resins different from the specific resin, such as polyimide precursors, polyimides, polybenzoxazole precursors, polybenzoxazoles, polyamideimide precursors, polyamideimides, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins.
Examples of other polyimide precursors, other polyimides, polybenzoxazole precursors, polybenzoxazoles, polyamideimide precursors, and polyamideimides include the compounds described in paragraphs 0017 to 0138 of WO 2022/145355, the disclosures of which are incorporated herein by reference.

When the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 1% by mass or more, still more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, relative to the total solid content of the resin composition.
The content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, still more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on the total solid content of the resin composition.
A preferred embodiment of the resin composition of the present invention may be an embodiment in which the content of the other resin is low. In this 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 resin composition. The lower limit of the content is not particularly limited, and may be 0% by mass or more.
The resin 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, the total amount is preferably in the above range.

<Metals or their salts, or metal complexes>
The resin composition of the present invention preferably contains a metal or a salt thereof, or a metal complex, and more preferably contains a metal complex.
When these compounds are contained, the metal species act as a catalyst, which promotes the reaction between the alkynyl group and moisture, and may improve adhesion.
The metal type in these compounds preferably includes titanium or silver.

As the metal or its salt, silver or a silver salt is preferred, and a silver salt is more preferred.
As the metal salt, an organic metal salt is preferred, and an organic silver salt is more preferred.
Examples of organic silver salts include silver acetate, silver benzoate, silver lactate, silver pyrophosphate, silver citrate, silver behenate, silver diethylcarbamate, silver stearate, silver tartrate, silver metasulfonate, silver trifluoroate, silver salts of alkyl esters, phenyl esters, or alkylphenyl esters of phosphoric acid or phosphorous acid, silver phosphofluoride, silver phthalocyanine, and silver ethylenediaminetetraacetate.

The metal complex is preferably a titanium complex, a zirconium complex or a hafnium complex, and more preferably a titanium complex.
Specific examples of titanium complexes are shown below in I) to VII):
I) Titanium chelate compounds: Titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability to the resin composition and a good curing 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), and titanium diisopropoxide bis(ethylacetoacetate).
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}], etc.
III) Titanocene compounds: for example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-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, etc.
VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate.
VII) Titanate coupling agents: for example, isopropyl tridodecylbenzenesulfonyl titanate.

It is also preferable that the metal complex contains a compound represented by the following formula (T-1).
In formula (T-1), M represents titanium, zirconium, or hafnium, l1 represents an integer of 0 to 2, l2 represents 0 or 1, l1 + l2 × 2 represents an integer of 0 to 2, m represents an integer of 0 to 4, n represents an integer of 0 to 2, and l1 + l2 + m + n × 2 = 4, each R ¹¹ represents independently a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenoxy group, R ¹² represents a substituted or unsubstituted hydrocarbon group, each R ² represents independently a group containing a structure represented by formula (T-2) below, each R ³ represents independently a group containing a structure represented by formula (T-2) below, and each X ^1A represents independently an oxygen atom or a sulfur atom.
In formula (T-2), X ¹ to X ³ each independently represent -C(-*)= or -N=, * represents a bonding site to another structure, and # represents a bonding site to a metal atom.

In formula (T-1), M is preferably titanium from the viewpoint of storage stability of the composition.
In formula (T-1), an embodiment in which l1 and l2 are 0 is also one of the preferred embodiments of the present invention.
In formula (T-1), m is preferably 2 or 4, and more preferably 2.
In formula (T-1), n is preferably 1 or 2, and more preferably 1.
Here, it is also preferred that l1 and l2 are 0 and m is 0, 2 or 4 in formula (T-1).

In formula (T-1), from the viewpoint of the stability of the metal complex, R ¹¹ is preferably a substituted or unsubstituted cyclopentadienyl ligand.
The cyclopentadienyl group, alkoxy group and phenoxy group in R ¹¹ may be substituted, but an unsubstituted embodiment is also one of the preferred embodiments of the present invention.

In formula (T-1), R ¹² is preferably a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrocarbon group having 2 to 10 carbon atoms.
The hydrocarbon group for R ¹² may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, with aromatic hydrocarbon groups being preferred.
The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, but a saturated aliphatic hydrocarbon group is preferred.
The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and even more preferably a phenylene group.
The substituent in R ¹² is preferably a monovalent substituent, such as a halogen atom, etc. When R ¹² is an aromatic hydrocarbon group, it may have an alkyl group as a substituent.
Among these, in formula (T-1), R ¹² is preferably an unsubstituted phenylene group, and the phenylene group in R ¹² is preferably a 1,2-phenylene group.

In formula (T-1), when m is 2 or more and two or more R ^2s are contained, the structures of the two or more R ^2s may be the same or different.
In formula (T-1), when n is 2 or more and two or more R ^3s are contained, the structures of the two or more R ^3s may be the same or different.

In formula (T-2), X ¹ to X ³ each independently represent -C(-*)= or -N=, and it is preferable that at least one represents -C(-*)=, and it is more preferable that at least two represent -C(-*)=.

Specific examples of compounds represented by formula (T-1) include, but are not limited to, compounds I-5 to I-8 in the examples.

When a metal or a salt thereof, or a metal complex is contained, the content thereof is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the specific resin. When the content is 0.05 part by mass or more, the heat resistance and chemical resistance of the obtained cured pattern are improved, and when the content is 10 parts by mass or less, the storage stability of the composition is superior.
The resin composition may contain two or more compounds corresponding to either a metal or a salt thereof, or a metal complex. When two or more compounds are contained, it is preferable that the total content thereof is within the above range.

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

The melting point of the polymerizable compound is preferably 60° C. or lower. The melting point is the melting point at 1 atmosphere, and is more preferably 40° C. or lower, and even more preferably 25° C. or lower.
By setting the melting point to 60° C. or less, the coating film becomes more fluid when dried and heated, and the flatness of the cured product can be improved.

Examples of polymerizable compounds include polymerizable compounds having radical polymerizable groups (radical crosslinking agents) and other crosslinking agents.

[Radical crosslinking agent]
The resin composition of the present invention preferably contains a radical crosslinking agent.
The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group containing an ethylenically unsaturated bond. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group.
Among these, a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferred, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferred.

The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds, and may also have three or more ethylenically unsaturated bonds.
The compound having two or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and even more preferably a compound having 2 to 6 ethylenically unsaturated bonds.
From the viewpoint of the film strength of the resulting pattern (cured product), it is also preferable that the 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.), their esters, and amides. Preferred are esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. Also suitable are addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, or sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxy groups, and dehydration condensation reaction products of monofunctional or polyfunctional carboxylic acids. Also suitable are addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having eliminable substituents such as halogeno groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols. As another example, compounds in which the above unsaturated carboxylic acids are replaced with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc. can also be used. Specific examples can be found in paragraphs 0113 to 0122 of JP 2016-027357 A, the contents of which are incorporated herein by reference.

The radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples of compounds having a boiling point of 100°C or higher under normal pressure include the compounds described in paragraph 0203 of WO 2021/112189, the contents of which are incorporated herein by reference.

Preferable radical crosslinking agents other than those mentioned above include the radical polymerizable compounds described in paragraphs 0204 to 0208 of WO 2021/112189, the contents of which are incorporated herein by reference.

Preferred radical crosslinking agents include 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 group is bonded via an ethylene glycol residue or a propylene glycol residue. Oligomeric types of these may also be used.

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

Suitable radical crosslinking agents include urethane acrylates such as those described in JP-B No. 48-041708, JP-A No. 51-037193, JP-B No. 02-032293, and JP-B No. 02-016765, as well as urethane compounds with an ethylene oxide skeleton such as those described in JP-B No. 58-049860, JP-B No. 56-017654, JP-B No. 62-039417, and JP-B No. 62-039418. Compounds with an amino structure or sulfide structure in the molecule, such as those described in JP-A Nos. 63-277653, 63-260909, and JP-A No. 01-105238, can also be used as radical crosslinking agents.

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 imparted by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxy groups of an aliphatic polyhydroxy compound. Particularly preferred is a radical crosslinking agent in which an acid group is imparted by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxy groups of an aliphatic polyhydroxy compound, in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include polybasic acid-modified acrylic oligomers M-510 and M-520 manufactured by Toagosei Co., Ltd.

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. When the acid value of the radical crosslinking agent is within the above range, it provides excellent handling during manufacturing and developability. It also provides good polymerizability. The acid value is measured in accordance with the description of JIS K 0070:1992.

From the viewpoint of pattern resolution and film stretchability, it is preferable to use a bifunctional methacrylate or acrylate for the resin composition.
Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexyl methyl ... Examples of usable surfactants include xanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, ethylene oxide (EO) adduct diacrylate of bisphenol A, propylene oxide (PO) adduct dimethacrylate of bisphenol A, propylene oxide (PO) adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, EO-modified isocyanuric acid diacrylate, EO-modified isocyanuric acid dimethacrylate, and other bifunctional acrylates and bifunctional methacrylates having a urethane bond. These may be used in combination of two or more types, if necessary.
For example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a formula weight of about 200 for the polyethylene glycol chain.
In the resin composition of the present invention, from the viewpoint of suppressing warpage of the pattern (cured product), a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent. Examples of the monofunctional radical crosslinking agent include (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 glycidyl ether. In order to suppress volatilization before exposure, compounds having a boiling point of 100°C or higher under normal pressure are also preferred as the monofunctional radical crosslinking agent.
Other examples of the bifunctional or higher functional radical crosslinking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.

If a radical crosslinking agent is contained, the content of the radical crosslinking agent is preferably more than 0% by mass and not more than 60% by mass, based on the total solids content of the resin composition. 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.

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

[Other crosslinking agents]
The resin composition of the present invention preferably contains a crosslinking agent other than the above-mentioned radical crosslinking agent.
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 a photoacid generator or a photobase generator, and is preferably a compound having, in its molecule, a plurality of groups that promote, by the action of an acid or a base, a reaction to form a covalent bond with another compound in the composition or a reaction product thereof.
The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
Other cross-linking agents include the compounds described in paragraphs 0179 to 0207 of WO 2022/145355, which are incorporated herein by reference.

[Polymerization initiator]
The resin composition of the present invention contains a polymerization initiator. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable that the resin composition contains a photopolymerization initiator.
The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular limitations on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible range is preferred. Alternatively, it may be an activator that reacts with a photoexcited sensitizer to generate active radicals.

The photoradical polymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 L mol ^cm in a wavelength range of about 240 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 preferably measured 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. Examples include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organic boron compounds, and iron arene complexes. For details, please refer to 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. Other examples include the compounds described in paragraphs 0065 to 0111 of JP 2014-130173 A and Japanese Patent No. 6,301,489 A, the peroxide-based photopolymerization initiators described in MATERIAL STAGE, pp. 37 to 60, Vol. 19, No. 3, 2019, the photopolymerization initiators described in WO 2018/221177 A, the photopolymerization initiators described in WO 2018/110179 A, the photopolymerization initiators described in JP 2019-043864 A, the photopolymerization initiators described in JP 2019-044030 A, and the peroxide-based initiators described in JP 2019-167313 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. Among commercially available products, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also suitable.

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, the aminoacetophenone initiators described in JP-A-10-291969 and the acylphosphine oxide initiators described in Japanese Patent No. 4225898 can be used, the contents of which are incorporated herein by reference.

Examples of α-hydroxyketone initiators that can be used include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF).

Examples of α-aminoketone initiators that can be used include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins B.V.), and IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF).

As aminoacetophenone initiators, acylphosphine oxide initiators, and metallocene compounds, for example, compounds described in paragraphs 0161 to 0163 of WO 2021/112189 can also be suitably used. The contents of this specification are incorporated herein by reference.

