Resin composition, cured product, laminate, method for producing cured product, method for producing laminate, method for producing semiconductor device, and semiconductor device

Abstract

Provided are: a resin composition containing a resin and a compound A1 represented by formula (A1-1), formula (A1-2), or formula (A1-3) and having a molar extinction coefficient of 1×103L∙mol-1∙cm-1 or less at a wavelength of 365 nm; 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; and a semiconductor device. In formula (A1-1), formula (A1-2), and formula (A1-3), R1 is an aromatic ring, R2 to R4 are organic groups, R2 to R4 may be the same as or different from each other, R5 to R10 are a hydrogen atom or an organic group, R5 to R10 may be the same as or different from each other, and R1 to R10 may bond to each other to form ring structures.

Description

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

[0001] 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, and a semiconductor device.

[0002] Nowadays, resin materials produced from resin compositions containing resins are being utilized in various fields. For example, cyclized resins such as polyimides are used in a variety of applications due to their excellent heat resistance and insulating properties. 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.

[0003] For example, in the above-mentioned applications, the cyclized resin such as polyimide is used in the form of a precursor of the cyclized resin such as a polyimide precursor, or a resin composition containing the cyclized resin. Such a resin composition can be applied to a substrate, for example, by coating to form a photosensitive film, and then, as necessary, exposed to light, developed, heated, or the like, to form a cured product on the substrate. In the cured product, the precursor of the cyclized resin such as a polyimide precursor is converted to a cyclized resin such as a polyimide. Since the resin composition can be applied by known coating methods, for example, it can be said to have excellent manufacturing adaptability, such as a high degree of design freedom in the shape, size, application position, etc., of the applied resin composition. In addition to the high performance of the cyclized resin, from the perspective of such excellent manufacturing adaptability, the industrial application of the above-mentioned resin composition is increasingly expected.

[0004] For example, Patent Document 1 describes a negative photosensitive resin composition containing (A) an alkali-soluble resin and (C1) two or more types of oxime ester photopolymerization initiators (C1-1) as a photopolymerization initiator, wherein the (C1-1) oxime ester photopolymerization initiator contains at least a (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator and a (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiator, wherein the (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator has a fused polycyclic skeleton containing an aromatic skeleton, the fused polycyclic skeleton being composed only of carbon atoms and hydrogen atoms, and the fused polycyclic skeleton and the fused polycyclic heterocyclic skeleton each having a structure in which at least one oxime ester structure is bonded or a structure in which at least one oxime ester carbonyl structure is bonded.

[0005] International Publication No. 2021 / 006315

[0006] Along with the miniaturization, high integration, and high frequency of devices, there is a demand for the production of fine cured products using resin compositions, that is, for the production of cured products with small minimum pattern dimensions that can be resolved using photolithography. In the present invention, the production of a cured product with small minimum pattern dimensions that can be resolved is also referred to as the production of a cured product with excellent resolution.

[0007] The present invention aims to provide a resin composition that can give a cured product with excellent resolution, 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.

[0008] Representative embodiments of the present invention are shown below: <1> A resin and a compound represented by the following formula (A1-1), (A1-2), or (A1-3), which has a molar absorption coefficient of 1×10 at a wavelength of 365 nm: ３ L.mol －１ ・cm －１ A resin composition comprising: Compound A1: In formula (A1-1), formula (A1-2), and formula (A1-3), R １is an aromatic ring, and R ２ ~R ４ is an organic group, and R ２ ~R ４ may be the same or different, and R ５ ~R １０ is a hydrogen atom or an organic group, and R ５ ~R １０ may be the same or different, R １ ~R １０ may be bonded to each other to form a ring structure. １ <3> A resin composition comprising a resin and a compound A2 represented by the following formula (A2-1), (A2-2), or (A2-3): In formula (A2-1), formula (A2-2), and formula (A2-3), R １ is an unsubstituted phenyl group, and R ２ ~R ４ is an organic group, and R ２ ~R ４ may be the same or different, R ５ ~R １０ is a hydrogen atom or an organic group, and R ５ ~R １０ may be the same or different, and R １ ~R １０ <4> The resin composition according to any one of <1> to <3>, wherein the resin is at least one resin selected from the group consisting of cyclized resins and precursors thereof. <5> The R ２ <1> to <4>, wherein each of the above is a structure represented by the following formula (R2-1) or formula (R2-2): In formula (R2-1) and formula (R2-2), R ２２ is an organic group, and * is a bonding site with an oxygen atom. ３ and the above R ４ <7> The resin composition according to any one of <1> to <5>, wherein R５ ~R １０ <8> The resin composition according to any one of <1> to <6>, wherein all of the following are hydrogen atoms. <9> The resin composition according to <1> or <2>, wherein the compound A1 is a compound represented by the following formula (A1-4): In formula (A1-4), R １ is an aromatic ring, and R ２３ is an alkyl group, an aryl group, or an alkoxy group, and R ３ and R ４ is a hydrogen atom or an organic group, and R ３ and R ４ may be bonded to each other to form a ring structure. <9> The resin composition according to <3>, wherein the compound A2 is a compound represented by the following formula (A2-4): In formula (A2-4), R １ is an unsubstituted phenyl group, and R ２３ is an alkyl group, an aryl group, or an alkoxy group, and R ３ and R ４ is a hydrogen atom or an organic group, and R ３ and R ４may bond to each other to form a ring structure. <10> The resin composition according to any one of <1> to <9>, wherein the resin is a polyimide or a polyimide precursor. <11> The resin composition according to any one of <1> to <10>, wherein the resin has a radically polymerizable group. <12> The resin composition according to any one of <1> to <11>, wherein the resin is used to form an interlayer insulating film for a redistribution layer. <13> A cured product obtained by curing the resin composition according to any one of <1> to <12>. <14> A laminate comprising two or more layers made of the cured product according to <13>, and a metal layer between any two adjacent layers made of the cured products. <15> A method for producing a cured product, comprising a film-forming step of applying the resin composition according to any one of <1> to <12> onto a substrate to form a film. <16> A method for producing a cured product according to <15>, 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. <17> A method for producing the cured product according to <15> or <16>, comprising a heating step of heating the film at 50 to 450°C. <18> A method for producing a laminate, comprising the method for producing a cured product according to any one of <15> to <17>. <19> A method for producing a semiconductor device, comprising the method for producing a cured product according to any one of <15> to <17>. <20> A semiconductor device, comprising the cured product according to <13>.

[0009] According to the present invention, there are provided a resin composition that can give a cured product with excellent resolution, 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.

[0010] The following describes the main embodiments of the present invention. However, the present invention is not limited to the explicitly described embodiments. 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 "process" refers not only to an independent process but also to a process that cannot be clearly distinguished from other processes as long as the process achieves its intended effect. In the description of a group (atomic group), a notation that does not specify whether it is substituted or unsubstituted encompasses both unsubstituted groups (atomic groups) and substituted groups (atomic groups). For example, the term "alkyl group" encompasses not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. In addition, examples of light used for exposure include actinic rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and electron beams. As used herein, "(meth)acrylate" refers to either or both of "acrylate" and "methacrylate," "(meth)acrylic" refers to either or both of "acrylic" and "methacrylic," and "(meth)acryloyl" refers to either or both of "acryloyl" and "methacryloyl." In the structural formulae herein, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. As used herein, the term "total solid content" refers to the total mass of all components of the composition excluding the solvent. Furthermore, as used herein, the term "solid content concentration" refers to the mass percentage of the components other than the solvent relative to the total mass of the composition. As used herein, 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, unless otherwise specified.In this specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, by 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, when NMP is not suitable as the eluent, for example, due to low solubility, THF (tetrahydrofuran) can also be used. Furthermore, unless otherwise specified, detection in GPC measurement is assumed to be performed using a UV (ultraviolet) detector at a wavelength of 254 nm. In this specification, when the positional relationship of each layer constituting a laminate is described as "above" or "below," it is sufficient that another layer is 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 with each other. Unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "above." Alternatively, if a resin composition layer is present, the direction from the substrate to the resin composition layer is referred to as "above," and the opposite direction is referred to as "below." Note that such vertical directions are defined for convenience in this specification, and in actual embodiments, the "above" direction in this specification may differ from the vertically upward direction. In this specification, unless otherwise specified, the composition may contain two or more compounds corresponding to each component contained in the composition. 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. In this specification, a combination of preferred embodiments is a more preferred embodiment.

[0011] (Resin Composition) The resin composition according to the first aspect of the present invention (hereinafter also simply referred to as "first resin composition") comprises a resin and a compound represented by formula (A1-1), formula (A1-2), or formula (A1-3) having a molar absorption coefficient of 1×10 at a wavelength of 365 nm. ３ L.mol －１ ・cm －１ and a compound A1 represented by the following formula (A2-1), (A2-2), or (A2-3). A resin composition according to a second aspect of the present invention (hereinafter also simply referred to as a "second resin composition") comprises a resin and a compound A2 represented by formula (A2-1), (A2-2), or (A2-3). Hereinafter, a resin composition corresponding to at least one of the first resin composition and the second resin composition will also be simply referred to as a "resin composition." Furthermore, a compound corresponding to at least one of the compound A1 and the compound A2 will also be referred to as a specific compound.

[0012] 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 to form a 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, for example, to form an insulating film for a semiconductor device, an interlayer insulating film for a redistribution layer, a stress buffer film, etc., and is preferably used to form an interlayer insulating film for a redistribution layer. Furthermore, the resin composition of the present invention is preferably a negative resin composition. In the present invention, negative development refers to development in which the unexposed portion is removed by development in exposure and development, and positive development refers to development in which the exposed portion is 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.

[0013] The resin composition of the present invention can provide a cured product with excellent resolution. The mechanism by which the above-mentioned effects are obtained is unknown, but is presumed to be as follows.

[0014] In recent years, the formation of patterns by exposure and development using resin compositions containing a resin and a photopolymerization initiator has been practiced in various fields. The present inventors have found that, because conventional photopolymerization initiators have a large molar absorption coefficient at a wavelength of 365 nm, when a film containing such a photopolymerization initiator is exposed to light, the exposure light (UV light) attenuates before reaching the bottom of the film, and a fine pattern may not be formed. The resin composition according to the first aspect of the present invention is represented by formula (A1-1), formula (A1-2), or formula (A1-3), and has a molar absorption coefficient at a wavelength of 365 nm of 1×10 ３ L.mol －１ ・cm －１ The resin composition according to the second aspect of the present invention includes a compound A2 represented by formula (A2-1), formula (A2-2), or formula (A2-3). The molar absorption coefficient of compound A1 at a wavelength of 365 nm is 1×10 ３ L.mol －１ ・cm －１ Compound A2 is R in each formula １ is an unsubstituted phenyl group. Such compound A2 is considered to have a small molar absorption coefficient at a wavelength of 365 nm. Since the specific compound (a compound corresponding to at least one of compound A1 and compound A2) has a small molar absorption coefficient at a wavelength of 365 nm, a film formed from a resin composition containing the specific compound exhibits low absorption of UV light (e.g., i-line). Therefore, attenuation of light reaching the lower part of the film (the side farther from the irradiated light) is suppressed. As a result, the pattern shape is favorable, making it possible to form a fine pattern with a taper angle close to perpendicular, resulting in excellent resolution. Furthermore, simply reducing the molar absorption coefficient of the photopolymerization initiator may reduce the amount of polymerization initiation species generated by exposure, resulting in reduced exposure sensitivity and insufficient polymerization, resulting in failure to form a pattern. Therefore, the present inventors discovered that by introducing a tertiary carbon into an appropriate position in a specific compound, it is possible to reduce the molar absorption coefficient while maintaining exposure sensitivity, and thus completed the present invention.