A more preferred example of a photoradical polymerization initiator is an oxime compound. 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 include compounds described in JP 2001-233842 A, compounds described in JP 2000-080068 A, compounds described in JP 2006-342166 A, compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), and compounds described in J. C. S. Compounds described in Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), compounds described in JP-A-2000-066385, compounds described in JP-A-2004-534797, compounds described in JP-A-2017-01976 ... Examples include compounds described in Patent Publication No. 6065596, compounds described in International Publication No. 2015/152153, compounds described in International Publication No. 2017/051680, compounds described in JP-A-2017-198865, compounds described in paragraphs 0025 to 0038 of International Publication No. 2017/164127, and compounds described in International Publication No. 2013/167515, the contents of which are incorporated herein by reference.

Preferred oxime compounds include, for example, compounds having the following structure: 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one. In resin compositions, it is particularly preferable to use an oxime compound as a photoradical polymerization initiator. Oxime compounds used as photoradical polymerization initiators have a linking group of >C=N-O-C(=O)- within the molecule.

Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04, and IRGACURE OXE 05 (manufactured by BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in JP 2012-014052 A), TR-PBG-304 and TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA ARCLES NCI-730, NCI-831, and ADEKA ARCLES NCI-930 (manufactured by ADEKA Corporation), DFI-091 (manufactured by Daito ChemiX Co., Ltd.), and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can also be used. In addition, an oxime compound having the following structure can also be used.

As the photoradical polymerization initiator, for example, an oxime compound having a fluorene ring described in paragraphs 0169 to 0171 of WO 2021/112189, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring, or an oxime compound having a fluorine atom can be used.
In addition, oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds having a carbazole skeleton to which a substituent having a hydroxy group is bonded, as described in paragraphs 0208 to 0210 of WO 2021/020359, the contents of which are incorporated herein by reference.

In addition, the compounds described in paragraphs 0113 to 0117 of JP 2023-058585 A can also be used as photopolymerization initiators. This description is incorporated herein by reference.

When the resin composition contains a photopolymerization initiator, the content thereof is preferably 0.1 to 30 mass% relative to the total solid content of the resin composition, more preferably 0.1 to 20 mass%, even more preferably 0.5 to 15 mass%, and even more preferably 1.0 to 10 mass%. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more types of photopolymerization initiators are contained, it is preferable that the total amount is in the above range.
In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, the crosslinking by the photopolymerization initiator may be further promoted by heating in an oven, a hot plate, or the like.

[Sensitizer]
The resin composition may contain a sensitizer. The sensitizer absorbs specific actinic radiation and becomes electronically excited. The electronically excited sensitizer comes into contact with 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 radical polymerization initiator or the photoradical polymerization initiator undergoes a chemical change and decomposes, generating a radical, an acid, or a base.
Usable sensitizers include benzophenone-based, Michler's ketone-based, coumarin-based, pyrazole azo-based, anilino azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, and indigo-based compounds.
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-dimethylaminobenzylideneindanone, and Non, 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-ethoxycarbonyl-7-dimethylaminocoumarin Phosphorus, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (ethyl 7-(diethylamino)coumarin-3-carboxylate), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate Examples of such an alkyl acrylate copolymer include soamyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, and 3',4'-dimethylacetanilide.
Other sensitizing dyes may also be used.
For details about the sensitizing dye, please refer to the descriptions in paragraphs 0161 to 0163 of JP-A-2016-027357, the contents of which are incorporated herein by reference.

When the resin composition 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 solids content of the resin composition. One type of sensitizer may be used alone, or two or more types may be used in combination.

[Chain transfer agent]
The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pages 683-684. Examples of chain transfer agents include compounds having -S-S-, -SO ₂ -S-, -N-O-, SH, PH, SiH, and GeH in the molecule, and dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthate compounds having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These donate hydrogen to low-activity radicals to generate radicals, or can generate radicals by being oxidized and then deprotonated. Thiol compounds are particularly preferred.

Furthermore, the chain transfer agent may be the compound described in paragraphs 0152-0153 of WO 2015/199219, the contents of which are incorporated herein by reference.

When the resin composition contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the total solids content of the resin composition. Only one type of chain transfer agent may be used, or two or more types may be used. When two or more types of chain transfer agents are used, the total amount is preferably within the above range.

In addition, it is one of the preferred embodiments of the present invention that the resin composition of the present invention contains two or more types of polymerization initiators.
Specifically, the resin composition of the present invention preferably contains a photopolymerization initiator and a thermal polymerization initiator described below, or contains the above-mentioned photoradical polymerization initiator and a photoacid generator.

By including a photopolymerization initiator and a thermal polymerization initiator described below, pattern formation by exposure becomes possible, and radical polymerization also becomes more likely to proceed during curing by a heating step described below, which may improve performance such as chemical resistance.
When a photopolymerization initiator and a thermal polymerization initiator described later are contained, the content of the thermal polymerization initiator is preferably 20 to 70 mass %, more preferably 30 to 60 mass %, relative to the total content of the photopolymerization initiator and the thermal polymerization initiator.

By including a photoradical polymerization initiator and a photoacid generator, performance such as resolution may be improved in some cases.
When a photopolymerization initiator and a photoacid generator are contained, the content ratio of the photoacid generator relative to the total content of the photopolymerization initiator and the photoacid generator is preferably 20 to 70 mass%, more preferably 30 to 60 mass%.

[Thermal polymerization initiator]
Examples of the thermal polymerization initiator include a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or promotes the polymerization reaction of a polymerizable compound. Addition of the thermal radical polymerization initiator can also promote the polymerization reaction of the resin and the polymerizable compound, thereby further improving solvent resistance.

Specific examples of thermal radical polymerization initiators include the compounds described in paragraphs 0074 to 0118 of JP 2008-063554 A, the contents of which are incorporated herein by reference.

If a thermal polymerization initiator is included, its content is preferably 0.1 to 30 mass% of the total solids content of the resin composition, 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. If two or more types of thermal polymerization initiators are included, it is preferable that the total amount be within the above range.

<Base Generator>
The resin composition of the present invention may contain a base generator. Here, the base generator is a compound that can generate a base by physical or chemical action. Preferred base generators include thermal base generators and photobase generators.
In particular, when the resin composition contains a precursor of a cyclized resin, the resin composition preferably contains a base generator. By containing the thermal base generator in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties and chemical resistance of the cured product can be improved, resulting in good performance as an interlayer insulating film for a rewiring layer included in, for example, a semiconductor package.
The base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines.
The base generator is not particularly limited, and known base generators can be used, such as carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, α-lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, and acyloxyimino compounds.

When the resin composition contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less.
The base generator 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.

<Solvent>
The 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.

Esters, for example, 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, γ-valerolactone, alkyl alkyloxyacetates (for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkyloxypropionates (for example, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2- Suitable examples include alkyl esters of alkyloxypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, and propyl 2-alkyloxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, and ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, and diethyl malonate.

Suitable examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

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.

Preferred amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-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 ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

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, methyl amyl alcohol, and diacetone alcohol.

From the perspective of improving the properties of the coated surface, it is also preferable to mix two or more 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, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, levoglucosenone, and dihydrolevoglucosenone, or a mixed solvent composed of two or more solvents, is preferred. Particularly preferred are a combination of dimethyl sulfoxide and γ-butyrolactone, a combination of dimethyl sulfoxide and γ-valerolactone, a combination of 3-methoxy-N,N-dimethylpropionamide and γ-butyrolactone, a combination of 3-methoxy-N,N-dimethylpropionamide, γ-butyrolactone and dimethyl sulfoxide, or a combination of N-methyl-2-pyrrolidone and ethyl lactate. Another preferred embodiment of the present invention is to further add toluene to these combined solvents in an amount of about 1 to 10% by mass, based on the total mass of the solvents.
In particular, from the viewpoint of storage stability of the resin composition, an embodiment in which γ-valerolactone is contained as a solvent is also one of the preferred embodiments of the present invention. In such an embodiment, the content of γ-valerolactone relative to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. The upper limit of the content is not particularly limited and may be 100% by mass. The content may be determined taking into consideration the solubility of components such as the specific resin contained in the resin composition, etc.
Furthermore, when dimethyl sulfoxide and γ-valerolactone are used in combination, the solvent preferably contains 60 to 90% by mass of γ-valerolactone and 10 to 40% by mass of dimethyl sulfoxide, more preferably 70 to 90% by mass of γ-valerolactone and 10 to 30% by mass of dimethyl sulfoxide, and even more preferably 75 to 85% by mass of γ-valerolactone and 15 to 25% by mass of dimethyl sulfoxide, relative to the total mass of the solvent.

Furthermore, the resin composition of the present invention preferably contains a solvent having a boiling point at 1 atmosphere of 50° C. to 300° C., and more preferably contains a solvent having a boiling point at 100° C. to 260° C. In the present invention, the boiling point of the solvent is the boiling point at 1 atmosphere.
According to such an embodiment, it is believed that a cured product having excellent solvent removability and resolution can be obtained.
The boiling point is preferably 150° C. or higher, more preferably 180° C. or higher, and even more preferably 200° C. or higher. The upper limit of the boiling point is preferably 250° C. or lower, more preferably 240° C. or lower, and even more preferably 230° C. or lower.
Furthermore, the resin composition of the present invention preferably contains two or more solvents having a boiling point of 100 to 260°C, more preferably two or more solvents having a boiling point of 150 to 250°C, and even more preferably two or more solvents having a boiling point of 180 to 230°C.
The content of the solvent having a boiling point of 100 to 260°C is preferably 40% by mass or more, more preferably 45% by mass or more, and even more preferably 50% by mass or more, based on the total mass of the composition. When two or more solvents having a boiling point of 100 to 260°C are contained, the total amount thereof is preferably within the above range.

From the standpoint of coatability, the solvent content is preferably an amount that results in a total solids concentration of the resin composition of the present invention of 5 to 80 mass%, more preferably an amount that results in a total solids concentration of 5 to 75 mass%, even more preferably an amount that results in a total solids concentration of 10 to 70 mass%, and even more preferably an amount that results in a total solids concentration of 20 to 70 mass%. The solvent content may be adjusted depending on the desired thickness of the coating film and the application method. When two or more solvents are used, the total amount is preferably within the above range.

<Metal adhesion improver>
The resin composition of the present invention preferably contains a metal adhesion improver from the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc. Examples of metal adhesion improvers include silane coupling agents having an alkoxysilyl group, 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, and amino compounds.

[Silane coupling agent]
Examples of silane coupling agents include the compounds described in paragraph 0316 of WO 2021/112189 and the compounds described in paragraphs 0067 to 0078 of JP 2018-173573 A, the contents of which are incorporated herein by reference. It is also preferable to use two or more different silane coupling agents, as described in paragraphs 0050 to 0058 of JP 2011-128358 A. It is also preferable to use the following compounds as the silane coupling agent. In the following formula, Me represents a methyl group, and Et represents an ethyl group. Furthermore, the following R represents a structure derived from a blocking agent in a blocked isocyanate group. The blocking agent may be selected depending on the desorption temperature, and examples include alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, and active methylene compounds. For example, caprolactam is preferred from the viewpoint of achieving a desorption temperature of 160 to 180°C. Commercially available products of such compounds include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).

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-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.
Furthermore, an oligomer type compound having a plurality of alkoxysilyl groups can also be used as the silane coupling agent.
Such oligomer-type compounds include compounds containing a repeating unit represented by the following formula (S-1).
In formula (S-1), R ^{1 S1} represents a monovalent organic group, R ^{1 S2} represents a hydrogen atom, a hydroxy group or an alkoxy group, and n represents an integer of 0 to 2.
R ^S1 preferably has a structure containing a polymerizable group. Examples of the polymerizable group include a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group), a (meth)acrylamide group, and a (meth)acryloyloxy group. A vinylphenyl group, a (meth)acrylamide group, or a (meth)acryloyloxy group is preferred, a vinylphenyl group or a (meth)acryloyloxy group is more preferred, and a (meth)acryloyloxy group is even more preferred.
R ^S2 is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group.
n represents an integer of 0 to 2, and is preferably 1.
Here, the structures of the repeating units represented by formula (S-1) contained in the oligomer-type compound may be the same.
Here, among the multiple repeating units represented by formula (S-1) contained in the oligomer-type compound, it is preferable that n is 1 or 2 in at least one, more preferably that n is 1 or 2 in at least two, and even more preferably that n is 1 in at least two.
As such oligomer type compounds, commercially available products can be used, and examples of commercially available products include KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

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

Other metal adhesion improvers that can be used include the compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP 2013-072935 A, the contents of which are incorporated herein by reference.

The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. By ensuring that the content is above the above lower limit, the adhesion between the pattern and the metal layer will be good, and by ensuring that the content is below 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 amount is within the above range.

<Migration inhibitor>
The resin composition of the present invention preferably further contains a migration inhibitor. By including the migration inhibitor, for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, migration of metal ions derived from the metal layer (or metal wiring) into the film can be effectively suppressed.

Migration inhibitors are not particularly limited, but include compounds having a heterocycle (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring), 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, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole are preferred.

Ion trapping agents that capture anions such as halogen ions can also be used as migration inhibitors.

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, the contents of which are incorporated herein by reference.

Specific examples of migration inhibitors include the following compounds:

Among these, the resin composition of the present invention preferably contains a compound having an azole structure (azole compound), and more preferably contains an azole compound and the above-mentioned silane coupling agent.

When the resin composition of the present invention 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%, relative to the total solids content of the resin composition.

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

<Light absorber>
The resin composition of the present invention also preferably contains a compound (light absorber) that reduces the absorbance of light at the exposure wavelength upon exposure.
Examples of the light absorber include the compounds described in paragraphs 0159 to 0183 of WO 2022/202647 and the compounds described in paragraphs 0088 to 0108 of JP 2019-206689 A. The contents of these compounds are incorporated herein by reference.

<Polymerization inhibitor>
The resin composition of the present invention preferably contains a polymerization inhibitor, such as a phenolic compound, a quinone compound, an amino compound, an N-oxyl free radical compound, a nitro compound, a nitroso compound, a heteroaromatic ring compound, or a metal compound.

Specific examples of polymerization inhibitor compounds include the compounds described in paragraph 0310 of WO 2021/112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenoxazine, and 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N-dioxide. The contents of this document are incorporated herein by reference.

When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20 mass%, more preferably 0.02 to 15 mass%, and even more preferably 0.05 to 10 mass%, based on the total solids content of the resin composition.

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

<Other additives>
The resin composition of the present invention may contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, UV absorbers, organic titanium compounds, antioxidants, photoacid generators, anti-aggregation agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliary agents (e.g., antifoaming agents, flame retardants, etc.), as needed, as long as the effects of the present invention are obtained. By appropriately incorporating these components, film properties and other properties can be adjusted. For details of these components, please refer to, for example, paragraphs 0183 and after of JP 2012-003225 A (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013/0034812), and paragraphs 0101-0104, 0107-0109 of JP 2008-250074 A, the contents of which are incorporated herein by reference. When these additives are incorporated, the total content is preferably 3% by mass or less of the solid content of the resin composition of the present invention.

[Surfactant]
As the surfactant, various surfactants can be used, such as a fluorine-based surfactant, a silicone-based surfactant, a hydrocarbon-based surfactant, etc. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

By including a surfactant in the resin composition of the present invention, the liquid properties (particularly fluidity) when the coating liquid composition is prepared are further improved, and the uniformity of the coating thickness and liquid saving can be further improved. In other words, when a film is formed using a coating liquid containing a surfactant, the interfacial tension between the surface to be coated and the coating liquid is reduced, improving the wettability of the surface to be coated and the coatability of the surface to be coated. This makes it possible to more effectively form a uniform film with minimal thickness unevenness.

Examples of fluorosurfactants include compounds described in paragraph 0328 of WO 2021/112189, the contents of which are incorporated herein by reference.
As the fluorine-based surfactant, a fluorine-containing polymer compound containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups or propyleneoxy groups) can also be preferably used, and examples thereof include the following compounds.

The weight average molecular weight of the compound is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000.
The fluorosurfactant may also 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 2010-164965 A, the contents of which are incorporated herein by reference. Commercially available products include 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. Fluorosurfactants 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, hydrocarbon surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants include the compounds described in paragraphs 0329 to 0334 of WO 2021/112189, the contents of which are incorporated herein by reference.

The surfactant may be used alone or in combination of two or more.
The content of the surfactant is preferably from 0.001 to 2.0% by mass, more preferably from 0.005 to 1.0% by mass, based on the total solid content of the composition.

[Inorganic particles]
Specific examples of inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.

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.
The above-mentioned average particle size of the inorganic particles is the primary particle size and also the volume average particle size, which can be measured by a dynamic light scattering method using, for example, a Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.).
When the above measurement is difficult, the measurement can also be performed by a centrifugal sedimentation light transmission method, an X-ray transmission method, or a laser diffraction/scattering method.

Other additives include the compounds described in paragraphs 0249-0282 and 0316-0358 of WO 2022/145355. The above descriptions are incorporated herein by reference.

<Characteristics of Resin Composition>
The viscosity of the resin composition of the present invention can be adjusted by the solids concentration of the resin composition. From the viewpoint of coating film thickness, it is preferably 1,000 mm ² /s to 12,000 ^{mm 2} /s, more preferably 2,000 mm ² /s to 10,000 ^{mm 2} /s, and even more preferably 2,500 mm ² /s to 8,000 ^{mm 2} /s. Within the above range, it is easy to obtain a highly uniform coating film. If it is 1,000 ^{mm 2} /s or more, it is easy to apply the film to a thickness required for, for example, an insulating film for rewiring, and if it is 12,000 mm ² /s or less, a coating film with excellent coating surface condition can be obtained.

When a cured product having a film thickness of 10 μm is formed using the resin composition of the present invention, the transmittance of the cured product at a wavelength of 365 nm is preferably 15% or more, more preferably 20% or more, and even more preferably 25% or more.
The upper limit of the transmittance is not particularly limited and may be 100%.
The cured product can be obtained, for example, by applying the resin composition of the present invention to a silicon wafer, drying it at 100°C for 5 minutes, exposing the entire surface to i-rays at an exposure energy of 500 mJ/ ^cm2 , and then heating it at a temperature increase rate of 10°C/min in a nitrogen atmosphere and at 230°C for 180 minutes.

<Restrictions on substances contained in resin composition>
The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If the water content is less than 2.0%, the storage stability of the resin composition is improved.
Methods for maintaining the moisture content include adjusting the humidity during storage and reducing the porosity of the container during storage.

From the viewpoint of insulating properties, the metal content of the 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, copper, chromium, and nickel, but this does not include metals contained as complexes of organic compounds with metals. When multiple metals are contained, it is preferable that the total amount of these metals is within the above range.

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

Considering the use of the resin composition of the present invention as a semiconductor material, the content of halogen atoms is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass from the viewpoint of wiring corrosion. Among them, those present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. 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.

Any conventional container known in the art can be used as a container for storing the resin composition of the present invention. For the purpose of preventing impurities from being mixed into the raw materials or the resin composition of the present invention, it is also preferable to use a multi-layer bottle whose inner wall is made up of six layers of six types of resin, or a bottle with a seven-layer structure made up of six types of resin. Examples of such containers include the container described in JP 2015-123351 A.

<Cured product of resin composition>
By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.
The cured product of the present invention is a cured product obtained by curing a resin composition.
The resin composition is preferably cured by heating, with the heating temperature being more preferably 120°C to 400°C, even more preferably 140°C to 380°C, and particularly preferably 170°C to 350°C. The form of the cured product of the resin composition is not particularly limited, and can be selected according to the application, such as film, rod, sphere, or pellet. In the present invention, the cured product is preferably in the form of a film. By patterning the resin composition, the shape of the cured product can be selected according to the application, such as forming a protective film on the wall surface, forming via holes for electrical conduction, adjusting impedance, capacitance, or internal stress, or imparting heat dissipation functionality. The film thickness of the cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less.
The shrinkage percentage of the resin composition of the present invention when cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage percentage refers to the percentage of volume change before and after curing of the resin composition, and can be calculated using the following formula.
Shrinkage rate [%] = 100 - (volume after curing / volume before curing) x 100

<Characteristics of the cured product of the resin composition>
The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, the cured product may have excellent mechanical properties.
The elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.
The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and even more preferably 230°C or higher.

<Preparation of Resin Composition>
The 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 carried out by a conventionally known method.
Examples of the mixing method include mixing with a stirring blade, mixing with a ball mill, and mixing by rotating a tank.
The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.

Filtration using a filter is preferably performed to remove foreign matter such as dust and fine particles from the resin composition of the present invention. The filter pore size is, for example, preferably 5 μm or less, more preferably 1 μm or less, even more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. When the filter material is polyethylene, HDPE (high-density polyethylene) is more preferable. The filter may be pre-washed with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or parallel. When multiple types of filters are used, filters with different pore sizes or materials may be combined. An example of a connection mode is a mode in which an HDPE filter with a pore size of 1 μm is connected in series as the first stage and an HDPE filter with a pore size of 0.2 μm is connected in series as the second stage. Various materials may also be filtered multiple times. When filtration is performed multiple times, circulating filtration may be used. Filtration may also be performed under pressure. When filtration is performed under pressure, the pressure to be applied is, for example, preferably 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, even more preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less.
In addition to filtration using a filter, impurities may be removed using an adsorbent. Filter filtration and impurity removal using an adsorbent may be combined. Known adsorbents can be used as the adsorbent. Examples of the adsorbent include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
After filtration using a filter, the resin composition filled in the bottle may be subjected to a degassing step by placing it under reduced pressure.

(Method for producing cured product)
The method for producing a cured product of the present invention preferably includes a film-forming step of applying the resin composition onto a substrate to form a film.
The method for producing a cured product more preferably includes the above-mentioned film formation step, an exposure step of selectively exposing the film formed in the film formation step, and a development step of developing the film exposed in the exposure step with a developer to form a pattern.
It is particularly preferable that the method for producing a cured product includes the above-mentioned film-forming step, the above-mentioned exposure step, the above-mentioned development step, and at least one of a heating step of heating the pattern obtained in the development step and a post-development exposure step of exposing the pattern obtained in the development step.
The method for producing a cured product preferably includes the film-forming step and the step of heating the film.
Each step will be described in detail below.

<Film formation process>
The resin composition of the present invention can be used in a film-forming process in which the resin composition is applied to a substrate to form a film.
The method for producing a cured product of the present invention preferably includes a film-forming step of applying the resin composition onto a substrate to form a film.

[Base material]
The type of substrate can be appropriately determined depending on the application and is not particularly limited. Examples of substrates include semiconductor production 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 (for example, substrates formed from metals, and substrates on which a metal layer is formed by plating, vapor deposition, etc.), paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, mold substrates, and electrode plates for plasma display panels (PDPs). The substrate is particularly preferably a semiconductor production substrate, and more preferably a silicon substrate, a Cu substrate, or a mold substrate.
These substrates may have a layer such as an adhesion layer made of hexamethyldisilazane (HMDS) or an oxide layer provided on the surface.
The shape of the substrate is not particularly limited, and may be circular or rectangular.
The size of the substrate is preferably, for example, a diameter of 100 to 450 mm, more preferably 200 to 450 mm, if it is circular, and preferably, a short side length of 100 to 1000 mm, more preferably 200 to 700 mm, if it is rectangular.
As the substrate, for example, a plate-shaped substrate, preferably a panel-shaped substrate (substrate) is used.

When a film is formed by applying a resin composition to the surface of a resin layer (e.g., a layer made of a cured product) or the surface of a metal layer, the resin layer or metal layer serves as the substrate.