[0015] However, Patent Document 1 does not describe a resin composition containing a compound.

[0016] The resin composition of the present invention will be described in detail below.

[0017] <Resin> The resin composition of the present invention contains a resin. The resin is not particularly limited, and resins known in the field of photolithography can be used without particular limitation, including at least one resin selected from the group consisting of cyclized resins and their precursors, 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. Among these, the resin composition of the present invention preferably contains at least one resin selected from the group consisting of cyclized resins and their precursors (hereinafter also referred to as "specific resin").

[0018] The resin preferably has a polymerizable group, more preferably a radically polymerizable group. When the resin has a radically polymerizable group, the resin composition of the present invention more preferably contains a radical crosslinking agent. If necessary, a sensitizer may further be contained. For example, a negative photosensitive film can be formed from such a resin composition.

[0019] <Specific Resin> The resin composition of the present invention preferably contains at least one resin (specific resin) selected from the group consisting of cyclized resins and their precursors. The cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in its main chain structure. In the present invention, the term "main chain" refers to the relatively longest bonded chain in the resin molecule, and the term "side chain" refers to any other bonded chain. Examples of cyclized resins include polyimide, polybenzoxazole, and polyamideimide. A precursor of a cyclized resin refers to a resin whose chemical structure changes upon external stimulation to become a cyclized resin. A resin whose chemical structure changes upon heating to become a cyclized resin is preferred, and a resin that undergoes a ring-closing reaction upon heating to form a ring structure to become a cyclized resin is more preferred. Examples of precursors of cyclized resins include polyimide precursors, polybenzoxazole precursors, and polyamideimide precursors.

[0020] As used herein, polyimide refers to a resin having a repeating unit containing an imide structure in its molecular chain, preferably a resin having a repeating unit containing an imide ring structure in its 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 its main chain, more preferably a resin having a repeating unit containing an imide ring structure in its main chain. As used herein, 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, more preferably a bonding site to a quaternary carbon atom. As used herein, 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.

[0021] In this specification, the term "polyimide precursor" refers to a resin that undergoes a change in chemical structure due to an external stimulus to become a polyimide, and is preferably a resin that undergoes a change in chemical structure due to heat to become a polyimide, and more preferably a resin that undergoes a ring-closing reaction due to heat to form a ring structure to become a polyimide. The preferred embodiments of the polyimide that are formed are as described above.

[0022] In this specification, polybenzoxazole refers to a resin having a repeating unit containing a benzoxazole structure in the molecular chain. When polybenzoxazole is a linear resin, it is preferable that the polybenzoxazole is 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 another structure.

[0023] In this specification, the polybenzoxazole precursor refers to a resin that undergoes a change in chemical structure due to an external stimulus to become polybenzoxazole, and is preferably a resin that undergoes a change in chemical structure due to heat to become polybenzoxazole, and more preferably a resin that undergoes a ring-closing reaction due to heat to form a ring structure to become polybenzoxazole. Preferred embodiments of the polybenzoxazole that are formed are as described above.

[0024] As used herein, polyamideimide refers to a resin having an amide structure in the molecular chain in addition to an imide structure, and is preferably a resin having a repeating unit containing an imide ring structure and an amide structure in the molecular chain. In this specification, the amide structure 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. As used herein, polyamideimide precursor refers to a resin whose chemical structure changes upon external stimulation to become a polyamideimide, preferably a resin whose chemical structure changes upon heating to become a polyamideimide, and more preferably a resin whose ring structure is formed by a ring-closing reaction upon heating to become a polyamideimide. Preferred aspects of the polyamideimide formed are as described above.

[0025] The resin composition preferably contains, as the specific resin, at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor. The resin composition preferably contains, as the specific resin, polyimide or a polyimide precursor.

[0026] [Polyimide Precursor] The polyimide precursor used in the present invention is not particularly limited in type, but preferably contains a repeating unit represented by the following formula (2). In formula (2), A １ and A ２are each independently an oxygen atom or —NR ｚ represents -, and R １１１ represents a divalent organic group, and R １１５ represents a tetravalent organic group, R １１３ and R １１４ each independently represents a hydrogen atom or a monovalent organic group; R ｚ represents a hydrogen atom or a monovalent organic group.

[0027] A in formula (2) １ and A ２ are each independently an oxygen atom or —NR ｚ -, and an oxygen atom is preferred. ｚ represents a hydrogen atom or a monovalent organic group, and preferably a hydrogen atom. １１１ represents a divalent organic group. Examples of the divalent organic group include groups containing a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, and a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferred, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferred. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a heteroatom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a heteroatom. R in formula (2) １１１ Examples of the group include groups represented by -Ar- and -Ar-L-Ar-, and the group represented by -Ar-L-Ar- is preferred, where each Ar is independently an aromatic group, L is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO ２ - or -NHCO-, or a group consisting of a combination of two or more of the above. The preferred ranges for these are as described above.

[0028] R １１１ is preferably derived from a diamine. Examples of diamines used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used. Specifically, R１１１ is preferably a diamine containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a heteroatom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a heteroatom. Examples of groups containing an aromatic group include the following.

[0029] In the formula, A represents a single bond or a divalent linking group, and is selected from the group consisting of a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —C(═O)—, —S—, and —SO ２ -, -NHCO-, or a group selected from a combination thereof, and is preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, or -SO ２ - is more preferably a group selected from -CH ２ -, -O-, -S-, -SO ２ -, -C(CF ３ ) ２ - or -C(CH ３ ) ２ In the formula, * represents a bonding site to another structure.

[0030] Specific examples of diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3-, or 1,4-diaminocyclohexane, 1,2-, 1,3-, or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane, and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3 ,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane parafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoparaterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether fluorene, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,At least one diamine selected from 4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolidine, and 4,4'-diaminoquaterphenyl can be mentioned.

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

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

[0033] R １１１ is preferably represented by -Ar-L-Ar- from the viewpoint of flexibility of the resulting organic film, wherein each Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO ２ Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO ２ The aliphatic hydrocarbon group here is preferably an alkylene group.

[0034] Also, R １１１From the viewpoint of i-line transmittance, it is preferable that is a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-line transmittance and ease of availability, it is more preferable that is a divalent organic group represented by formula (61). Formula (51) In formula (51), R ５０ ~R ５７ are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and R ５０ ~R ５７ At least one of R is a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site with the nitrogen atom in formula (2). ５０ ~R ５７ Examples of the monovalent organic group include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). In formula (61), R ５８ and R ５９ are each independently a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site with the nitrogen atom in formula (2). Examples of diamines that give the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These may be used alone or in combination of two or more.

[0035] R １１１ The number of carbon atoms in R is preferably 4 or more, more preferably 4 to 50, and even more preferably 4 to 40. １１１ may be a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by any one of the following formulas (V-1) to (V-10): By being 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), the chemical resistance and flatness of the cured product are improved. In formula (V-2), R Ｘ１are each independently a hydrogen atom, an alkyl group, or a halogenated alkyl group. Ｘ２ and R Ｘ３ each independently represents a hydrogen atom or a substituent, R Ｘ２ and R Ｘ３ may bond to form a ring structure. Ｘ５ are each independently a hydrogen atom, an alkyl group, or a halogenated alkyl group.

[0036] In formula (V-2), R 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 a group in which at least one hydrogen atom of an alkyl group has been substituted with a halogen atom. The halogen atom is preferably F or Cl, and more preferably F. In formula (V-3), R Ｘ２ and R Ｘ３ are each preferably independently a hydrogen atom. Ｘ２ and R Ｘ３ When R Ｘ２ and R Ｘ３ The structure formed by bonding is a single bond, —O— or —C(R) ２ - is preferred, and -O- or -C(R) ２ R represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom. 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 a group in which at least one hydrogen atom of an alkyl group has been substituted with a halogen atom. As the halogen atom, F or Cl is preferred, and F is more preferred.

[0037] R １１１is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-1), R １１１ is preferably a group represented by the following formula (V-1-2): １１１ represents the bonding site with the two nitrogen atoms to which n is bonded, and n1 represents an integer of 1 to 5. Furthermore, the hydrogen atoms in the following structures may be further substituted with a group represented by formula (RP-1) described below or a known substituent such as a hydrocarbon group.

[0038] R １１１ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-2), R １１１ is preferably a group represented by the following formula (V-2-3) or formula (V-2-4), and from the viewpoint of reducing the dielectric constant of the cured product, it is preferably a group represented by formula (V-2-4). Ｘ１ represents a single bond or —O—, and * represents R １１１ represents the bonding site with the two nitrogen atoms to which R is bonded. Ｘ１ The definitions and preferred embodiments of are as described above. In addition, the hydrogen atoms in these structures may be further substituted with a group represented by formula (RP-1) described below or a known substituent such as a hydrocarbon group.

[0039] R １１１ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-3), R １１１ is preferably a group represented by the following formula (V-3-3) or formula (V-3-4), and from the viewpoint of reducing the dielectric constant of the cured product, is preferably a group represented by formula (V-3-3). In the following formulas, * represents R １１１ represents the bonding site with the two nitrogen atoms to which R is bonded. Ｘ２ and R Ｘ３ The definitions and preferred embodiments of are as described above. In addition, the hydrogen atoms in these structures may be further substituted with a group represented by formula (RP-1) described below or a known substituent such as a hydrocarbon group.

[0040] R１１１ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-4), R １１１ is preferably a group represented by the following formula (V-4-2) or formula (V-4-3): １１１ represents the bonding site to the two nitrogen atoms to which n 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 atoms in the following structures may be further substituted with a group represented by formula (RP-1) described below 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.

[0041] R １１１ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-5), R １１１ is preferably a group represented by the following formula (V-5-2): １１１ represents the bonding site with the two nitrogen atoms to which the two are bonded. Furthermore, the hydrogen atoms in formula (V-5-2) may be further substituted with a group represented by formula (RP-1) described below 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. However, it is also preferable that none of the hydrogen atoms in the structure represented by (V-5-2) is substituted.

[0042] R １１１ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-6), R １１１ is preferably a group represented by the following formula (V-6-2): １１１ represents the bonding site with the two nitrogen atoms to which the two are bonded. In addition, the hydrogen atoms in the following structures may be further substituted with a group represented by formula (RP-1) described below or a known substituent such as a hydrocarbon group.

[0043] R １１１is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-7), R １１１ is preferably a group represented by the following formula (V-7-2): １１１ represents the bonding site with the two nitrogen atoms to which the two are bonded. In addition, the hydrogen atoms in the following structures may be further substituted with a group represented by formula (RP-1) described below or a known substituent such as a hydrocarbon group.

[0044] R １１１ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-8), R １１１ is preferably a group represented by the following formula (V-8-2): １１１ represents the bonding site with the two nitrogen atoms to which R is bonded. Ｘ５ The definition and preferred embodiments of are as described above. In addition, the hydrogen atoms in the following structures may be further substituted with a group represented by formula (RP-1) described below or a known substituent such as a hydrocarbon group.

[0045] R １１１ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-9), R １１１ is preferably a group represented by the following formula (V-9-2): １１１ represents the bonding site with the two nitrogen atoms to which the two are bonded. In addition, the hydrogen atoms in the following structures may be further substituted with a group represented by formula (RP-1) described below or a known substituent such as a hydrocarbon group.

[0046] R １１１ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-10), R １１１ is preferably a group represented by the following formula (V-10-2): １１１represents the bonding site with the two nitrogen atoms to which the two are bonded. In addition, the hydrogen atoms in the following structures may be further substituted with a group represented by formula (RP-1) described below or a known substituent such as a hydrocarbon group.