The resin composition is preferably applied to a substrate by coating.
Specific examples of the application method include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating, or inkjet coating is preferred, and from the viewpoint of uniformity of film thickness and productivity, spin coating and slit coating are more preferred. By adjusting the solid content concentration of the resin composition and coating conditions depending on the application method, a film of the desired thickness can be obtained. In addition, the application method can be appropriately selected depending on the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, inkjet coating, etc. are preferred, and for rectangular substrates, slit coating, spray coating, inkjet coating, etc. are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes.
Alternatively, a coating film formed by applying the coating to a temporary support in advance using the above-mentioned application method may be transferred onto the substrate.
As for the transfer method, the production 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 addition, a process for removing excess film from the edge of the substrate may be performed, such as edge bead rinsing (EBR) or back rinsing.
Before applying the resin composition to the substrate, a pre-wetting step may be employed in which the substrate is coated with various solvents to improve the wettability of the substrate, and then the resin composition is applied.

<Drying process>
After the film-forming step (layer-forming step), the film may be subjected to a step (drying step) of drying the formed film (layer) to remove the solvent.
That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film forming step.
The drying step is preferably carried out after the film-forming step and before the exposure step.
The drying temperature of the film in the drying step is preferably 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. Drying may also be performed under reduced pressure. The drying time is, for example, 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.

<Exposure process>
The film may be subjected to an exposure step to selectively expose the film to light.
The method for producing a cured product may include an exposure step of selectively exposing the film formed in the film formation step to light.
Selective exposure means that only a portion of the film is exposed, and selective exposure results in exposed and unexposed areas of the film.
The exposure dose is not particularly limited as long as it can cure the resin composition of the present invention, but is preferably 50 to 10,000 mJ/cm ² and more preferably 200 to 8,000 mJ/cm ² in terms of exposure energy at a wavelength of 365 nm.

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

In terms of the exposure wavelength, in relation to the light source, (1) semiconductor laser (wavelengths 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 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, 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, etc. For the resin composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferred, and exposure with i-line is more preferred from the viewpoint of exposure sensitivity.
The exposure method is not particularly limited as long as it is a method that exposes at least a part of the film made of the resin composition of the present invention, and examples thereof include exposure using a photomask and exposure by laser direct imaging.

<Post-exposure baking step>
The film may be subjected to a step of heating after exposure (post-exposure baking step).
That is, the method for producing a cured product of the present invention may include a post-exposure baking step in which the film exposed in the exposure step is heated.
The post-exposure baking step can be carried out after the exposure step and before the development step.
The heating temperature in the post-exposure baking step is preferably 50°C to 140°C, more preferably 60°C to 120°C.
The heating time in the post-exposure baking step is preferably from 30 seconds to 300 minutes, more preferably from 1 minute to 10 minutes.
The temperature rise rate in the post-exposure heating step from the starting temperature to the maximum heating temperature is preferably 1 to 12° C./min, more preferably 2 to 10° C./min, and even more preferably 3 to 10° C./min.
The temperature rise rate may be changed during heating as needed.
The heating means in the post-exposure baking step is not particularly limited, and known means such as a hot plate, an oven, and an infrared heater can be used.
It is also preferable that the heating be carried out in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.

<Developing process>
After exposure, the film may be subjected to a development step in which it is developed with a developer to form a pattern.
That is, the method for producing a cured product of the present invention may include a development step in which the film exposed in the exposure step is developed with a developer to form a pattern.
Development removes either the exposed or unexposed portions of the film, forming a pattern.
Here, development in which the non-exposed portions of the film are removed by the development process is called negative development, and development in which the exposed portions of the film are removed by the development process is called positive development.

[Developer]
The developer used in the development step may be an aqueous alkaline solution or a developer containing an organic solvent.

When the developer is an alkaline aqueous solution, basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts, of which TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine are preferred, with TMAH being more preferred. 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.

When the developer contains an organic solvent, the compounds described in paragraph 0387 of WO 2021/112189 can be used as the organic solvent. The contents of this document are incorporated herein by reference. Suitable alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutylcarbinol, and triethylene glycol, and suitable amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

When the developer contains an organic solvent, the organic solvent can be used alone or in combination of two or more. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide is more preferred, and a developer containing cyclopentanone is particularly preferred.

When the developer contains an organic solvent, the content of the organic solvent relative to the total weight of the developer is preferably 50% by weight or more, more preferably 70% by weight or more, even more preferably 80% by weight or more, and particularly preferably 90% by weight or more. The above content may also be 100% by weight.

When the developer contains an organic solvent, the developer may further contain at least one of a basic compound and a base generator. When at least one of the basic compound and the base generator in the developer penetrates into the pattern, the performance of the pattern, such as breaking elongation, may be improved.

As the basic compound, an organic base is preferred from the viewpoint of reliability when it remains in the film after curing (adhesion to the substrate when the cured product is further heated).
The basic compound is preferably a basic compound having an amino group, and is preferably a primary amine, a secondary amine, a tertiary amine, an ammonium salt, or a tertiary amide. In order to promote the imidization reaction, a primary amine, a secondary amine, a tertiary amine, or an ammonium salt is preferred, a secondary amine, a tertiary amine, or an ammonium salt is more preferred, a secondary amine or a tertiary amine is even more preferred, and a tertiary amine is particularly preferred.
From the viewpoint of the mechanical properties (elongation at break) of the cured product, it is preferable that the basic compound is one that is unlikely to remain in the cured film (the obtained cured product), and from the viewpoint of promoting cyclization, it is preferable that the amount of the basic compound that remains is unlikely to decrease due to vaporization or the like before heating.
Therefore, the boiling point of the basic compound is preferably 30°C to 350°C, more preferably 80°C to 270°C, and even more preferably 100°C to 230°C at normal pressure (101,325 Pa).
The boiling point of the basic compound is preferably higher than the temperature obtained by subtracting 20° C. from the boiling point of the organic solvent contained in the developer, and more preferably higher than the boiling point of the organic solvent contained in the developer.
For example, when the boiling point of the organic solvent is 100°C, the basic compound used preferably has a boiling point of 80°C or higher, more preferably 100°C or higher.
The developer may contain only one kind of basic compound or two or more kinds of basic compounds.

Specific examples of basic compounds include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, butanediamine, 1,5-diamino Examples include pentane, N-methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, dimethylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, N,N,N,N-tetramethylethylenediamine, and N,N,N,N-tetramethyl-1,3-propanediamine.

Preferred embodiments of the base generator are the same as those of the base generator contained in the composition described above. In particular, it is preferable that the base generator be a thermal base generator.

When the developer contains at least one of a basic compound and a base generator, the content of the basic compound or the base generator is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the developer. The lower limit of the content is not particularly limited, but is preferably, for example, 0.1% by mass or more.
When the basic compound or base generator is solid in the environment in which the developer is used, the content of the basic compound or base generator is preferably 70 to 100 mass % based on the total solid content of the developer.
The developer may contain only one kind of at least one of a basic compound and a base generator, or may contain two or more kinds. When two or more kinds of at least one of a basic compound and a base generator are used, the total amount thereof is preferably within the above range.

The developer may further contain other components.
Examples of other components include known surfactants and known defoaming agents.

[Method of Supplying Developer]
The method of supplying the developer is not particularly limited as long as it can form a desired pattern, and includes a method of immersing a substrate on which a film has been formed in the developer, puddle development in which the developer is supplied to a film formed on a substrate using a nozzle, 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 employed 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, and this process may be repeated multiple times.
Methods for supplying the developer in the development step 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 on the substrate by ultrasonic waves or the like, and a step in which these are combined.

The development time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the developer during development is not particularly specified, but is preferably 10 to 45°C, and more preferably 18 to 30°C.

In the development process, after treatment with the developer, the pattern may be further washed (rinsed) with a rinse solution. Alternatively, a rinse solution may be supplied before the developer in contact with the pattern has completely dried.

[Rinse solution]
When the developer is an alkaline aqueous solution, for example, water can be used as the rinse liquid. When the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (for example, water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinse liquid.

When the rinse liquid contains an organic solvent, examples of the organic solvent include the same organic solvents as those exemplified when the developer contains an organic solvent.
The organic solvent contained in the rinse liquid is preferably different from the organic solvent contained in the developer, and more preferably an organic solvent that has a lower solubility for the pattern than the organic solvent contained in the developer.

When the rinse solution contains an organic solvent, the organic solvent can be used alone or in combination of two or more. Preferred organic solvents are cyclopentanone, gamma-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME, with cyclopentanone, gamma-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME being more preferred, and cyclohexanone and PGMEA being even more preferred.

When the rinse solution contains an organic solvent, the organic solvent preferably accounts for 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, of the total mass of the rinse solution. Alternatively, the organic solvent may account for 100% by mass of the total mass of the rinse solution.

The rinse liquid may contain at least one of a basic compound and a base generator.
Although not particularly limited, when the developer contains an organic solvent, one preferred embodiment of the present invention is one in which the rinse liquid contains an organic solvent and at least one of a basic compound and a base generator.
Examples of the basic compound and base generator contained in the rinse solution include the compounds exemplified as the basic compound and base generator that may be contained in the above-mentioned developer containing an organic solvent, and preferred embodiments are also the same.
The basic compound and base generator contained in the rinse solution may be selected in consideration of the solubility in the solvent in the rinse solution.

When the rinse solution contains at least one of a basic compound and a base generator, the content of the basic compound or the base generator is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the rinse solution. The lower limit of the content is not particularly limited, but is preferably, for example, 0.1% by mass or more.
When the basic compound or base generator is solid in the environment in which the rinse solution is used, the content of the basic compound or base generator is also preferably 70 to 100 mass % based on the total solid content of the rinse solution.
When the rinse solution contains at least one of a basic compound and a base generator, the rinse solution may contain only one kind of at least one of a basic compound and a base generator, or may contain two or more kinds. When there are two or more kinds of at least one of a basic compound and a base generator, the total amount thereof is preferably within the above range.

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

[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 thereof include a method of immersing the substrate in the rinse liquid, a method of supplying the rinse liquid to the substrate by puddling, a method of supplying the rinse liquid to the substrate by showering, and a method of continuously supplying the rinse liquid onto the substrate by means of a straight nozzle or the like.
From the viewpoints of the permeability of the rinse liquid, the removability of non-image areas, and production efficiency, the rinse liquid can 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, and 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.
The method of supplying the rinse liquid in the rinsing step may include a step of continuously supplying the rinse liquid to the substrate, a step of keeping the rinse liquid substantially stationary on the substrate, a step of vibrating the rinse liquid on the substrate by ultrasonic waves or the like, and a combination of these steps.

The rinsing time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the rinse solution during rinsing is not particularly specified, but is preferably 10 to 45°C, and more preferably 18 to 30°C.

The development process may include a step of contacting the pattern with a processing liquid after treatment with a developer or after washing the pattern with a rinse liquid. It may also be possible to employ a method in which the processing liquid is supplied before the developer or rinse liquid in contact with the pattern has completely dried.

The treatment liquid may include a treatment liquid containing at least one of water and an organic solvent, and at least one of a basic compound and a base generator.
Preferred aspects of the organic solvent, and at least one of the basic compound and the base generator are the same as the preferred aspects of the organic solvent, and at least one of the basic compound and the base generator used in the rinse liquid described above.
The method of supplying the processing liquid to the pattern can be the same as the method of supplying the rinse liquid described above, and the preferred embodiments are also the same.

The content of the basic compound or base generator in the treatment liquid is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the treatment liquid. The lower limit of the content is not particularly limited, but is preferably, for example, 0.1% by mass or more.
Furthermore, when the basic compound or base generator is solid in the environment in which the treatment liquid is used, the content of the basic compound or base generator is preferably 70 to 100 mass % relative to the total solid content of the treatment liquid.
When the treatment liquid contains at least one of a basic compound and a base generator, the treatment liquid may contain only one kind of at least one of a basic compound and a base generator, or may contain two or more kinds. When there are two or more kinds of at least one of a basic compound and a base generator, it is preferable that the total amount thereof is in the above range.

<Heating process>
The pattern obtained by the development step (if a rinsing step is performed, the pattern after rinsing) may be subjected to a heating step in which the pattern obtained by the development step is heated.
That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained in the development step.
The method for producing a cured product of the present invention may also include a heating step of heating a pattern obtained by another method without performing a development step, or a film obtained in the film-forming step.
In the heating step, the resin such as the polyimide precursor is cyclized to form a resin such as a polyimide.
Furthermore, crosslinking of unreacted crosslinkable groups in the specific resin or in the crosslinking agent other than the specific resin also proceeds.
The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, even more preferably 150 to 250°C, still more preferably 160 to 250°C, and particularly preferably 160 to 230°C.

The heating step is preferably a step in which the cyclization reaction of the polyimide precursor is promoted within the pattern by the action of the base generated from the base generator due to heating.

The heating step is preferably carried out at a temperature increase rate of 1 to 12°C/min from the temperature at the start of heating to the maximum heating temperature. The temperature increase rate is more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min. By setting the temperature increase rate to 1°C/min or more, it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity, and by setting the temperature increase rate to 12°C/min or less, it is possible to alleviate residual stress in the cured product.
Additionally, in the case of a rapid heating oven, the heating rate from the initial temperature to the maximum heating temperature is preferably 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 up to the maximum heating temperature begins. For example, when the resin composition of the present invention is applied to a substrate and then dried, this is the temperature of the film (layer) after drying. For example, it is preferable to raise 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 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

In particular, when forming a multilayer laminate, from the viewpoint of adhesion between layers, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, and particularly preferably 120°C or higher.
The upper limit of the heating temperature is preferably 350°C or less, more preferably 250°C or less, and even more preferably 240°C or less.

Heating may be performed in stages. For example, the temperature may be increased from 25°C to 120°C at a rate of 3°C/min, held at 120°C for 60 minutes, increased from 120°C to 180°C at a rate of 2°C/min, and held at 180°C for 120 minutes. It is also preferable to treat the film while irradiating it with ultraviolet light, as described in U.S. Pat. No. 9,159,547. Such a pretreatment step can improve the film properties. The pretreatment step may be performed for a short period of time, preferably from 10 seconds to 2 hours, more preferably from 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps. For example, a first pretreatment step may be performed in the range of 100 to 150°C, followed by a second pretreatment step in the range of 150 to 200°C.
Furthermore, after heating, the material may be cooled, and in this case, the cooling rate is preferably 1 to 5° C./min.

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

<Post-development exposure step>
The pattern obtained by the development step (if a rinsing step is performed, the pattern after rinsing) may be subjected to a post-development exposure step in which the pattern after the development step is exposed to light, instead of or in addition to the heating step.
That is, the method for producing a cured product of the present invention may include a post-development exposure step of exposing the pattern obtained by the development step. The method for producing a cured product of the present invention may include both a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step.
In the post-development exposure step, for example, a reaction in which cyclization of a polyimide precursor or the like progresses due to exposure of a photobase generator to light, or a reaction in which elimination of an acid-decomposable group progresses due to exposure of a photoacid generator to light, can be promoted.
In the post-development exposure step, it is sufficient that at least a part of the pattern obtained in the development step is exposed, but it is preferable that the entire pattern is exposed.
The exposure dose in the post-development exposure step is preferably 50 to 20,000 mJ/cm ² , more preferably 100 to 15,000 mJ/cm ² , in terms of exposure energy at a wavelength to which the photosensitive compound has sensitivity.
The post-development exposure step can be carried out using, for example, the light source used in the exposure step described above, and it is preferable to use broadband light.

<Metal layer formation process>
The pattern obtained by the development step (which is preferably subjected to at least one of the heating step and the post-development exposure step) may be subjected to a metal layer forming step in which a metal layer is formed on the pattern.
That is, the method for producing a cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on the pattern obtained by the development step (preferably the pattern has been subjected to at least one of a heating step and a post-development exposure step).

The metal layer is not particularly limited and any existing metal species can be used, including copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum 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, JP 2004-101850 A, U.S. Pat. No. 7,888,181, and U.S. Pat. No. 9,177,926 can be used. Examples of suitable methods include photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and combinations of these. More specific examples include patterning methods that combine sputtering, photolithography, and etching, and patterning methods that combine photolithography and electroplating. Preferred plating methods include electroplating using copper sulfate or copper cyanide plating solutions.

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

<Application>
Examples of fields to which the cured product manufacturing method of the present invention or the cured product can be applied include insulating films for electronic devices, interlayer insulating films for rewiring layers, stress buffer films, etc. Other examples include etching patterns for sealing films, substrate materials (base films, coverlays, and interlayer insulating films for flexible printed circuit boards), and insulating films for packaging applications such as those described above. For these applications, see, for example, Science & Technology Co., Ltd.'s "High Performance Polyimide and Application Technology," April 2008, edited by Masaaki Kakimoto, CMC Technical Library's "Fundamentals and Development of Polyimide Materials," published November 2011, and Japan Polyimide and Aromatic Polymer Research Association's "Latest Polyimide Fundamentals and Applications," NTS, August 2010.

The method for producing the cured product of the present invention, or the cured product of the present invention, can also be used to produce printing plates such as offset printing plates or screen printing plates, to etch molded parts, and to produce protective lacquers and dielectric layers in electronics, particularly microelectronics.

(Laminate and method for manufacturing laminate)
The laminate of the present invention refers to a structure having a plurality of layers each made of the cured product of the present invention.
The laminate is a laminate including two or more layers made of a cured product, and may be a laminate including three or more layers.
Of the two or more layers made of the cured product contained in the laminate, at least one is a layer made of the cured product of the present invention, and from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product associated with the shrinkage, it is also preferable that all of the layers made of the cured product contained in the laminate are layers made of the cured product of the present invention.

In other words, the method for producing a laminate of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes repeating the method for producing a cured product of the present invention multiple times.

The laminate of the present invention preferably includes two or more layers made of a cured product, and a metal layer between any two of the layers made of the cured product. The metal layer is preferably formed by the metal layer-forming step.
That is, the method for producing a laminate of the present invention preferably further includes a metal layer-forming step of forming a metal layer on the layer made of the cured product, between the steps for producing a cured product that are performed multiple times. Preferred aspects of the metal layer-forming step are as described above.
As the laminate, for example, a laminate including at least a layer structure in which three layers, a layer made of a first cured product, a metal layer, and a layer made of a second cured product, are laminated in this order, can be mentioned as a preferred example.
It is preferable that the layer made of the first cured product and the layer made of the second cured product are both layers made of the cured product of the present invention. The resin composition of the present invention used to form the layer made of the first cured product and the resin composition of the present invention used to form the layer made of the second cured product 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.

<Lamination process>
The method for producing the laminate of the present invention preferably 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) at least one of a heating process and a post-development exposure process, which are carried out again on the surface of the pattern (resin layer) or metal layer in this order. However, at least one of the (a) film formation process and the (d) heating process and the post-development exposure process may be repeated. Furthermore, after at least one of the (d) heating process and the post-development exposure process, the (e) metal layer formation process may be included. It goes without saying that the lamination process may further include the above-mentioned drying 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 exposure step, the heating step, or the metal layer formation step. An example of a surface activation treatment is plasma treatment. Details of the surface activation treatment will be described later.

The lamination step is preferably carried out 2 to 20 times, more preferably 2 to 9 times.
For example, a structure of 2 to 20 resin layers, such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, is preferred, and a structure of 2 to 9 resin layers is more preferred.
The above layers may be the same or different in composition, shape, film thickness, etc.

In a particularly preferred embodiment of the present invention, after providing a metal layer, a cured product (resin layer) of the resin composition of the present invention is further formed to cover the metal layer. Specific examples include an embodiment in which the following steps are repeated in this order: (a) film formation step, (b) exposure step, (c) development step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step; or an embodiment in which the following steps are repeated in this order: (a) film formation step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step. By alternately performing the lamination step of laminating layers of the resin composition of the present invention (resin layers) and the metal layer formation step, it is possible to alternately laminate layers of the resin composition of the present invention (resin layers) and metal layers.

(Surface activation treatment step)
The method for producing a laminate of the present invention preferably includes a surface activation treatment step of subjecting at least a portion of the metal layer and the resin composition layer to a surface activation treatment.
The surface activation treatment step is usually performed after the metal layer formation step, but the resin composition layer may be subjected to the surface activation treatment step after the above-mentioned development step (preferably after at least one of the heating step and the post-development exposure step) and then the metal layer formation step may be performed.
The surface activation treatment may be performed on at least a portion of the metal layer, or on at least a portion of the resin composition layer after exposure, or on at least a portion of both the metal layer and the resin composition layer after exposure. The surface activation treatment is preferably performed on at least a portion of the metal layer, and it is preferable to perform the surface activation treatment on part or all of the region of the metal layer on which the resin composition layer is formed on the surface. In this way, by performing the surface activation treatment on the surface of the metal layer, it is possible to improve the adhesion with the resin composition layer (film) provided on the surface.
The surface activation treatment is preferably performed on a part or all of the resin composition layer (resin layer) after exposure. By performing the surface activation treatment on the surface of the resin composition layer in this way, it is possible to improve the adhesion with a metal layer or a resin layer provided on the surface that has been surface-activated. In particular, when negative development is performed, for example, if the resin composition layer is cured, it is less susceptible to damage due to the surface treatment, and adhesion is likely to be improved.
The surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of WO 2021/112189, the contents of which are incorporated herein by reference.

(Semiconductor device and its manufacturing method)
The present invention also discloses a semiconductor device comprising the cured product or laminate of the present invention.
The present invention also discloses a method for producing a semiconductor device, which includes the method for producing the cured product of the present invention or the method for producing the laminate.
As specific examples of semiconductor devices using the resin composition of the present invention for forming an interlayer insulating film for a rewiring layer, the descriptions in paragraphs 0213 to 0218 and FIG. 1 of JP-A-2016-027357 can be referred to, and the contents of these can be incorporated into this specification.

(resin)
The resin of the present invention has a repeating unit represented by formula (1-1) and a group represented by formula (B-1).
In formula (1-1), ^X1 represents an organic group having 4 or more carbon atoms, ^Y1 represents an organic group having 4 or more carbon atoms, ^R1 each independently represents a structure represented by formula (R-1) below, m represents an integer of 0 to 4, n represents an integer of 0 or more, and n+m is an integer of 1 or more.
In formula (R-1), L ¹ represents a linking group having a valence of a1+1, A ¹ represents a polymerizable group, a1 represents an integer of 1 or more, and * represents a bonding site with X ¹ or Y ¹ in formula (1-1).
In formula (B-1), R ¹ represents a divalent linking group, Z ¹ represents a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms or a silicon atom, when Z ¹ is the alkylene group, n is 1, and R ² represents a hydrogen atom or a monovalent organic group, when Z ¹ is the silicon atom, n is 3, and each R ² independently represents a monovalent organic group, and * represents a bonding site to another structure.

Preferred embodiments of formula (1-1) and formula (B-1) in the resin of the present invention are the same as the preferred embodiments of these formulas in the specific resin in the resin composition of the present invention described above.
Other preferred aspects of the resin of the present invention are the same as the preferred aspects of the specific resin described above.

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

<Synthesis Example>
[Synthesis of 3-chloropropyl methacrylate]
In a flask, 25.00 g (264 mmol) of 3-chloropropanol, 25.1 g (316.8 mmol) of pyridine, and 150 g of tetrahydrofuran were dissolved and cooled to −10° C. to 0° C. Subsequently, 29.03 g (277.2 mmol) of methacrylic acid chloride was added dropwise using a dropping funnel over 30 minutes, and the mixture was heated to 20° C. to 25° C. and stirred for 3 hours.
Subsequently, the reaction solution was transferred to a 2 L separatory funnel and diluted with 1 L of ethyl acetate. After that, the reaction solution was washed twice with 500 mL of water, twice with 300 mL of 0.5 N (mol/L) aqueous hydrochloric acid, twice with 500 mL of saturated aqueous sodium bicarbonate, and 500 mL of saturated saline, and then dried over magnesium sulfate. After that, 0.02 g of p-methoxyphenol was added, and the solvent was removed using an evaporator to obtain 40 g of 3-chloropropyl methacrylate.