[0047] Others, R １１１ may be a group described in paragraphs 0042 to 0053 of JP-A No. 2023-003421. １１１ It is preferable that R does not contain an imide structure in its structure. １１１ It is preferable that R does not contain a urethane bond, a urea bond, or an amide bond in the structure. １１１ It is preferable that R does not contain an ester bond in the structure. １１１ It is preferable that the copolymer does not contain an imide structure, a urethane bond, a urea bond, or an amide bond, and it is more preferable that the copolymer does not contain an imide structure, a urethane bond, a urea bond, an amide bond, or an ester bond.

[0048] R in formula (2) １１５ represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is more preferred. In formula (5) or formula (6), * each independently represents a bonding site to another structure. In formula (5), R １１２ represents a single bond or a divalent linking group, and is a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ２ -, -NHCO-, and a group selected from a combination thereof are preferred, and a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, and -SO ２ - is more preferably a group selected from -CH ２ -, -C(CF ３ ) ２ -, -C(CH ３ ) ２ -, -O-, -CO-, -S- and -SO ２ It is more preferably a divalent group selected from the group consisting of -.

[0049] R １１５ The number of carbon atoms in the group is preferably 4 or more, more preferably 4 to 50, and even more preferably 4 to 40.

[0050] Among these, R １１５ 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 the above formulas (V-1) to (V-10), the chemical resistance and flatness of the cured product are improved. １１５ 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), it is possible to obtain effects such as suppressing the generation of development residues, lowering the dielectric constant of the cured product, and reducing the thermal expansion coefficient.By using 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-6) to (V-10), it is possible to obtain effects such as improving the transmittance of ultraviolet light, making it difficult for the pattern of the cured product to become tapered, and widening the tolerance for the exposure dose.

[0051] R １１５ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-1), R １１５ is preferably a group represented by the following formula (V-1-1): In the following formula, * represents R in formula (2). １１５ represents bonding sites with the four carbonyl groups to which n1 is bonded, and n1 represents an integer of 0 to 5, and is also preferably an integer of 1 to 5. Furthermore, the hydrogen atoms in the following structures may be further substituted with a group represented by formula (RP-1) described below or a known substituent such as a hydrocarbon group.

[0052] R １１５ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-2), R １１５ is preferably a group represented by the following formula (V-2-1) or formula (V-2-2), and from the viewpoint of lowering the amine value in the resin, it is preferably a group represented by formula (V-2-2). In this specification, a bond crossing a side of a ring structure means that it substitutes one of the hydrogen atoms in the ring structure. In the following formula, L Ｘ１represents a single bond or —O—, and * represents R １１５ represents the bonding site with the four carbonyl groups to which R is bonded. Ｘ１ The definitions and preferred embodiments of are as described above. In addition, the hydrogen atoms in these structures may be further substituted with a group represented by formula (RP-1) described below or a known substituent such as a hydrocarbon group.

[0053] R １１５ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-3), R １１５ is preferably a group represented by the following formula (V-3-1) or formula (V-3-2), and from the viewpoint of reducing the dielectric constant of the cured product, is preferably a group represented by formula (V-3-2). In the following formulas, * represents R １１５ represents the bonding site with the four carbonyl groups to which R is bonded. Ｘ２ and R Ｘ３ The definitions and preferred embodiments of are as described above. In addition, the hydrogen atoms in these structures may be further substituted with a group represented by formula (RP-1) described below or a known substituent such as a hydrocarbon group.

[0054] R １１５ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-4), R １１５ is preferably a group represented by the following formula (V-4-1): In the following formula (V-4-1), * represents R １１５ represents bonding sites with the four carbonyl groups to which n1 is bonded, and n1 represents an integer of 0 to 5. Furthermore, the hydrogen atoms in formula (V-4-1) may be further substituted with a group represented by formula (RP-1) described below 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. However, it is also preferable that none of the hydrogen atoms in the structure represented by (V-4-1) is substituted.

[0055] R １１５is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-5), R １１５ is preferably a group represented by the following formula (V-5-1): In the following formula, * represents R in formula (2). １１５ represents the bonding sites with the four carbonyl groups to which the carbonyl groups are bonded. Furthermore, the hydrogen atoms in formula (V-5-1) may be further substituted with a group represented by formula (RP-1) described below 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. However, it is also preferable that none of the hydrogen atoms in the structure represented by (V-5-1) is substituted.

[0056] R １１５ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-6), R １１５ is preferably a group represented by the following formula (V-6-1): In the following formula, * represents R in formula (2). １１５ represents the bonding sites with the four carbonyl groups to which the carbonyl groups are bonded. In addition, the hydrogen atoms in the following structure may be further substituted with a group represented by formula (RP-1) described below or a known substituent such as a hydrocarbon group.

[0057] R １１５ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-7), R １１５ is preferably a group represented by the following formula (V-7-1): In the following formula, * represents R １１５ represents the bonding sites with the four carbonyl groups to which the carbonyl groups are bonded. In addition, the hydrogen atoms in the following structure may be further substituted with a group represented by formula (RP-1) described below or a known substituent such as a hydrocarbon group.

[0058] R １１５ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-8), R １１５ is preferably a group represented by the following formula (V-8-1): In the following formula, * represents R １１５ represents the bonding site with the four carbonyl groups to which R is bonded.Ｘ５ The definition and preferred embodiments of are as described above. In addition, the hydrogen atoms in the following structures may be further substituted with a group represented by formula (RP-1) described below or a known substituent such as a hydrocarbon group.

[0059] R １１５ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-9), R １１５ is preferably a group represented by the following formula (V-9-1): In the following formula, * represents R １１５ represents the bonding sites with the four carbonyl groups to which the carbonyl groups are bonded. In addition, the hydrogen atoms in the following structure may be further substituted with a group represented by formula (RP-1) described below or a known substituent such as a hydrocarbon group.

[0060] R １１５ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-10), R １１５ is preferably a group represented by the following formula (V-10-1): In the following formula, * represents R １１５ represents the bonding sites with the four carbonyl groups to which the carbonyl groups are bonded. In addition, the hydrogen atoms in the following structures may be further substituted with known substituents such as a group represented by formula (RP-1) described below or a hydrocarbon group.

[0061] Others, R １１５ may be a tetracarboxylic acid residue remaining after removal of the anhydride group from a tetracarboxylic acid dianhydride described in paragraphs 0055 to 0057 of JP-A No. 2023-003421.

[0062] Also, R １１５ It is preferable that R does not contain an imide structure in its structure. １１５ In the present invention, the urethane bond is *—O—C(═O)—NR Ｎ - is a bond represented by *, and R Ｎ represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom. Ｎis preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom. Ｎ —C(═O)—NR Ｎ - is a bond represented by *, and R Ｎ R each independently represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom. Ｎ Preferred embodiments of R are as described above. １１５ It is preferable that R does not contain an ester bond in its structure. In the present invention, an ester bond is a bond represented by *--O--C(=O)--*. Among these, R １１５ It is preferable that the copolymer does not contain an imide structure, a urethane bond, a urea bond, or an amide bond, and it is more preferable that the copolymer does not contain an imide structure, a urethane bond, a urea bond, an amide bond, or an ester bond.

[0063] Also, R １１５ is a structure represented by the following formula (X-3), or X in the structure represented by formula (X-3): ２ or a hydrogen atom of a group represented by ３ The hydrogen atom of the group represented by formula (RP-1) below may be substituted with a group represented by formula (RP-1). In formula (X-3), X ２ each independently represents a trivalent linking group; L ３ represents a divalent linking group, and * represents a bonding site with another structure. ２ and L ３ A preferred embodiment of the formula (X-2) is ２ and L ３ This is the same as the preferred embodiment of the above.

[0064] R １１５ Specifically, R may be a tetracarboxylic acid residue remaining after removal of the anhydride group from a tetracarboxylic dianhydride. １１５ The tetracarboxylic acid dianhydride may contain only one kind or two or more kinds of tetracarboxylic acid dianhydride residues as a structure corresponding to the formula (I). The tetracarboxylic acid dianhydride is preferably represented by the following formula (O). In formula (O), R １１５ represents a tetravalent organic group. １１５ The preferred range of R in formula (2) is １１５ The same applies to the preferred range of .

[0065] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfidetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2 2,3,3',4'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and alkyl and alkoxy derivatives having 1 to 6 carbon atoms thereof.

[0066] Further, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017 / 038598 are also preferred examples.

[0067] Among these, R in formula (2) １１５ and R １１１ Preferably, all of them contain a ring structure, and more preferably, all of them contain an aromatic ring structure. １１５ and R １１１ is preferably an organic group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of the above formulas (V-1) to (V-10), and more preferably an organic group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of the above formulas (V-1) to (V-4). Preferred aspects of these groups are as described above.

[0068] In formula (2), R １１１ and R １１５ At least one of R may have an OH group. １１１ Examples of the amino acid residue include residues of bisaminophenol derivatives.

[0069] [Group represented by formula (RP-1)] In formula (2), R １１１ and R １１５ At least one of them may contain a group represented by formula (RP-1). In formula (RP-1), L １ represents a 1+1-valent linking group, A １ represents a polymerizable group, a1 represents an integer of 1 or more, * represents R １１５ or R １１１ It represents the binding site with other structures in the molecule.

[0070] In formula (RP-1), L １ is preferably a group represented by the following formula (L-2). In formula (L-2), Z ２ -O-, -NR Ｎ -, -C(=O)O- or -C(=O)NR Ｎ represents -, and R Ｎ represents a hydrogen atom or a monovalent organic group; when a1 is 1, Lｘ represents a single bond or a divalent linking group, and when a1 is 2 or more, L ｘ represents a linking group having a valence of a1+1, a1 represents an integer of 1 or more, * represents R １１５ or R １１１ represents a bonding site with another structure in formula (RP-1), and # represents a bonding site with another structure in formula (RP-1). １ represents the binding site with

[0071] In formula (L-2), Z ２ is preferably —O— or —C(═O)O—. ２ Ga-NR Ｎ -, then 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. ｘ is preferably an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, even more preferably an alkylene group having 1 to 4 carbon atoms, and particularly preferably a methylene group. ｘ 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 (RP-1).

[0072] In formula (RP-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.

[0073] Among these, A １is 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, from the viewpoint of reactivity, a (meth)acryloxy group is preferred. Furthermore, from the viewpoint of reducing the dielectric loss tangent of the cured product, a maleimide group or a vinylphenyl group is preferred. In particular, A in formula (RP-1) contained in formula (2) １ At least one of the groups 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.

[0074] Among these, A in formula (RP-1) １ is a vinylphenyl group, and L １ is preferably a group represented by formula (L-2-1). In formula (L-2-1), L Ｘ２ represents a hydrocarbon group, a1 represents an integer of 1 or more, * represents R １１５ or R １１１ represents a bonding site with another structure in formula (RP-1), and # represents a bonding site with another structure in formula (RP-1). １ In formula (L-2-1), L Ｘ２ is preferably an aliphatic saturated hydrocarbon group. 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 (RP-1).

[0075] In addition, A in formula (RP-1) １ is a maleimide group, and L １ is a group represented by formula (L-2), and L in formula (L-2) Ｘis preferably 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, but is preferably an aromatic hydrocarbon group. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, more preferably an aromatic hydrocarbon group having 6 carbon atoms. Examples of heteroatoms in the aromatic heterocyclic group include an oxygen atom, a nitrogen atom, and a sulfur atom. The number of heteroatoms in the aromatic heterocyclic group is preferably 1 or 2. Furthermore, the aromatic heterocyclic group is preferably a 5- or 6-membered ring containing the above 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 be linear, branched, cyclic, or have a structure represented by a combination thereof. The number of carbon atoms in the aliphatic saturated hydrocarbon group having 4 or more carbon atoms is preferably 4 to 20, more preferably 5 to 10.