[Synthesis of AA-1a]
48.65 g (225 mmol) of 3,3'-dihydroxybenzidine and 375 mL of dimethylformamide were mixed in a 1 L flask. Under ice cooling, 98.21 g (450 mmol) of di-t-butyl dicarbonate was added dropwise. After the completion of the dropwise addition, the mixture was stirred at 60°C for 5 hours. After the reaction was completed and the mixture was cooled to room temperature, 35 mg of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 68.68 g (450 mmol) of p-chloromethylstyrene, 74.63 g (540 mmol) of potassium carbonate, and 8.96 g (54.0 mmol) of potassium iodide were added, and the mixture was stirred at 60°C for 3 hours. After the reaction was completed, the mixture was filtered by suction filtration, and the filtrate was added dropwise to 500 mL of water. White crystals precipitated, and the precipitated solid was recovered by suction filtration. The obtained white solid was purified by recrystallization using 1,000 mL of acetone at 60°C. 125 g (yield 85.6%) of the following intermediate AA-1a was obtained.
The structure of AA-1a is shown below: The structure was confirmed to be as shown below by ¹ H-NMR spectrum.

[Synthesis of AA-2a to AA-4a]
AA-2a was synthesized in the same manner as AA-1a, except that 3,3'-dihydroxybenzidine was replaced with 2,2-bis(3-amino-4-hydroxyphenyl)propane.
AA-3a was synthesized in the same manner as AA-1a, except that chloromethylstyrene was changed to 10-chloro-3-decyne.
AA-4a was synthesized in the same manner as AA-1a, except that chloromethylstyrene was replaced with the 3-chloropropyl methacrylate synthesized above.
The structures of AA-2a to AA-4a are shown below: The structures were confirmed to be as shown below by ¹ H-NMR spectrum.

[Synthesis of AA-1]
75.0 g (115.6 mmol) of (AA-1a) and 500 mL of methylene chloride were mixed in a 1 L flask. 131.8 g (1156 mmol) of trifluoroacetic acid was added at room temperature, and then the mixture was stirred at 40°C for 5 hours. After the reaction was completed, 250 mL of methanol was added dropwise under ice cooling, followed by 117.0 g (1156 mmol) of triethylamine. Pale yellow crystals were precipitated, and the precipitated solid was recovered by suction filtration. The mixture was suspended and washed in 750 mL of methanol, yielding 40.5 g (73% yield) of (AA-1). The structure of AA-1 is shown below. The structure was confirmed to be as shown below by ¹ H-NMR spectrum.

[Synthesis of AA-2 to AA-4]
AA-2 to AA-4 were synthesized in the same manner as for AA-1, except that one of AA-2a to AA-4a was used instead of AA-1a.

[Synthesis Example SP-1: Synthesis of Polyimide (SP-1)]
30.0 g (57.64 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride and 0.08 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical were dissolved in 120 g of N-methylpyrrolidone (NMP) to obtain a solution. Subsequently, 9.34 g (25.36 mmol) of 4,4'-bis(3-aminophenoxy)biphenyl and 11.38 g (25.36 mmol) of AA-1 were dissolved in 100 g of NMP and added dropwise to the solution over 1 hour at a temperature of 10 to 25°C. After stirring at 25°C for 2 hours, 1.49 g (12.68 mmol) of 4-aminophenylacetylene was added and the mixture was further stirred at 25°C for 2 hours. Subsequently, 18.2 g of pyridine and 14.7 g of acetic anhydride were added, and the mixture was reacted at 80°C for 4 hours. After completion of the reaction, the mixture was cooled to 25°C and diluted with 200 g of tetrahydrofuran. Subsequently, the reaction solution was added dropwise to a mixture of 2.0 L of methanol and 0.5 L of water, stirred for 15 minutes, and then the polyimide resin was filtered. Next, the resin was reslurried in 1 L of water, filtered, and then reslurried again in 1 L of methanol, filtered, and dried under reduced pressure at 40°C for 10 hours. Subsequently, the dried resin was dissolved in 250 g of tetrahydrofuran, 40 g of ion exchange resin (MB-1: manufactured by Organo Corporation) was added, and the mixture was stirred for 4 hours. The ion exchange resin was removed by filtration, and then the polyimide resin was precipitated in 2 L of methanol and stirred for 15 minutes. The polyimide resin was collected by filtration and dried under reduced pressure at 45°C for 1 day to obtain polyimide resin (SP-1).
The resulting polyimide (SP-1) had a weight-average molecular weight of 20,100 and a number-average molecular weight of 8,000. Polyimide (SP-1) is a resin having a repeating unit represented by the following formula (SP-1). The structure of the repeating unit was determined from ¹ H-NMR spectrum. In the following structure, the subscripts of the repeating units represent the molar ratio of each repeating unit.

[Synthesis Examples SP-2 to SP-5, SP-9 to SP-11: Synthesis of Polyimides (SP-2 to SP-5, SP-9 to SP-11)]
SP-2 to SP-5 and SP-9 to SP-11 were synthesized in the same manner as SP-1, except that the raw material diamine, amine, and acid anhydride were changed. The weight average molecular weight and number average molecular weight are shown in the table below. Each polyimide is a resin having a repeating unit represented by the following formula. The structure of the repeating unit was determined from ¹ H-NMR spectrum. In the following structures, the subscripts of the repeating units indicate the molar ratio of each repeating unit.

[Synthesis Example SP-6: Synthesis of Polyimide (SP-6)]
30.0 g (57.64 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride was dissolved in 130 g of N-methylpyrrolidone (NMP). Subsequently, 5.61 g (25.94 mmol) of HAB (manufactured by Wakayama Seika Kogyo Co., Ltd.), 5.51 g (25.94 mmol) of m-tolidine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 2.21 g (11.53 mmol) of heptylaniline were added while washing with 50 g of NMP. The mixture was stirred at a temperature ranging from 20 to 50°C for 30 minutes, after which 10 g of toluene was added. The mixture was reacted at 200°C for 4 hours under a nitrogen flow and then cooled to 25°C.
Subsequently, 2.36 g (16.34 mmol) of 1-chloro-2-octane, 19.92 g (144 mmol) of potassium carbonate, and 2.39 g (14 mmol) of potassium iodide were added, and the mixture was reacted at 110 ° C. for 15 hours. Then, 15.3 g (100 mmol) of 4-(chloromethyl)styrene and 0.1 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical were added, and the mixture was reacted at 95 ° C. for an additional 15 hours. Subsequently, the reaction solution was cooled to 25 ° C., diluted with 200 g of tetrahydrofuran, and the salt in the reaction solution was filtered with filter paper. The reaction solution was then added dropwise to a mixture of 1.8 L of methanol and 0.6 L of water, stirred for 15 minutes, and the polyimide resin was filtered. Next, the resin was reslurried in 1 L of water and filtered, and then reslurried again in 1 L of methanol and filtered, and dried under reduced pressure at 40 ° C. for 8 hours. Next, the dried resin was dissolved in 300 g of tetrahydrofuran, and 40 g of ion exchange resin (MB-1: manufactured by Organo Corporation) was added. The mixture was stirred for 4 hours. The ion exchange resin was removed by filtration, and then the polyimide resin was precipitated in 2 L of methanol and stirred for 15 minutes. The polyimide resin was collected by filtration and dried at 45°C under reduced pressure for 1 day to obtain polyimide resin (SP-6). The resulting polyimide resin SP-6 had a weight average molecular weight of 18,900 and a number average molecular weight of 7,800. Polyimide (SP-6) is a resin having a repeating unit represented by the following formula (SP-6). The structure of the repeating unit was determined from ¹ H-NMR spectrum. In the following structure, the subscripts of the repeating units indicate the molar ratio of each repeating unit.

[Synthesis Example SP-7: Synthesis of Polyimide (SP-7)]
SP-7 was synthesized in the same manner as SP-6, except that the diamine raw material and 4-(chloromethyl)styrene were changed to 1-chlorododecane and 3-chloropropyl methacrylate.
The polyimide resin SP-7 had a weight average molecular weight of 25,100 and a number average molecular weight of 9,200. Polyimide (SP-7) is a resin having a repeating unit represented by the following formula (SP-7). The structure of the repeating unit was determined from ¹ H-NMR spectrum. In the following structure, the subscripts of the repeating units represent the molar ratio of each repeating unit.

[Synthesis of 6-maleimidohexanoic acid chloride]
In a recovery flask equipped with a thermometer and a calcium chloride tube, 7.92 g (37.5 mmol) of 6-maleimidohexanoic acid was dissolved in 30 g of tetrahydrofuran, 0.1 g of N,N'-dimethylformamide was added, and the mixture was cooled to 0°C while stirring with a magnetic stirrer. Subsequently, 4.85 g (38.25 mmol) of oxalyl chloride was added dropwise, and the mixture was stirred at 0°C to 10°C for 1 hour. Subsequently, the temperature was raised to 25°C, and the mixture was stirred for 2 hours to synthesize 6-maleimidohexanoic acid chloride.

[Synthesis Example SP-8: Synthesis of Polyimide (SP-8)]
30.0 g (57.64 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride was dissolved in 130 g of N-methylpyrrolidone (NMP). Subsequently, 3.20 g (12.39 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane, 4.02 g (15.56 mmol) of 1,4-phenylenediamine, and 2.18 g (11.53 mmol) of 4-[(trimethylsilyl)ethynyl]aniline were added while washing with 50 g of NMP. The mixture was stirred at a temperature ranging from 20 to 50°C for 30 minutes, after which 10 g of toluene was added. The mixture was reacted at 200°C for 4 hours under a nitrogen flow and then cooled to 25°C. Next, the above-synthesized 6-maleimidohexanoic acid chloride THF solution (37.5 mmol), 6.13 g of pyridine (77.5 mmol), and 0.10 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical were added, and the mixture was reacted at 25°C for 2 hours, then heated to 45°C, and stirred for an additional 10 hours. The reaction solution was then cooled to 25°C, diluted with 200 g of tetrahydrofuran, and added dropwise to a mixture of 2.0 L of methanol and 0.5 L of water. The mixture was stirred for 15 minutes, and the polyimide resin was filtered. Next, the above resin was reslurried in 1 L of water and filtered, and then reslurried again in 1 L of methanol and filtered, and dried under reduced pressure at 40°C for 10 hours. Next, the above resin was diluted with 200 g of tetrahydrofuran, and added dropwise to a mixture of 2.0 L of methanol and 0.5 L of water. The mixture was stirred for 15 minutes, and the polyimide resin was filtered. Next, the above resin was reslurried in 1 L of water, filtered, and then reslurried again in 1 L of methanol, filtered, and dried under reduced pressure at 40°C for 10 hours. The dried resin was dissolved in 250 g of tetrahydrofuran, and 40 g of an ion exchange resin (MB-1, manufactured by Organo Corporation) was added. The mixture was stirred for 4 hours. The ion exchange resin was removed by filtration, and then the polyimide resin was precipitated in 2 L of methanol and stirred for 15 minutes. The polyimide resin was collected by filtration and dried under reduced pressure at 45°C for 1 day to obtain polyimide resin (SP-8). The weight average molecular weight of the resulting polyimide resin SP-8 was 21,000, and the number average molecular weight was 8,500.

The table below shows the ethylenically unsaturated bond valence (C=C valence, the content of ethylenically unsaturated bonds relative to the total mass of the resin) and alkynyl group value of SP-1 to SP-11.
From the structure of each resin, it is considered that the ethylenically unsaturated bond value in each resin is the same as the polymerizable group value and the radically polymerizable group value.

The ethylenically unsaturated bond value was calculated by the following method.
0.1 g of the resin was dissolved in 0.9 g of deuterated dimethyl sulfoxide, and then the solution was measured by ¹ H-NMR to calculate the amount of ethylenically unsaturated bonds. The number of ¹ H-NMR measurements was 640.
Tetramethylsilane was used as a standard substance, and the molar amount of ethylenically unsaturated bonds in the resin was calculated from the ratio of the integrated intensity of the peak attributable to the ethylenically unsaturated bond in ^{the 1} H-NMR chart to the integrated intensity of the peak attributable to the standard substance, the amount of the standard substance, and the amount of the resin.

The alkynyl value was calculated by the following method: 0.1 g of resin was dissolved in 0.9 g of deuterated dimethyl sulfoxide or 1.9 g of deuterated chloroform, and then measured by ¹ H-NMR to calculate the amount of ethylenically unsaturated bonds. The number of ¹ H-NMR measurements was 640.
Tetramethylsilane was used as a reference substance, and the molar amount of ethylenically unsaturated bonds in the resin was calculated from the ratio of the integrated intensity of the peak attributable to the ethylenically unsaturated bond in ^{the 1} H-NMR chart to the integrated intensity of the peak attributable to the reference substance, the amount of the reference substance, and the amount of the resin.

Synthesis Example SA-1: Synthesis of Polyimide Precursor (SA-1)
7.42 g (34.0 mmol) of pyromellitic anhydride, 17.7 g (34.0 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride), 17.8 g (137 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 22.8 g (289 mmol) of pyridine, and 75 g of diglyme were mixed and stirred at 60°C for 5 hours to produce pyromellitic anhydride and the diester of 4,4'-(4,4''-isopropylidenediphenoxy)bis(phthalic anhydride) and 2-hydroxyethyl methacrylate. Subsequently, the mixture was cooled to -10°C, and 17.70 g (141 mmol) of thionyl chloride was added dropwise over 90 minutes. The mixture was stirred for 2 hours, resulting in a white precipitate of pyridinium hydrochloride. Next, 13.0 g (61.2 mmol) of m-tolidine and 1.39 g (6.8 mmol) of 4-[(trimethylsilyl)ethynyl]aniline dissolved in 100 mL of NMP (N-methyl-2-pyrrolidone) were added dropwise over 2 hours. Subsequently, 10.0 g (217 mmol) of ethanol was added, and the mixture was stirred for 2 hours. The polyimide precursor was then precipitated in 4 L of water, and the water-polyimide precursor mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor was collected by filtration, stirred again in 4 L of water for 30 minutes, and filtered again. The resulting polyimide precursor was then dried under reduced pressure at 45°C for 2 days to obtain polyimide precursor (SA-1). The resulting polyimide precursor (SA-1) had a weight-average molecular weight of 30,600 and a number-average molecular weight of 12,800. Polyimide precursor (SA-1) is a resin having two repeating units represented by the following formula (SA-1). The structure of the repeating units was determined from ¹ H-NMR spectrum. In the following structure, the subscripts of the repeating units represent the molar ratio of each repeating unit.

[Synthesis Example SA-2: Synthesis of Polyimide Precursor (SA-2)]
SA-2 was synthesized in the same manner as SA-1. The weight-average molecular weight of SA-2 was 25,800 and the number-average molecular weight was 11,000. Polyimide precursor (SA-2) is a resin having two repeating units represented by the following formula (SA-2). The structure of the repeating units was determined from ¹ H-NMR spectrum. In the following structure, the subscripts of the repeating units represent the molar ratio of each repeating unit.

[Synthesis Example SA-3: Synthesis of Polyimide Precursor (SA-3)]
35.4 g (68.0 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride), 15.9 g (122.4 mmol) of 2-hydroxyethyl methacrylate, 2.57 g (20.4 mmol) of 3-octyn-1-ol, 0.05 g of hydroquinone, 22.8 g (289 mmol) of pyridine, and 75 g of diglyme were mixed and stirred at 60°C for 5 hours to produce a diester of 4,4'-(4,4''-isopropylidenediphenoxy)bis(phthalic anhydride) and 2-hydroxyethyl methacrylate. Subsequently, the mixture was cooled to -10°C, and 17.70 g (141 mmol) of thionyl chloride was added dropwise over 90 minutes. The mixture was stirred for 2 hours, yielding a white precipitate of pyridinium hydrochloride. Next, 13.0 g (61.2 mmol) of m-tolidine and 0.797 g (6.8 mmol) of 4-aminophenylacetylene dissolved in 100 mL of NMP (N-methyl-2-pyrrolidone) were added dropwise over 2 hours. Subsequently, 10.0 g (217 mmol) of ethanol was added, and the mixture was stirred for 2 hours. The polyimide precursor was then precipitated in 4 L of water, and the water-polyimide precursor mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor was collected by filtration, stirred again in 4 L of water for 30 minutes, and filtered again. The resulting polyimide precursor was then dried under reduced pressure at 45°C for 2 days to obtain polyimide precursor (SA-3). The resulting polyimide precursor (SA-3) had a weight-average molecular weight of 35,900 and a number-average molecular weight of 14,900. Polyimide precursor (SA-3) is a resin having two repeating units represented by the following formula (SA-3). The structure of the repeating units was determined from ¹ H-NMR spectrum. In the following structure, the subscripts of the repeating units represent the molar ratio of each repeating unit.

The ethylenically unsaturated bond valence (C=C valence, the content of ethylenically unsaturated bonds relative to the total mass of the resin) and alkynyl group value of SA-1 to SA-3 are shown in the table below.
The ethylenically unsaturated bond valence and alkynyl group value are measured by the same methods as those used in SP-1 to SP-11.
From the structure of each resin, it is considered that the ethylenically unsaturated bond value in each resin is the same as the polymerizable group value and the radically polymerizable group value.

[Synthesis of Comparative Compound A-1]
To a flask equipped with a stirrer, condenser, and thermometer, 41.4 g (114 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 57.29 g (125.0 mmol) of bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid)1,4-phenylene were added while removing water, and 492.43 g of γ-butyrolactone was added. The mixture was stirred at 60°C for 1.5 hours. Subsequently, 50 mL of toluene was added, and the mixture was heated to 180°C while flowing nitrogen at a flow rate of 200 mL/min. The mixture was stirred for 3 hours and then cooled to room temperature. The resulting polymerization solution was diluted with acetone to prepare a diluent. The diluent was then added dropwise to a 3/1 water/methanol mixed solution to precipitate a white solid. The resulting white solid was collected and vacuum dried at 120°C to obtain 90 g of polymer.
Next, 73.86 g of the polymer obtained above (150.0 mmol in terms of hydroxyl groups), 23.27 g (150.0 mmol) of 2-isocyanatoethyl methacrylate, and 828.3 g of γ-butyrolactone (GBL) were placed in a reaction vessel equipped with a stirrer and a condenser. The temperature was then raised to 120°C with stirring, and the mixture was allowed to react for 6 hours. The resulting reaction solution was then diluted with acetone to prepare a diluted solution, and the diluted solution was then added dropwise to a 2:1 water/methanol mixed solution to precipitate a white solid. The resulting white solid was collected and vacuum-dried at 40°C to obtain 85.8 g of A-1. The weight-average molecular weight (Mw) of A-1 was 32,200, and the number-average molecular weight (Mn) was 12,800. ¹ H-NMR spectroscopy confirmed that the structure represented by the following formula (A-1) was the main component of A-1: ^{The 1} H-NMR measurement results showed that the introduction rate of crosslinking groups was 50%.

Examples and Comparative Examples
In each example, the components shown in the table below were mixed to obtain a resin composition. In each comparative example, the components shown in the table below were mixed to obtain a comparative composition.
Specifically, the content of each component shown in the table is the amount (parts by mass) shown in the "Amount Added" column of each column in the table.
The resulting resin composition and comparative composition were filtered under pressure using a polytetrafluoroethylene filter with a pore width of 0.5 μm.
In the table, "-" indicates that the composition does not contain the corresponding component.

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

〔resin〕
SP-1 to SP-11: SP-1 to SP-11 synthesized above
SA-1 to SA-3: SA-1 to SA-3 synthesized above
A-1: A-1 synthesized above

[Polymerizable compound]
B-1: 1,12-dodecanediol dimethacrylate (melting point: 25°C or less)
B-2: 1,9-nonanediol dimethacrylate (melting point: 25°C or less)
B-3: 1,10-decanediol dimethacrylate (melting point: 25°C or less)
B-4: SR-209: SR-209 (manufactured by Sartomer, melting point: 25°C or less)
B-5: ADPH: Dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., melting point: 25°C or less)

〔solvent〕
In the table, the descriptions "DMSO/GBL" and "DMSO/γ-valerolactone" indicate that a mixture of DMSO and GBL in a mixing ratio (mass ratio) of DMSO:GBL = 20:80 was used, and a mixture of DMSO and γ-valerolactone in a mixing ratio (mass ratio) of DMSO:γ-valerolactone = 20:80 was used.
3-MCH: 3-methylcyclohexanone

[Polymerization initiators (all trade names)]
OXE-01: IRGACURE OXE 01 (manufactured by BASF)
OXE-02: IRGACURE OXE 02 (manufactured by BASF)
OXE-03: IRGACURE OXE 03 (manufactured by BASF)
Irgcue 784 (manufactured by BASF)
・CPI-310B (manufactured by San-Apro Co., Ltd.)

[Migration inhibitor]
E-1 to E-7: Compounds having the following structure

[Metal adhesion improver]
F-1 to F-3: Compounds having the following structure
F-4: X-12-1293 (Shin-Etsu Chemical Co., Ltd.)
F-5: KBM-51073 (Shin-Etsu Chemical Co., Ltd.)
F-6: X-12-1214A (Shin-Etsu Chemical Co., Ltd.)

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

[Metal complex or metal salt]
I-1: TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd.)
I-2: TC-401 (manufactured by Matsumoto Fine Chemical Co., Ltd.)
I-3: TC-800 (manufactured by Matsumoto Fine Chemical Co., Ltd.)
I-4: TC-810 (manufactured by Matsumoto Fine Chemical Co., Ltd.)
I-5: Compound having the following structure I-6: Compound having the following structure I-7: Compound having the following structure I-8: Compound having the following structure
I-9: Silver benzoate (I) (Tokyo Chemical Industry Co., Ltd.)
I-10: Silver(II) pyridine-2-carboxylate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Surfactant]
J-1: Nonion E-212 (manufactured by NOF Corporation)
J-2: MEGAFACE EFS-801 (manufactured by Dainippon Ink Co., Ltd.)
J-3: Shin-Etsu Silicone KF6028 (manufactured by Shin-Etsu Chemical Co., Ltd.)

For each of the resin compositions prepared in each Example, when a film-like cured product having a film thickness of 10 μm was formed, the transmittance of light having a wavelength of 365 nm was 30% or more. The film-like cured product was obtained by applying the resin composition to a silicon wafer, drying it at 100°C for 5 minutes, exposing the entire surface to i-rays with an exposure energy of 500 mJ/ ^cm2 , and then heating it at a heating rate of 10°C/min in a nitrogen atmosphere and at 230°C for 180 minutes.
The transmittance was measured using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

<Evaluation>
[Evaluation conditions for copper adhesion]
Each of the filtered resin compositions was applied to a copper substrate by spin coating to form a layer of resin composition. The silicon wafer with the resulting curable resin composition layer applied was dried on a hot plate at 100°C for 5 minutes to form a uniform resin composition layer of 20 μm thickness on the copper substrate. The resin composition layer on the copper substrate was exposed to light using a stepper (Nikon NSR 2005 i9C) with an exposure energy of 500 mJ/ ^cm2 using a 100 μm square photomask, and then developed for 60 seconds with the developer listed in the "Development Method (Developer)" column in the table, followed by rinsing with propylene glycol monomethyl ether acetate (PGMEA) for 15 seconds to obtain a 100 μm square resin layer. Furthermore, the temperature was increased at a rate of 10°C/min under a nitrogen atmosphere until the temperature described in the "Temperature" column of the "Curing Conditions" in the table was reached. After that, this temperature was maintained for the time described in the "Curing Time" column of the "Curing Conditions" in the table, and resin film 2 was obtained.
The shear strength of a 100 μm square resin film 2 on a copper substrate was measured using a bond tester (CondorSigma, manufactured by XYZTEC Corporation) under an environment of 25° C. and 65% relative humidity (RH). The greater the shear strength, the greater the adhesion, resulting in a more favorable result.
A: Shear force exceeds 35 gf B: Shear force exceeds 30 gf but is 35 gf or less C: Shear force is 30 gf or less However, 1 gf is 0.00980665 N.