[0076] In formula (RP-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 one of the preferred embodiments of the present invention.

[0077] The number of ester bonds contained in formula (RP-1) is preferably 1 or 0.

[0078] R in formula (2) １１３ and R １１４ each independently represents 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. １１３ and R １１４ Preferably, at least one of R contains a polymerizable group, and more preferably, both of R １１３ and R １１４It is also preferable that at least one of the groups 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 a radically polymerizable group is preferred. 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 possessed by 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 (e.g., a vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III), with a group represented by the following formula (III) being preferred.

[0079]

[0080] 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 with 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. ２０１ Examples of the alkylene group include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, and a dodecamethylene group; a 1,2-butanediyl group, a 1,3-butanediyl group; a —CH ２ CH(OH)CH ２ alkylene groups such as ethylene and propylene groups; ２ CH(OH)CH ２More preferred are alkylene groups such as ethylene and propylene, or polyalkyleneoxy groups. In the present invention, a 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 a polyalkyleneoxy group contains multiple alkyleneoxy groups with different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, a block arrangement, or an arrangement having an alternating pattern. The number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent if the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 6, even more preferably 2 to 5, even more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2. The alkylene group may also have a substituent. Preferred substituents include alkyl groups, aryl groups, and halogen atoms. The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoint of solvent solubility and solvent resistance, the polyalkyleneoxy group is preferably a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, more preferably a polyethyleneoxy group or a polypropyleneoxy group, and even more preferably a polyethyleneoxy group. In the group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, the ethyleneoxy groups and propyleneoxy groups may be arranged randomly, in blocks, or in an alternating pattern. The preferred embodiments of the number of repeating ethyleneoxy groups and the like in these groups are as described above.

[0081] In formula (2), R １１３is a hydrogen atom, or R １１４ When is a hydrogen atom, the polyimide precursor may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

[0082] In formula (2), R １１３ and R １１４ At least one of the groups may be a polarity conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxy group. Preferred examples include an acetal group, a ketal group, a silyl group, a silyl ether group, and a tertiary alkyl ester group. From the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferred. Specific examples of the acid-decomposable group include a tert-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tert-butoxycarbonylmethyl group, and a trimethylsilyl ether group. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.

[0083] The polyimide precursor preferably contains fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more and 20% by mass or less.

[0084] Furthermore, for the purpose of improving adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specific examples include embodiments using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, or the like as the diamine.

[0085] The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having a repeating unit represented by formula (2-A). When the polyimide precursor contains a repeating unit represented by formula (2-A), it becomes possible to further widen the width of the exposure latitude. Formula (2-A) In formula (2-A), A １ and A ２ represents an oxygen atom, R １１１ and R １１２ each independently represents a divalent organic group; R １１３ and R １１４ each independently represents a hydrogen atom or a monovalent organic group; R １１３ and R １１４ At least one of the groups is a group containing a polymerizable group, and it is preferred that both of the groups are groups containing a polymerizable group.

[0086] A １ , A ２ , R １１１ , R １１３ and R １１４ are each independently A in formula (2). １ , A ２ , R １１１ , R １１３ and R １１４ The same definition and preferred range are also the same. １１２ is R in formula (5). １１２ The same applies to the preferred range.

[0087] The polyimide precursor may contain one type of repeating unit represented by formula (2), or may contain two or more types. It may also contain a structural isomer of the repeating unit represented by formula (2). The polyimide precursor may also contain other types of repeating units in addition to the repeating unit of formula (2).

[0088] In one embodiment of the polyimide precursor of the present invention, the content of the repeating unit represented by formula (2) is 50 mol% or more of all repeating units. The total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the polyimide precursor except for the terminal repeating units may be repeating units represented by formula (2).

[0089] The weight-average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. The number-average molecular weight (Mn) of the polyimide precursor is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The molecular weight dispersity of the polyimide precursor 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 precursor is not particularly specified, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 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 polyimide precursors as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide precursor 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 polyimide precursors as a single resin are each within the above-mentioned ranges.

[0090] 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 less than 50%, and even more preferably less than 30%, from the viewpoint of the film strength, insulating properties, etc. of the resulting organic film. The lower limit of the imidization rate may be 0% or more, or may be 5% or more, or may be 10% or more. The imidization rate refers to the ratio (%) of the molar amount of imide ring structures to the total molar amount of amic acid structures, amic acid ester structures, and imide ring structures.

[0091] [Polyimide] The polyimide used in the present invention may be an alkali-soluble polyimide, or may be a polyimide soluble in a developer containing an organic solvent as a main component. In this specification, alkali-soluble polyimide refers to a polyimide that dissolves at 0.1 g or more in 100 g of a 2.38 mass % aqueous tetramethylammonium solution at 23°C. From the viewpoint of pattern formability, a polyimide that dissolves at 0.5 g or more is preferred, and a polyimide that dissolves at 1.0 g or more is even more preferred. The upper limit of the solubility is not particularly limited, but is preferably 100 g or less. From the viewpoint of the film strength and insulating properties of the resulting organic film, the polyimide is preferably a polyimide having multiple imide structures in its main chain.

[0092] -Fluorine Atom- From the viewpoint of the film strength of the obtained organic film, it is also preferable that the polyimide contains a fluorine atom. The fluorine atom is, for example, R １３２ or R in the repeating unit represented by formula (4) described below １３１ and R in the repeating unit represented by formula (4) described below is preferably included. １３２ or R in the repeating unit represented by formula (4) described below １３１ The amount of fluorine atoms relative to the total mass of the polyimide is preferably 5% by mass or more and 20% by mass or less.

[0093] -Silicon Atom- From the viewpoint of the film strength of the obtained organic film, it is also preferable that the polyimide contains a silicon atom. The silicon atom is, for example, R in the repeating unit represented by formula (4) described later. １３１ and R in the repeating unit represented by formula (4) described below is preferably included. １３１ It is more preferable that the silicon atom or the organic modified (poly)siloxane structure described below is contained in the polyimide. The silicon atom or the organic modified (poly)siloxane structure may be contained in a side chain of the polyimide, but is preferably contained in the main chain of the polyimide. The amount of silicon atoms relative to the total mass of the polyimide is preferably 1 mass % or more and 20 mass % or less.

[0094] - Ethylenically unsaturated bond - From the viewpoint of the film strength of the obtained organic film, it is preferable that the polyimide has an ethylenically unsaturated bond. The polyimide may have the ethylenically unsaturated bond at the end of the main chain or in a side chain, but it is preferable that the ethylenically unsaturated bond is in a side chain. The ethylenically unsaturated bond is preferably radically polymerizable. The ethylenically unsaturated bond is formed by the R １３２ or R １３１ and R １３２ or R １３１ Among these, the ethylenically unsaturated bond is more preferably contained as a group having an ethylenically unsaturated bond in R １３１ and R １３１ Examples of the group having an ethylenically unsaturated bond include a group having an optionally substituted vinyl group directly bonded to an aromatic ring, such as a vinyl group, an allyl group, or a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, a group represented by the above formula (RP-1), and a group represented by the following formula (IV).

[0095]

[0096] In formula (IV), R ２０represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and is preferably a hydrogen atom or a methyl group.

[0097] In formula (IV), R ２１ represents an alkylene group having 2 to 12 carbon atoms, —O—CH ２ CH(OH)CH ２ -, -C(=O)O-, -O(C=O)NH-, a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and particularly preferably 2 or 3 carbon atoms; the number of repeating alkyleneoxy groups is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3 carbon atoms), or a group combining two or more of these. The alkylene group having 2 to 12 carbon atoms may be any of linear, branched, and cyclic alkylene groups, or alkylene groups represented by a combination thereof. The alkylene group having 2 to 12 carbon atoms is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.

[0098] Among these, R ２１ is preferably a group represented by any one of the following formulae (R1) to (R3), and more preferably a group represented by formula (R1). In formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group in which two or more of these are bonded together; X represents an oxygen atom or a sulfur atom; * represents a bonding site with another structure; and ● represents R ２１ In formulas (R1) to (R3), a preferred embodiment of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms as L is R in formula (IV). ２１The preferred embodiments are the same as those of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms. In formula (R1), X is preferably an oxygen atom. In formulas (R1) to (R3), * has the same meaning as * in formula (IV), and the preferred embodiments are also the same. The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having an isocyanato group and an ethylenically unsaturated bond (e.g., 2-isocyanatoethyl methacrylate). The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (e.g., 2-hydroxyethyl methacrylate). The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (e.g., glycidyl methacrylate).

[0099] In formula (IV), * represents a bonding site to another structure, and is preferably a bonding site to the main chain of the polyimide.

[0100] The amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.0005 to 0.05 mol / g.

[0101] -Polymerizable group other than a group having an ethylenically unsaturated bond- The polyimide may have a polymerizable group other than a group having an ethylenically unsaturated bond. Examples of the polymerizable group other than a group having an ethylenically unsaturated bond include an epoxy group, a cyclic ether group such as an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a methylol group. Examples of the polymerizable group other than a group having an ethylenically unsaturated bond include R in the repeating unit represented by formula (4) below. １３１ The amount of polymerizable groups other than groups having an ethylenically unsaturated bond relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0102] - Polarity conversion group - The polyimide may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the polyimide is R １１３ and R １１４ The polarity conversion group is, for example, R in the repeating unit represented by formula (4) described later. １３１ , R １３２ , contained in the terminals of polyimides, etc.

[0103] -Acid Value- When the polyimide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of the polyimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and even more preferably 70 mgKOH / g or more. The acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and even more preferably 200 mgKOH / g or less. When the polyimide is subjected to development using a developer containing an organic solvent as a main component (e.g., "solvent development"), the acid value of the polyimide is preferably 1 to 35 mgKOH / g, more preferably 2 to 30 mgKOH / g, and even more preferably 5 to 20 mgKOH / g. The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. From the viewpoint of achieving both storage stability and developability, the acid group contained in the polyimide preferably has a pKa of 0 to 10, more preferably 3 to 8. pKa refers to the equilibrium constant Ka of a dissociation reaction in which a hydrogen ion is released from an acid, expressed as its negative common logarithm, pKa. In this specification, pKa refers to a value calculated using ACD / ChemSketch (registered trademark) unless otherwise specified. For pKa, reference may be made to the value listed in the "Revised 5th Edition Chemistry Handbook: Basics" compiled by the Chemical Society of Japan. When the acid group is a polyvalent acid such as phosphoric acid, the pKa is the first dissociation constant. As such an acid group, the polyimide preferably contains at least one selected from the group consisting of a carboxy group and a phenolic hydroxy group, and more preferably a phenolic hydroxy group.

[0104] -Phenol Hydroxy Group- From the viewpoint of ensuring an appropriate development rate with an alkaline developer, the polyimide preferably has a phenolic hydroxy group. The polyimide may have the phenolic hydroxy group at the end of the main chain or on a side chain. The phenolic hydroxy group can be, for example, R in the repeating unit represented by formula (4) described below. １３２ or R １３１ The amount of phenolic hydroxy groups relative to the total mass of the polyimide is preferably 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.

[0105] The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but it is preferable that it contains a repeating unit represented by the following formula (4). In formula (4), R １３１ represents a divalent organic group, and R １３２ represents a tetravalent organic group. When the compound has a polymerizable group, the polymerizable group is １３１ and R １３２ or may be located at the end of the polyimide as shown in the following formula (4-1) or formula (4-2): In formula (4-1), R １３３ is a polymerizable group, and the other groups have the same meanings as in formula (4). In formula (4-2), R １３４ and R １３５ At least one of the groups is a polymerizable group, and if it is not a polymerizable group, it is an organic group, and the other group has the same meaning as in formula (4).

[0106] Examples of the polymerizable group include the above-mentioned group containing an ethylenically unsaturated bond and a crosslinkable group other than the above-mentioned group having an ethylenically unsaturated bond. １３１ represents a divalent organic group. The divalent organic group is R １１１Among these, the divalent organic group is preferably a group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of the above formulas (V-1) to (V-10), and more preferably a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of the above formulas (V-1) to (V-10), and which has a group represented by formula (RP-1) as a substituent in the structure. R １３１ The diamine residues include those remaining after removal of the amino groups of the diamine. Examples of the diamine include aliphatic, cycloaliphatic, and aromatic diamines. Specific examples include R in the formula (2) of the polyimide precursor. １１１ Examples include:

[0107] R １３１ is preferably a diamine residue having at least two alkylene glycol units in the main chain, in order to more effectively suppress the occurrence of warping during firing, more preferably a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and even more preferably a diamine residue of the above diamine that does not contain an aromatic ring.

[0108] Examples of diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule include, but are not limited to, Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, and D-4000 (all trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.

[0109] R １３２ represents a tetravalent organic group. The tetravalent organic group is R １１５ Examples of the group R are the same as those of the group R, and the preferred ranges are also the same. １１５The four bonds of the tetravalent organic group exemplified by: are bonded to the four —C(═O)— moieties in formula (4) to form a condensed ring.

[0110] R １３２ Examples of the tetracarboxylic acid residues include those remaining after removal of the anhydride groups from tetracarboxylic dianhydrides. １１５ From the viewpoint of the strength of the organic film, R １３２ is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

[0111] R １３１ and R １３２ It is also preferable that at least one of R １３１ Preferred examples of R include 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18). １３２ As the above, (DAA-1) to (DAA-5) are more preferred examples.

[0112] The polyimide preferably contains fluorine atoms in its structure, and the content of fluorine atoms in the polyimide is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0113] To improve adhesion to the substrate, the polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specific examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0114] In order to improve the storage stability of the resin composition, it is preferable that the main chain terminals of the polyimide are blocked with a terminal blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound. Among these, it is more preferable to use a monoamine, and preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, and 1-carboxy 2-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, and multiple different terminal groups may be introduced by reacting multiple terminal-capping agents.

[0115] -Imidization rate (ring closure rate)- 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.

[0116] Polyimide is a polymer in which all repeating units are R １３１ and R １３２ The repeating unit may contain the repeating unit represented by the above formula (4) in which the combination of R１３１ and R １３２ The polyimide may contain a repeating unit represented by the formula (4) above, which contains two or more different combinations of repeating units. In addition to the repeating unit represented by the formula (4), the polyimide may contain other types of repeating units. Examples of other types of repeating units include the repeating unit represented by the formula (2) above.

[0117] Polyimides can be synthesized by, for example, reacting a tetracarboxylic dianhydride with a diamine (partially substituted with a monoamine end-capping agent) at low temperature, reacting a tetracarboxylic dianhydride with a diamine (partially substituted with an acid anhydride, monoacid chloride compound, or monoactive ester compound end-capping agent) at low temperature, preparing a diester from a tetracarboxylic dianhydride with an alcohol and then reacting it with a diamine (partially substituted with a monoamine end-capping agent) in the presence of a condensing agent, preparing a diester from a tetracarboxylic dianhydride with an alcohol and then converting the remaining dicarboxylic acid to an acid chloride and reacting it with a diamine (partially substituted with a monoamine end-capping agent), or by completely imidizing the resulting polyimide precursor using a known imidization reaction method, or by terminating the imidization reaction midway to introduce a partial imide structure, or by blending a fully imidized polymer with the polyimide precursor to introduce a partial imide structure. Other known polyimide synthesis methods can also be used.

[0118] The weight-average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. By setting 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 (e.g., breaking elongation), the weight-average molecular weight is particularly preferably 15,000 or more. The number-average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The molecular weight dispersity of the polyimide 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, and even more preferably 6.0 or less. When the resin composition contains multiple types of polyimides as specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one type of polyimide are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple types of polyimides as one resin are each within the above ranges.

[0119] [Polybenzoxazole Precursor] Examples of the polybenzoxazole precursor include the compounds described in paragraphs 0073 to 0095 of WO 2022 / 145355. The above descriptions are incorporated herein by reference.

[0120] [Polybenzoxazole] Examples of polybenzoxazole include the compounds described in paragraphs 0096 to 0103 of WO 2022 / 145355. The above descriptions are incorporated herein by reference.

[0121] [Polyamideimide Precursor] Examples of the polyamideimide precursor include the compounds described in paragraphs 0104 to 0119 of WO 2022 / 145355. The above descriptions are incorporated herein by reference.

[0122] In addition, when the specific resin is a polyamide-imide precursor, R １１５is a structure represented by the following formula (X-2), or X in the structure represented by formula (X-2): ２ or a hydrogen atom of a group represented by ３ In the above embodiment, the hydrogen atom of the group represented by formula (2) may be substituted with a group represented by formula (RP-1). １ , A ２ , R １１１ , R １１３ and R １１４ The preferred embodiments are as described above. In formula (X-2), X ２ each independently represents a trivalent linking group; L ３ represents a divalent linking group, and * represents a bonding site to another structure.

[0123] In formula (X-2), X ２ 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, 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. Examples of the linking group include -O-, -S-, -C(=O)-, -S(=O) ２Preferred are -, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these, and more preferred are -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. Furthermore, 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 may have all of the hydrogen atoms substituted with halogen atoms, but it is preferable 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.

[0124] Also, X ２ 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 referred to as a tricarboxylic acid compound. Two of the three carboxy groups in the tricarboxylic acid compound may be converted to acid anhydrides. Examples of tricarboxylic acid compounds that 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.

[0125] X ２ It is preferable that X does not contain an imide structure in its structure. ２It is preferable that X does not contain a urethane bond, a urea bond, or an amide bond in the structure. ２ It is preferable that X does not contain an ester bond in the structure. ２ It is preferable that the copolymer does not contain an imide structure, a urethane bond, a urea bond, or an amide bond, and it is more preferable that the copolymer does not contain an imide structure, a urethane bond, a urea bond, an amide bond, or an ester bond.

[0126] Specifically, the tricarboxylic acid compound is preferably a tricarboxylic acid compound containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined via a single bond or a linking group, and more preferably a tricarboxylic acid compound containing an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined via a single bond or a linking group.

[0127] 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 bonded with a single bond, —O—, —CH ２ -, -C(CH ３ ) ２ -, -C(CF ３ ) ２ -, -SO ２ These compounds may be compounds in which two carboxy groups are anhydride (e.g., trimellitic anhydride), or compounds in which at least one carboxy group is halogenated (e.g., trimellitic anhydride chloride).

[0128] In formula (X-2), L ３is 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. Examples of the linking group include -O-, -S-, -C(=O)-, -S(=O) ２ Preferred are -, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these, and more preferred are -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. Furthermore, 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 may have all of the hydrogen atoms substituted with halogen atoms, but it is preferable 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.

[0129] [Polyamideimide] Examples of polyamideimide include the compounds described in paragraphs 0120 to 0133 of WO 2022 / 145355, the disclosure of which is incorporated herein by reference.

[0130] [Method for producing polyimide precursors, etc.] Polyimides, etc., can be produced, for example, by the method described in paragraphs 0134 to 0136 of WO 2022 / 145355. The above description is incorporated herein by reference. Alternatively, synthesis may be carried out with reference to other known methods.

[0131] [Content] The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the resin composition. Furthermore, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition. The resin composition of the present invention may contain only one type of specific resin, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0132] It is also preferable that the resin composition of the present invention contains at least two kinds of resins. Specifically, the resin composition of the present invention may contain a total of two or more kinds of the specific resin and other resins described later, or may contain two or more kinds of specific resins, but it is preferable that the resin composition of the present invention contains two or more kinds of specific resins. When the resin composition of the present invention contains two or more kinds of specific resins, for example, a polyimide precursor having a structure derived from a dianhydride (R １１５ ) preferably contains two or more different polyimide precursors.

[0133] <Other Resins> The resin composition of the present invention may contain the specific resin described above and another resin (hereinafter simply referred to as "other resin") different from the specific resin. Examples of other resins include 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. For example, by further adding a (meth)acrylic resin, a resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained. For example, instead of or in addition to the polymerizable compound described below, a resin having a high polymerizable group value and a weight average molecular weight of 20,000 or less (for example, a polymerizable group content of 1×10 per 1 g of resin) can be used. －３ By adding a (meth)acrylic resin (having a molecular weight of 1000 to 1000 mol / g or more) to the resin composition, it is possible to improve the coatability of the resin composition and the solvent resistance of the pattern (cured product).

[0134] 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, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total solid content of the resin composition. When the resin composition of the present invention contains other resins, the content of the other resins is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on the total solid content of the resin composition. A preferred embodiment of the resin composition of the present invention may also be an embodiment in which the content of the other resin is low. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the resin composition. The lower limit of the content is not particularly limited, as long as it is 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.

[0135] <Specific Compound> <Compound A1> The first resin composition is a compound represented by the following formula (A1-1), formula (A1-2), or formula (A1-3), which has a molar absorption coefficient of 1×10 at a wavelength of 365 nm. ３ L.mol －１ ・cm －１ The present invention includes Compound A1, which is shown below. In this specification, unless otherwise specified, a structure represented by a chemical formula includes all of its stereoisomers. For example, the structure represented by Formula (A1-1) includes both diastereomers such as syn-isomers and anti-isomers. In formula (A1-1), formula (A1-2), and formula (A1-3), R １ is an aromatic ring, and R ２ ~R ４ is an organic group, and R ２~R ４ may be the same or different, and R ５ ~R １０ is a hydrogen atom or an organic group, and R ５ ~R １０ may be the same or different, and R １ ~R １０ may be bonded to each other to form a ring structure.

[0136] [Molar absorption coefficient] The molar absorption coefficient of compound A1 at a wavelength of 365 nm is 5 × 10 ２ L.mol －１ ・cm －１ Preferably, it is 2×10 or less. ２ L.mol －１ ・cm －１ More preferably, it is 1×10 or less. ２ L.mol －１ ・cm －１ The lower limit of the molar extinction coefficient is not particularly limited, and it is more preferably 0 L mol or less. －１ ・cm －１ Any value greater than ε is sufficient. Here, the molar extinction coefficient is measured by the following method. 12.5 mg of compound A1 is weighed and dissolved in 100 mL of acetonitrile to prepare a 0.125 g / L solution of compound A1. 2 mL of this solution is taken and diluted to 25 mL with acetonitrile to prepare a 0.01 g / L solution of compound A1. The absorbance of this solution at a wavelength of 365 nm is measured using a spectrophotometer (Hitachi High-Tech Corporation, UH-4150), and the molar extinction coefficient ε is calculated using the following formula. Alternatively, if the solubility of compound A1 is low and all 12.5 mg does not dissolve in 100 mL of acetonitrile, 10.0 mg of compound A1 may be dissolved in 1000 mL of acetonitrile to prepare a 0.01 g / L solution. In addition, when the absorbance of a 0.01 g / L solution is too high to measure, the amount of compound A1 and the amount of acetonitrile may be appropriately changed and the measurement may be carried out, and the molar absorption coefficient may be calculated by the following formula. Formula: Molar absorption coefficient ε (L mol －１ ・cm －１ )=A / (C×l) (A: absorbance, C: concentration (mol / L), l: optical path length (cm))

[0137] [Formula (A1-1)] -R １ - In formula (A1-1), R １ R may be an aromatic hydrocarbon group or an aromatic heterocyclic group, but is preferably an aromatic hydrocarbon group which may have a substituent, and more preferably a phenyl group which may have a substituent. Examples of heteroatoms in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. １ The aromatic ring in may have a substituent (R １ In the above embodiment, the hydrogen atoms in the aromatic ring may be substituted with a substituent, but in another preferred embodiment, the aromatic ring is an unsubstituted aromatic ring. １ is preferably an unsubstituted aromatic hydrocarbon ring group, and more preferably an unsubstituted phenyl group. １ Examples of the substituent in the aromatic ring in the formula (I) include an alkyl group, an alkoxy group, an amino group which may have a substituent, a nitro group, a halogen atom, or a substituent linked via a sulfide structure, a sulfone structure, a sulfoxide structure, or a carbonyl structure.