[Evaluation of dielectric constant]
Each resin composition or comparative composition prepared in each Example and Comparative Example was applied to a 12-inch silicon wafer by spin coating to form a resin composition layer. The silicon wafer to which the resulting resin composition layer was applied was dried on a hot plate at 100°C for 5 minutes, forming a resin composition layer with a uniform thickness of 15 μm on the silicon wafer. The resin composition layer on the silicon wafer was exposed to light using a stepper (Nikon NSR 2005 i9C) at an exposure energy of 500 mJ/ ^cm2 . The exposed resin composition layer (resin layer) was heated at a heating rate of 10°C/min under a nitrogen atmosphere and heated at the temperature specified in the "Temperature" column under "Curing Conditions" in the table for the time specified in the "Curing Time" column under "Curing Conditions" in the table to obtain a cured layer (resin layer) of the resin composition layer.
The cured layer (resin film) after curing was immersed in a 4.9% by mass aqueous solution of hydrofluoric acid, and the cured film was peeled off from the silicon wafer.
The relative permittivity (Dk) and dielectric loss tangent (Df) of the film sample at 28 GHz were measured by a resonator perturbation method.
The dielectric loss tangent was evaluated according to the following evaluation criteria, and the evaluation results are shown in the "Dielectric loss tangent (Df)" column in the table.
<Measurement method>
Split Cylinder Resonator (CR-728)
(Device configuration)
Network analyzer: N5230A (Keysight)
-Evaluation criteria-
A: The dielectric loss tangent (Df) was less than 0.06.
B: The dielectric loss tangent (Df) was 0.06 to less than 0.08.
C: The dielectric loss tangent (Df) was 0.08 or more.

[Evaluation of insulation reliability]
The resin composition or comparative composition prepared in each Example and Comparative Example was applied to a copper substrate by spin coating to form a layer of the resin composition or comparative composition. The copper substrate on which the resulting resin composition layer or comparative composition layer was formed was dried on a hot plate at 100°C for 5 minutes to form a 5 μm thick, uniform resin composition layer or comparative composition layer on the copper substrate. The resin composition layer or comparative composition layer on the copper substrate was exposed to i-rays using a stepper (Nikon NSR 2005 i9C) with an exposure energy of 500 mJ/ ^cm2 and a photomask with a 100 μm square unmasked area. The resin composition layer or comparative composition layer on the copper substrate was then developed for 60 seconds with the developer listed in the "Development Method (Developer)" column in the table, and rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a 100 μm square resin layer. Furthermore, the coating was heated in a heating oven under a nitrogen atmosphere at the temperature and for the curing time described in the "Curing Conditions" column of the table to form a resin layer (pattern).
After the resin layer and copper substrate were left in a thermostatic chamber at 175°C for 1000 hours, cross-sectional SEM (scanning electron microscope) measurement was carried out to evaluate the void area ratio between the copper substrate and the resin layer. The void area ratio was calculated using the following formula.
Void area ratio (%)=(area of voids observed by SEM measurement)/(total area of resin layer)×100
The obtained void area ratio was evaluated according to the following evaluation criteria. The evaluation results are shown in the "Insulation reliability" column in the table. The smaller the void area ratio, the better the reliability of the cured film after HTS (High Temperature Storage Test). It can be said that voids are less likely to occur between the metal layer and the cured product even after a long period of time has passed, and the better the insulation reliability.
-Evaluation criteria-
A: The void area ratio was 0.1% or less.
B: The void area ratio was more than 0.1% and 0.3% or less.
C: The void area ratio exceeded 0.3%.

[Evaluation of moisture resistance]
The resin composition or comparative composition prepared in each Example and Comparative Example was applied to a copper substrate by spin coating to form a layer of the resin composition or comparative composition. The copper substrate on which the resulting resin composition layer or comparative composition layer was formed was dried on a hot plate at 100°C for 5 minutes to form a 5 μm thick, uniform resin composition layer or comparative composition layer on the copper substrate. The resin composition layer or comparative composition layer on the copper substrate was exposed to i-rays using a stepper (Nikon NSR 2005 i9C) with an exposure energy of 500 mJ/ ^cm2 and a photomask with a 100 μm square unmasked area. The resin composition layer or comparative composition layer on the copper substrate was then developed for 60 seconds with the developer listed in the "Development Method (Developer)" column in the table, and rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a 100 μm square resin layer. Furthermore, the composition was heated in a nitrogen atmosphere at the temperature described in the "Temperature" column of the "Curing Conditions" in the table for the time described in the "Curing Time" column of the "Curing Conditions" in the table using a heating oven to form a resin layer (pattern).
The resin composition layer and copper substrate were left in a chamber at 100°C and 100% RH for 100 hours. Cross-sectional SEM (scanning electron microscope) measurements were performed to evaluate the void area ratio between the copper substrate and the resin layer. The void area ratio was calculated using the following formula:
Void area ratio (%)=(area of voids observed by SEM measurement)/(total area of resin layer)×100
The obtained void area ratio value was evaluated according to the following evaluation criteria. The smaller the void area ratio, the better the PCT (wet heat) resistance of the cured film, and the less likely voids are to occur between the metal layer and the cured product even after a long period of time has passed.
A: The void area ratio was 0.2% or less.
B: The void area ratio was more than 0.2% and 0.5% or less.
C: The void area ratio was more than 0.5% and 1% or less.
D: The void area ratio exceeded 1%.

These results show that the resin composition according to the present invention produces a cured product with excellent adhesion to metal. In comparison, the cured product produced from the composition according to Comparative Example 1, which does not contain the specified resin, exhibits poor adhesion.

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

<Examples 102 to 118>
In Example 101, evaluation was carried out in the same manner as in Example 101, except that the resin composition used in Example 1 was changed to the compositions used in Examples 2 to 18, respectively.
In all the examples, the interlayer insulating film for the redistribution layer had excellent insulating properties, and the semiconductor device operated without any problems.

Claims (29)

a resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor, the resin having an alkynyl group in which a hydrogen atom may be substituted with a monovalent substituent, and a polymerizable group;
a polymerization initiator,
A resin composition used to form an insulating film. The resin composition according to claim 1, wherein the alkynyl group is a group in which one hydrogen atom has been removed from an internal alkyne. The resin composition according to claim 1 or 2, wherein the resin is selected from the group consisting of polyimide and polybenzoxazole. The resin composition according to claim 1 or 2, wherein the alkynyl group is present on a side chain or at the end of the main chain of the resin. The resin composition according to claim 1 or 2, wherein the resin has a group represented by the following formula (B-1) as the group containing an alkynyl group:
In formula (B-1), R ¹ represents a divalent linking group, Z ¹ represents a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms or a silicon atom, when Z ¹ is the alkylene group, n is 1, and R ² represents a hydrogen atom or a monovalent organic group, when Z ¹ is the silicon atom, n is 3, and each R ² independently represents a monovalent organic group, and * represents a bonding site to another structure. The resin composition according to claim 1 or 2, wherein the alkynyl group value of the resin is 0.01 to 1.0 mmol/g. The resin composition according to claim 1 or 2, wherein the polymerizable group value of the resin is 0.2 to 4.0 mmol/g. The resin composition according to claim 1 or 2, wherein when the resin composition is used to form a film-like cured product having a film thickness of 10 μm, the cured product has a transmittance of 15% or more for light with a wavelength of 365 nm. The resin composition according to claim 1 or 2, wherein the resin contains a repeating unit represented by the following formula (1-1):
In formula (1-1), ^X1 represents an organic group having 4 or more carbon atoms, ^Y1 represents an organic group having 4 or more carbon atoms, ^R1 each independently represents a structure represented by formula (R-1) below, m represents an integer of 0 to 4, n represents an integer of 0 or more, and n+m is an integer of 1 or more.
In formula (R-1), L ¹ represents a linking group having a valence of a1+1, A ¹ represents a polymerizable group, a1 represents an integer of 1 or more, and * represents a bonding site with X ¹ or Y ¹ in formula (1-1). The resin composition according to claim 9, wherein at least one of A ¹ in formula (R-1) in formula (1-1) is a vinylphenyl group. X ¹ and Y ¹ in formula (1-1) each include a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of the following formulas (V-1) to (V-4): The resin composition according to claim 9.
In formula (V-2), R 1 and ^X1 each independently represent a hydrogen atom, an alkyl group or a halogenated alkyl group.
In formula (V-3), R 1 ^X2 and R ^{1 X3} each independently represent a hydrogen atom or a substituent, and R ^{1 X2} and R 1 ^X3 may be bonded to form a ring structure. The resin composition according to claim 1 or 2, wherein the radical polymerizable group value of the resin is 0.2 to 3.0 mmol/g. The resin composition according to claim 1 or 2, which contains a metal or its salt, or a metal complex. The resin composition according to claim 1 or 2, which contains a metal complex. The resin composition according to claim 1 or 2, further comprising a polymerizable compound having a melting point of 60°C or less. The resin composition according to claim 1 or 2, further comprising an azole compound and a silane coupling agent. The resin composition according to claim 1 or 2, containing a solvent having a boiling point of 100 to 260°C at 1 atmosphere. The resin composition according to claim 17, wherein the content of the solvent having a boiling point of 100 to 260°C is 40 mass% or more based on the total mass of the composition. The resin composition according to claim 17, comprising two or more solvents having a boiling point of 100 to 260°C. The resin composition according to claim 1 or 2, which is used to form an interlayer insulating film for a redistribution layer. A cured product obtained by curing the resin composition described in claim 1 or 2. A laminate comprising two or more layers made of the cured product according to claim 21, and including a metal layer between any of the layers made of the cured product. A method for producing a cured product, comprising a film-forming step of applying the resin composition described in claim 1 or 2 onto a substrate to form a film. The method for producing a cured product according to claim 23, comprising an exposure step of selectively exposing the film to light and a development step of developing the film with a developer to form a pattern. The method for producing a cured product described in claim 23, which includes a heating step of heating the film at 50 to 450°C. A method for producing a laminate, comprising the method for producing a cured product described in claim 23. A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured product according to claim 23. A semiconductor device comprising the cured product described in claim 21. A copolymer having a repeating unit represented by formula (1-1) and a group represented by formula (B-1):
resin.
In formula (1-1), ^X1 represents an organic group having 4 or more carbon atoms, ^Y1 represents an organic group having 4 or more carbon atoms, ^R1 each independently represents a structure represented by formula (R-1) below, m represents an integer of 0 to 4, n represents an integer of 0 or more, and n+m is an integer of 1 or more.
In formula (R-1), L ¹ represents a linking group having a valence of a1+1, A ¹ represents a polymerizable group, a1 represents an integer of 1 or more, and * represents a bonding site with X ¹ or Y ¹ in formula (1-1).
In formula (B-1), R ¹ represents a divalent linking group, Z ¹ represents a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms or a silicon atom, when Z ¹ is the alkylene group, n is 1, and R ² represents a hydrogen atom or a monovalent organic group, when Z ¹ is the silicon atom, n is 3, and each R ² independently represents a monovalent organic group, and * represents a bonding site to another structure.