[0138] -R ２ - In formula (A1-1), R ２ is preferably a structure represented by the following formula (R2-1) or formula (R2-2), and more preferably a structure represented by the following formula (R2-1). In formula (R2-1) and formula (R2-2), R ２２ is an organic group, and * is a bonding site with an oxygen atom. ２２ is preferably an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, still more preferably an alkyl group having 1 to 4 carbon atoms, a phenyl group, a naphthyl group, or an alkoxy group having 1 to 4 carbon atoms, and most preferably a methyl group, a phenyl group, a methoxy group, or an ethoxy group.

[0139] -R ３and R ４ - In formula (A1-1), R ３ and R ４ are preferably alkyl groups which may be bonded to each other. ３ and R ４ is more preferably an alkyl group having a total of 2 to 20 carbon atoms, even more preferably an alkyl group having a total of 2 to 12 carbon atoms, and particularly preferably an alkyl group having a total of 2 to 8 carbon atoms. ３ and R ４ When R ３ and R ４ is preferably an alkylene group having 4 to 8 carbon atoms, and ２ CH ２ CH ２ CH ２ - or -CH ２ CH ２ CH ２ CH ２ CH ２ Among these, R ３ and R ４ are both methyl groups, or are bonded to each other to form a ring, -CH ２ CH ２ CH ２ CH ２ - or -CH ２ CH ２ CH ２ CH ２ CH ２ - is most preferred.

[0140] -R ５ and R ６ -R ５ is preferably a hydrogen atom. ５ is not a hydrogen atom, R ５ R is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group. ６ is preferably a hydrogen atom. ６ When is not a hydrogen atom, a preferred embodiment is R ５ is the same as the preferred embodiment when is not a hydrogen atom.

[0141] [Formula (A1-2)] In formula (A1-2), R １ , R ２ , R ３ , R ４ , R ５ and R ６ A preferred embodiment of the formula (A1-1) is １ , R ２ , R ３ , R ４ , R ５ and R ６ In formula (A1-2), R ７ and R ８ In the preferred embodiments, R ５ In particular, R ５ ~R ８ are preferably all hydrogen atoms.

[0142] [Formula (A1-3)] In formula (A1-3), R １ , R ２ , R ３ , R ４ , R ５ and R ６ A preferred embodiment of the formula (A1-1) is １ , R ２ , R ３ , R ４ , R ５ and R ６ In formula (A1-3), R ７ , R ８ , R ９ and R １０ In the preferred embodiments, R ５ In particular, R ５ ~R １０ are preferably all hydrogen atoms.

[0143] [Formula (A1-4)] Compound A1 is preferably a compound represented by the following formula (A1-4). In formula (A1-4), R １ is an aromatic ring, and R ２３ is an alkyl group, an aryl group, or an alkoxy group, and R ３ and R４ is a hydrogen atom or an organic group, and R ３ and R ４ may be bonded to each other to form a ring structure.

[0144] In formula (A1-4), R １ , R ３ and R ４ A preferred embodiment of the formula (A1-1) is R １ , R ３ and R ４ In formula (A1-4), R ２３ A preferred embodiment of the formula (R2-1) is ２２ This is the same as the preferred embodiment of the above.

[0145] <Compound A2> The second resin composition of the present invention contains a compound A2 represented by the following formula (A2-1), formula (A2-2), or formula (A2-3). In formula (A2-1), formula (A2-2), and formula (A2-3), R １ is an unsubstituted phenyl group, and R ２ ~R ４ is an organic group, and R ２ ~R ４ may be the same or different, and R ５ ~R １０ is a hydrogen atom or an organic group, and R ５ ~R １０ may be the same or different, and R １ ~R １０ may be bonded to each other to form a ring structure.

[0146] [Molar absorption coefficient] The molar absorption coefficient of Compound A2 at a wavelength of 365 nm is 5 × 10 ２ L.mol －１ ・cm －１ Preferably, it is 2×10 or less. ２ L.mol －１ ・cm －１ More preferably, it is 1×10 or less. ２ L.mol －１ ・cm －１ The lower limit of the molar extinction coefficient is not particularly limited, and it is more preferably 0 L mol or less. －１ ・cm－１ Here, the molar absorption coefficient is measured by the same method as the molar absorption coefficient of the compound A1 described above.

[0147] [Formula (A2-1)] In formula (A2-1), R ２ , R ３ , R ４ , R ５ and R ６ A preferred embodiment of the formula (A1-1) is ２ , R ３ , R ４ , R ５ and R ６ This is the same as the preferred embodiment of the above.

[0148] [Formula (A2-2)] In formula (A2-2), R ２ , R ３ , R ４ , R ５ , R ６ , R ７ and R ８ A preferred embodiment of the formula (A1-2) is ２ , R ３ , R ４ , R ５ , R ６ , R ７ and R ８ In particular, R ５ ~R ８ are preferably all hydrogen atoms.

[0149] [Formula (A2-3)] In formula (A2-3), R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ and R １０ A preferred embodiment of the formula (A1-3) is ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ and R １０ In particular, R５ ~R １０ are preferably all hydrogen atoms.

[0150] [Formula (A2-4)] Compound A2 is preferably a compound represented by the following formula (A2-4). In formula (A2-4), R １ is an unsubstituted phenyl group, and R ２３ is an alkyl group, an aryl group, or an alkoxy group, and R ３ and R ４ is a hydrogen atom or an organic group, and R ３ and R ４ may be bonded to each other to form a ring structure.

[0151] In formula (A2-4), R １ , R ３ and R ４ A preferred embodiment of the formula (A1-1) is R １ , R ３ and R ４ In formula (A2-4), R ２３ A preferred embodiment of the formula (R2-1) is ２２ This is the same as the preferred embodiment of the above.

[0152] [Radical Generation] The specific compound is preferably a compound that generates radicals upon exposure to light with a wavelength of 300 to 400 nm. Whether or not the specific compound generates radicals upon exposure can be determined by the following method. A composition is prepared by dissolving 1 g of the specific compound and 5 g of methyl methacrylate in NMP, and the composition is exposed to exposure light with a wavelength of 300 to 400 nm at 1500 mJ / cm. ２ If 0.1 g or more of polymethyl methacrylate is generated in the composition after the above irradiation, the specific compound is determined to be a compound that generates radicals when exposed to light with a wavelength of 300 to 400 nm. In particular, from the viewpoint of exposure sensitivity, the specific compound is preferably a compound that generates alkyl radicals.

[0153] [Molecular Weight] The molecular weight of the specific compound is preferably less than 2,000, more preferably 1,000 or less, and even more preferably 500 or less. The lower limit of the molecular weight is not particularly limited, but is preferably 200 or more.

[0154] [Synthesis Method] The specific compound can be synthesized, for example, by the method described in the Examples below. Alternatively, the specific compound may be synthesized using other known synthesis methods, and the synthesis method is not particularly limited.

[0155] [Specific Examples] Specific examples of the specific compound include, but are not limited to, the compounds used in the examples described below, and the compounds described below.

[0156] [Content] The content of the specific compound relative to the total solid content of the resin composition of the present invention is preferably 0.05 to 30% by mass. The lower limit is more preferably 0.1% by mass or more, even more preferably 0.2% by mass or more, and particularly preferably 0.5% by mass or more. The upper limit is more preferably 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 7% by mass or less. Furthermore, when the content of the specific resin is taken as 100 parts by mass, the content of the specific compound is preferably 0.05 to 30 parts by mass, more preferably 0.1 to 15 parts by mass, even more preferably 0.2 to 10 parts by mass, and particularly preferably 0.5 to 7 parts by mass. One type of specific compound may be used alone, or two or more types may be used in combination. When two or more types are used in combination, the total amount thereof preferably falls within the above-mentioned range.

[0157] <Polymerizable Compound> The resin composition of the present invention preferably contains a polymerizable compound. Examples of the polymerizable compound include a polymerizable compound having a radical polymerizable group (radical crosslinking agent) and other crosslinking agents.

[0158] [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.

[0159] 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. The radical crosslinking agent may 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 obtained 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.

[0160] 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.

[0161] 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 a nucleophilic substituent such as a hydroxyl group, amino group, or sulfanyl group with monofunctional or polyfunctional isocyanates or epoxies, 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 an electrophilic substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as a halogeno group or a tosyloxy group with monofunctional or polyfunctional alcohols, amines, or thiols. As another example, it is also possible to use a group of compounds in which the above-mentioned unsaturated carboxylic acids are replaced with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc. Specific examples can be found in paragraphs 0113 to 0122 of JP 2016-027357 A, the contents of which are incorporated herein by reference.

[0162] 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.

[0163] Other preferred radical crosslinking agents 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.

[0164] 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.)), and 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. Oligomers of these agents can also be used.

[0165] Commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, SR-209, 231, and 239, which are difunctional methacrylates having four ethyleneoxy chains (all manufactured by Sartomer Corporation), DPCA-60, a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, a trifunctional acrylate having three isobutyleneoxy chains (all manufactured by Nippon Kayaku Co., Ltd.), and urethane oligomers such as Examples of such an ester 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).

[0166] 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, and urethane compounds having 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 having an amino structure or a 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.

[0167] 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 obtained by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound to provide an acid group. Particularly preferred is a radical crosslinking agent obtained by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound to provide an acid group, 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.

[0168] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH / g, more preferably 1 to 100 mgKOH / g. When the acid value of the radical crosslinking agent is within the above range, the agent has excellent handleability in production and developability. Furthermore, the agent has good polymerizability. The acid value is measured in accordance with the description of JIS K 0070:1992.

[0169] The radical crosslinking agent is preferably a radical crosslinking agent having at least one selected from the group consisting of a urea bond and a urethane bond (hereinafter also referred to as "crosslinking agent U"). Examples of crosslinking agent U include the compounds described in paragraphs 0133 to 0143 of WO 2023 / 190064, the contents of which are incorporated herein by reference.

[0170] From the viewpoints of pattern resolution and film elasticity, 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 ... 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 can be used. Two or more of these can be mixed and used as needed. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a formula weight of approximately 200 for the polyethylene glycol chain. From the viewpoint of suppressing warpage of the pattern (cured product), a monofunctional radical crosslinking agent can preferably be used as the radical crosslinking agent in the resin composition of the present invention.Preferred examples of monofunctional radical crosslinking agents 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. Preferred monofunctional radical crosslinking agents include compounds having a boiling point of 100°C or higher under normal pressure in order to suppress volatilization before exposure. Other examples of bifunctional or higher radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0171] When 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 solid 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.

[0172] The radical crosslinking agent may be used alone or in combination of two or more. When two or more types are used in combination, the total amount thereof is preferably within the above range.

[0173] [Other Crosslinking Agents] The resin composition of the present invention preferably contains another crosslinking agent different from the radical crosslinking agent described above. The other crosslinking agent refers to a crosslinking agent other than the radical crosslinking agent described above. Preferably, the other crosslinking agent is a compound having a plurality of groups in the molecule that promote the reaction of forming a covalent bond with other compounds in the composition or their reaction products upon exposure to light by a photoacid generator or a photobase generator. Preferably, the other crosslinking agent is a compound having a plurality of groups in the molecule that promote the reaction of forming a covalent bond with other compounds in the composition or their reaction products under the action of an acid or base. Examples of other crosslinking agents include the compounds described in paragraphs 0179 to 0207 of WO 2022 / 145355. The above descriptions are incorporated herein by reference.

[0174] The content of the other crosslinking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass, based on the total solid content of the resin composition. Only one type of other crosslinking agent may be contained, or two or more types may be contained. When two or more types of other crosslinking agents are contained, the total amount thereof is preferably within the above range.

[0175] [Polymerization Initiator] The resin composition of the present invention may contain a polymerization initiator. The polymerization initiator referred to here does not include compounds that fall under the specific compounds described above. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator. Furthermore, from the viewpoint of resolution, an embodiment that does not contain a photopolymerization initiator is also a preferred embodiment of the present invention. The content of the photopolymerization initiator that does not fall under the specific compound relative to the total solid content of the resin composition of the present invention is preferably 1% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0.01% by mass or less. The lower limit of the content is not particularly limited and may be 0% by mass. The photopolymerization initiator is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible light range is preferred. Alternatively, the resin composition may be an activator that reacts with a photoexcited sensitizer to generate active radicals.

[0176] The photoradical polymerization initiator has a capacity of at least about 50 L·mol within a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). －１ ・cm －１ It is preferable that the compound contains at least one compound having a molar absorption coefficient of

[0177] 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 of these compounds, 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. Further, paragraphs 0065 to 0111 of JP 2014-130173 A, compounds described in Japanese Patent No. 6301489, MATERIAL STAGE 37 to 60p, vol. 19, No. 3,2019 described peroxide-based photopolymerization initiators, photopolymerization initiators described in WO 2018 / 221177, photopolymerization initiators described in WO 2018 / 110179, photopolymerization initiators described in JP 2019-043864 A, photopolymerization initiators described in JP 2019-044030 A, peroxide-based initiators described in JP 2019-167313 A can be mentioned, the contents of which are incorporated herein by reference.

[0178] Examples of ketone compounds include the compounds described in paragraph 0087 of JP 2015-087611 A, the contents of which are incorporated herein by reference. As a commercially available product, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

[0179] In one embodiment of the present invention, a hydroxyacetophenone compound, an aminoacetophenone compound, or an acylphosphine compound can be suitably used as the photoradical polymerization initiator. More specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 or an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, the contents of which are incorporated herein by reference.

[0180] 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).

[0181] 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).

[0182] As the aminoacetophenone initiator, acylphosphine oxide initiator, and metallocene compound, 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.

[0183] As the photoradical polymerization initiator, an oxime compound is more preferably used. By using an oxime compound, it is possible to more effectively improve the exposure latitude. An oxime compound is particularly preferred because it has a wide exposure latitude (exposure margin) and also functions as a photocuring accelerator.

[0184] Specific examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), compounds described in J. C. S. Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232) described compounds, compounds described in JP-A-2000-066385, compounds described in JP-T-2004-534797, compounds described in JP-A-2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in WO 2015 / 152153, compounds described in WO 2017 / 051680, compounds described in JP-A-2017-198865, compounds described in paragraphs 0025 to 0038 of WO 2017 / 164127, compounds described in WO 2013 / 167515 and the like, the contents of which are incorporated herein.

[0185] 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 the resin composition, it is particularly preferable to use an oxime compound as a photoradical polymerization initiator. The oxime compound as a photoradical polymerization initiator has a linking group of >C=N-O-C(=O)- in the molecule.

[0186]

[0187] Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (manufactured by BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in JP 2012-014052 A), TR-PBG-304, 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 (SARTOMER Also, an oxime compound having the following structure can be used.

[0188] Examples of photoradical polymerization initiators include oxime compounds having a fluorene ring, oxime compounds having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring, and oxime compounds having a fluorine atom, as described in paragraphs 0169 to 0171 of WO 2021 / 112189. Also usable are oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds in which a substituent having a hydroxy group is bonded to a carbazole skeleton, as described in paragraphs 0208 to 0210 of WO 2021 / 020359. The contents of these compounds are incorporated herein by reference.

[0189] Among these, the photopolymerization initiator preferably contains a compound represented by the following formula (P-1).

[0190] In addition, compounds described in paragraphs 0113 to 0117 of JP-A No. 2023-058585 can also be used as the photopolymerization initiator, the disclosure of which is incorporated herein by reference.

[0191] When the resin composition contains a photopolymerization initiator, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass, based on the total solid content of the resin composition. 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, the total amount is preferably within the above range. Note that the photopolymerization initiator may also function as a thermal polymerization initiator, and therefore crosslinking by the photopolymerization initiator may be further promoted by heating in an oven, hot plate, or the like.

[0192] [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 undergoes electron transfer, energy transfer, heat generation, and other actions. This causes the thermal radical polymerization initiator or the photoradical polymerization initiator to undergo a chemical change and decompose, generating a radical, acid, or 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 the compounds described in paragraph 0202 of WO 2023 / 190064.

[0193] Among these, the compound represented by the following formula (AN-1) or (AN-2) (hereinafter also referred to as "compound AN") is preferred as the sensitizer because of its high sensitizing effect. In formula (AN-1), R １１ and R １２ each independently represents a hydrogen atom or a monovalent organic group; R １１ and R １２ At least one of Ar contains a group represented by formula (R-1), １represents an aromatic ring structure which may have a substituent or a condensed ring, n1 represents an integer of 2 or more, when n1 is 2, X represents a single bond or a divalent linking group, and when n1 is 3 or more, X represents an n1-valent linking group. ２１ and R ２２ each independently represents a hydrogen atom or a monovalent organic group; R ２１ and R ２２ At least one of Ar contains a group represented by formula (R-1), ２ represents an aromatic ring structure which may have a substituent or a condensed ring, and n2 represents an integer of 1 or more. In formula (R-1), R Ｒ１ and R Ｒ２ each independently represents a hydrogen atom or a monovalent organic group, and m R Ｒ１ may be the same or different, and m R Ｒ２ may be the same or different, m represents an integer of 2 or more, and * represents a bonding site to another structure.

[0194] In formula (AN-1), R １１ and R １２ is preferably a group represented by formula (R-1). １１ and R １２ is a hydrogen atom or a monovalent organic group other than the group represented by formula (R-1), R １１ and R １２ Preferably, one of the groups is a monovalent organic group different from the group represented by formula (R-1). Examples of the monovalent organic group different from the group represented by formula (R-1) include an alkyl group and an aryl group, with an alkyl group being preferred and a methyl group being more preferred.

[0195] In the group represented by formula (R-1), R Ｒ１ and R Ｒ２ each independently represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom or a methyl group. Ｒ１ and R Ｒ２are all hydrogen atoms. In formula (R-1), m represents an integer of 2 or more, preferably an integer of 2 to 4, more preferably 2 or 3, and even more preferably 2. Specific examples of the group represented by formula (R-1) are listed below, but the present invention is not limited to these. In the following specific examples, * has the same meaning as * in formula (R-1).

[0196] In formula (AN-1), Ar １ represents an aromatic ring structure which may have a substituent or a condensed ring. １ The aromatic ring structure in may be either an aromatic hydrocarbon ring structure or an aromatic heterocyclic ring structure, but is preferably an aromatic hydrocarbon ring structure, and more preferably a benzene ring structure. Examples of the substituent include an alkyl group, an aryl group, a halogen atom, etc., preferably an alkyl group, and more preferably a methyl group. Examples of the fused ring include a cycloalkane, an aromatic ring, etc., and is preferably a cyclopropane ring.

[0197] In formula (AN-1), n1 represents an integer of 2 to 4, preferably 2 or 3, and more preferably 2.

[0198] In formula (AN-1), when n1 is 2, X represents a single bond or a divalent linking group. The divalent linking group is preferably an alkylene group, a haloalkylene group, an arylene group, or a group represented by a combination thereof. The hydrogen atoms in these groups may be substituted with known substituents such as hydroxy groups and halogen atoms. The alkylene group is preferably an alkylene group having 1 to 4 carbon atoms, and more preferably a methylene group, ethylene group, or isopropylene group. The arylene group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, but is preferably an aromatic hydrocarbon group, and more preferably a phenylene group.

[0199] In formula (AN-1), when n1 is 3 or more, X represents an n1-valent linking group. The n1-valent linking group is preferably an aliphatic hydrocarbon group, an aromatic group, or a group represented by a combination thereof. The hydrogen atoms in these groups may be substituted with known substituents such as hydroxy groups. The aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, more preferably a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms. The aromatic group is preferably an aromatic hydrocarbon group, more preferably an aromatic hydrocarbon group having 6 carbon atoms.

[0200] In formula (AN-2), R ２１ and R ２２ A preferred embodiment of the formula (AN-1) is １１ and R １２ This is the same as the preferred embodiment of the above.

[0201] In formula (AN-2), Ar ２ represents an aromatic ring structure which may have a substituent or a condensed ring. Examples of the aromatic ring structure include a benzene ring structure, a carbazole ring structure, and a fluorene ring structure. Examples of the substituent include an alkyl group, an aryl group, and a halogen atom, with an alkyl group being preferred and a methyl group being more preferred. Examples of the condensed ring include a cycloalkane and an aromatic ring, with a cyclopropane ring being preferred.

[0202] In formula (AN-2), n2 is preferably an integer of 1 to 3, and more preferably 1 or 2.

[0203] Furthermore, the compound AN is preferably a compound represented by the following formula (an-1), (an-2), or (an-3).

[0204] 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 still more preferably 0.5 to 10 mass %, based on the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more types.

[0205] [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 those having -S-S-, -SO ２ Examples of compounds that can be used include compounds having -S-, -N-O-, SH, PH, SiH, and GeH, and dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthate compounds having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These compounds can donate hydrogen to low-activity radicals to generate radicals, or can be oxidized and then deprotonated to generate radicals. Thiol compounds are particularly preferred.

[0206] In addition, the chain transfer agent may be a compound described in paragraphs 0152 to 0153 of WO 2015 / 199219, the contents of which are incorporated herein by reference.

[0207] 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, relative to 100 parts by mass of the total solid 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 content thereof is preferably within the above range.

[0208] [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 a thermal radical polymerization initiator can also promote the polymerization reaction of the resin and the polymerizable compound, thereby further improving solvent resistance.

[0209] Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated herein by reference.

[0210] When a thermal polymerization initiator is contained, 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%, and even more preferably 0.5 to 15 mass%. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more types of thermal polymerization initiators are contained, it is preferable that the total amount is in the above range.

[0211] <Base Generator> The resin composition of the present invention may contain a base generator. Here, the base generator is a compound capable of generating 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 a thermal base generator in the resin composition, the cyclization reaction of the precursor can be promoted, for example, by heating, and the mechanical properties and chemical resistance of the cured product can be improved, resulting in excellent performance as an interlayer insulating film for a rewiring layer included in 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. Examples of known base generators include 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. Specific examples of non-ionic base generators include the compounds described in paragraphs 0249 to 0275 of WO 2022 / 145355. The above descriptions are incorporated herein by reference.

[0212] Examples of the base generator include, but are not limited to, the following compounds:

[0213]

[0214] The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

[0215] Specific preferred compounds for the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of WO 2018 / 038002.

[0216] Specific examples of ammonium salts include, but are not limited to, the following compounds:

[0217] Specific examples of iminium salts include, but are not limited to, the following compounds:

[0218] The base generator is preferably an amine in which the amino group is protected with a t-butoxycarbonyl group, from the viewpoints of storage stability and generating a base by deprotection during curing.

[0219] Examples of amine compounds protected by a t-butoxycarbonyl group include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, and 2-amino-1,3-propanediol. alcohol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzyl alcohol, diethanolamine diamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidyl)-2-propanol, 1,4-butanolbis(3-aminopropyl)ethanol ter, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybis(ethylamine), 1,14-diamino-3,6,9,12-tetraoxatetradecane, 1-aza-15-crown-5-ether, diethylene glycol bis(3-aminopropyl)ether, 1,11-diamino-3,6,9-trioxaundecane, or compounds in which the amino group of an amino acid or a derivative thereof is protected with a t-butoxycarbonyl group, but are not limited to these.

[0220] When the resin composition contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass per 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, even 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. One or more types of base generators can be used. When two or more types are used, the total amount is preferably within the above range.

[0221] <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.

[0222] Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, 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.)), 3-alkyloxypropionic acid alkyl esters (for example, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters ...alkyloxypropionate, ethyl 3-alkyloxypropionate, 2-alkyloxypropionic acid alkyl esters (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (for example, methyl 3-alkyloxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (for example, methyl 3- Preferred examples thereof include alkyl esters of alkyloxypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), 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.

[0223] 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.

[0224] Suitable examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0225] Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0226] A preferred example of the sulfoxides is dimethyl sulfoxide.

[0227] Preferred examples of the 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.

[0228] Preferred examples of ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0229] Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.

[0230] From the viewpoint of improving the properties of the coated surface, it is also preferable to mix two or more kinds of solvents.

[0231] 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. An embodiment in which toluene is further added to these combined solvents in an amount of approximately 1 to 10% by mass, based on the total mass of the solvent, is also a preferred embodiment of the present invention. In particular, from the viewpoint of the storage stability of the resin composition, an embodiment in which γ-valerolactone is included as a solvent is also a preferred embodiment 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 above content is not particularly limited and may be 100% by mass. The above 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 mass% of γ-valerolactone and 10 to 40 mass% of dimethyl sulfoxide, more preferably 70 to 90 mass% of γ-valerolactone and 10 to 30 mass% of dimethyl sulfoxide, and even more preferably 75 to 85 mass% of γ-valerolactone and 15 to 25 mass% of dimethyl sulfoxide, relative to the total mass of the solvent.

[0232] Furthermore, the resin composition of the present invention preferably contains one or more solvents selected from the group consisting of γ-butyrolactone and N-methyl-2-pyrrolidone, and ethyl lactate as solvents. The inclusion of ethyl lactate results in excellent film-forming properties. This is thought to be because ethyl lactate has low hydrophilicity, and its inclusion suppresses resin precipitation due to moisture in residual solvent when the composition is dried. In the above embodiment, the total content of one or more solvents selected from the group consisting of γ-butyrolactone and N-methyl-2-pyrrolidone and ethyl lactate is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, based on the total mass of the solvent. The upper limit of the content is not particularly limited, as long as it is 100% by mass or less. In the above-mentioned embodiment, the content of the one or more solvents selected from the group consisting of γ-butyrolactone and N-methyl-2-pyrrolidone relative to the total content of the one or more solvents selected from the group consisting of γ-butyrolactone and N-methyl-2-pyrrolidone and ethyl lactate is preferably 80 to 99.9 mass%, more preferably 90 to 99.5 mass%, and even more preferably 90 to 99.0 mass%. In the above-mentioned embodiment, the resin composition of the present invention preferably further contains dimethyl sulfoxide as a solvent. The inclusion of dimethyl sulfoxide improves the storage stability of the composition. This is presumably because dimethyl sulfoxide has high polarity, which suppresses aggregation of the resin in the composition. When dimethyl sulfoxide is contained, the content of dimethyl sulfoxide relative to the total mass of the solvent is preferably 10 to 40 mass%, more preferably 15 to 35 mass%, and even more preferably 20 to 30 mass%.

[0233] From the viewpoint of coatability, the content of the solvent is preferably an amount such that the total solids concentration of the resin composition of the present invention is 5 to 80 mass%, more preferably an amount such that the total solids concentration is 5 to 75 mass%, even more preferably an amount such that the total solids concentration is 10 to 70 mass%, and even more preferably an amount such that the total solids concentration is 20 to 70 mass%. The solvent content may be adjusted depending on the desired thickness of the coating film and the coating method. When two or more solvents are contained, the total amount of the solvents is preferably within the above range.

[0234] <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 the metal adhesion improver include a silane coupling agent having an alkoxysilyl group, an aluminum-based adhesion aid, a titanium-based adhesion aid, a compound having a sulfonamide structure, a compound having a thiourea structure, a phosphoric acid derivative compound, a β-ketoester compound, and an amino compound.

[0235] [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 formula below, 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.).

[0236]

[0237] 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- Examples of suitable silane coupling agents include (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 may be used alone or in combination of two or more. Furthermore, oligomeric compounds having multiple alkoxysilyl groups may also be used as silane coupling agents. Examples of such oligomeric compounds include compounds containing a repeating unit represented by the following formula (S-1): In formula (S-1), R Ｓ１ represents a monovalent organic group, R Ｓ２ represents a hydrogen atom, a hydroxy group or an alkoxy group, and n represents an integer of 0 to 2. Ｓ１is preferably 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, preferably 1. Here, the structures of the multiple repeating units represented by formula (S-1) contained in the oligomer-type compound may be the same. Here, of 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. Such oligomer-type compounds can be commercially available products, and an example of a commercially available product is KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0238] [Aluminum-Based Adhesion Aid] Examples of aluminum-based adhesion aids include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0239] Other metal adhesion improvers that can be used include the compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP-A-2013-072935, the contents of which are incorporated herein by reference.

[0240] 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, relative to 100 parts by mass of the specific resin. By ensuring that the content is equal to or greater than the above lower limit, the adhesion between the pattern and the metal layer is improved, and by ensuring that the content is equal to or less than the above upper limit, the heat resistance and mechanical properties of the pattern are improved. 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.

[0241] <Migration Inhibitor> The resin composition of the present invention preferably further contains a migration inhibitor. By including a 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 inhibited.

[0242] The migration inhibitor is not particularly limited, but examples thereof include compounds having a heterocycle (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, 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, 3,5-diamino-1,2,4-triazole, and 8-azaadenine, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole are preferably used.

[0243] As the migration inhibitor, an ion trapping agent that traps anions such as halogen ions can also be used.

[0244] Other migration inhibitors include the rust inhibitors described in paragraph 0094 of JP-A-2013-015701, the compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, the compounds described in paragraph 0052 of JP-A-2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of JP-A-2012-194520, and the compounds described in paragraph 0166 of WO 2015 / 199219. The contents of this specification are incorporated herein by reference.

[0245] Specific examples of the migration inhibitor include the following compounds.

[0246]

[0247] 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%, based on the total solid content of the resin composition.

[0248] The migration inhibitor may be one kind or two or more kinds. When two or more kinds of migration inhibitors are used, the total amount thereof is preferably within the above range.

[0249] <Light absorber> The resin composition of the present invention preferably contains a compound (light absorber) whose absorbance at the exposure wavelength is reduced by 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.

[0250] It is also preferable to include a compound having the following structure as the light absorber.

[0251] The content of the light absorber relative to the total solid content of the resin composition of the present invention is not particularly limited, but is preferably 0.1 to 20 mass%, more preferably 0.5 to 10 mass%, and even more preferably 1 to 5 mass%.

[0252] <Polymerization Inhibitor> The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

[0253] Specific examples of the polymerization inhibitor 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, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N-dioxide, and the like, the contents of which are incorporated herein by reference.

[0254] 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 solid content of the resin composition.

[0255] The polymerization inhibitor may be one kind or two or more kinds. When two or more kinds of polymerization inhibitors are used, the total amount thereof is preferably within the above range.

[0256] <Other Additives> The resin composition of the present invention may contain various additives, as needed, within the scope of obtaining the effects of the present invention, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet 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.). By appropriately incorporating these components, it is possible to adjust properties such as film physical properties. For details of these components, please refer to, for example, the descriptions in paragraphs 0183 and after of JP 2012-003225 A (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812 ), and the descriptions in paragraphs 0101 to 0104 and 0107 to 0109 of JP 2008-250074 A, the contents of which are incorporated herein by reference. When these additives are blended, the total content thereof is preferably 3% by mass or less of the solid content of the resin composition of the present invention.

[0257] [Surfactant] Various surfactants can be used as the surfactant, 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.

[0258] By adding a surfactant to the resin composition of the present invention, the liquid properties (particularly fluidity) of the coating liquid composition when prepared are further improved, and the uniformity of the coating thickness and the liquid saving can be further improved. That is, 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. Therefore, it is possible to more suitably form a uniform film with small thickness unevenness.

[0259] Examples of fluorine-based surfactants include the compounds described in paragraph 0328 of WO 2021 / 112189, the contents of which are incorporated herein by reference. As the fluorine-based surfactant, fluorine-containing polymer compounds 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, propyleneoxy groups) can also be preferably used, and examples thereof include the following compounds.

[0260] The weight-average molecular weight of the above compound is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. As the fluorosurfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used. 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.

[0261] The fluorine content in the fluorine-containing surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-containing surfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and liquid saving, and also has good solubility in the composition.

[0262] 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.

[0263] The surfactant may be used alone or in combination of two or more. The content of the surfactant is preferably 0.001 to 2.0 mass %, more preferably 0.005 to 1.0 mass %, based on the total solid content of the composition.

[0264] [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.

[0265] The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, even more preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. The above average particle size of the inorganic particles is the primary particle size and also the volume average particle size. The volume average particle size can be measured, for example, by dynamic light scattering using a Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurement is difficult, it can also be measured by centrifugal sedimentation light transmission method, X-ray transmission method, or laser diffraction / scattering method.

[0266] [Organotitanium Compound] When the resin composition contains an organotitanium compound, a resin layer having excellent chemical resistance can be formed even when cured at low temperatures.

[0267] Usable organic titanium compounds include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of organic titanium compounds 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, etc. 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, etc. VII) Titanate coupling agents: for example, isopropyl tridodecylbenzenesulfonyl titanate, etc.

[0268] Among these, from the viewpoint of better chemical resistance, the organic titanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

[0269] It is also preferable to contain a compound represented by the following formula (T-1) as the organotitanium compound or in place of the organotitanium compound. In formula (T-1), M is titanium, zirconium, or hafnium, l1 is an integer of 0 to 2, l2 is 0 or 1, l1 + l2 × 2 is an integer of 0 to 2, m is an integer of 0 to 4, n is an integer of 0 to 2, l1 + l2 + m + n × 2 = 4, and R １１ are each independently a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenoxy group; R １２ is a substituted or unsubstituted hydrocarbon group, R ２ are each independently a group containing a structure represented by the following formula (T-2), and R ３ are each independently a group containing a structure represented by the following formula (T-2), Ａ are each independently an oxygen atom or a sulfur atom. In formula (T-2), X １ ~X ３ each independently represents -C(-*)= or -N=, * represents a bonding site to another structure, and # represents a bonding site to a metal atom.

[0270] In formula (T-1), from the viewpoint of storage stability of the composition, M is preferably titanium. 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 preferable that in formula (T-1), l1 and l2 are 0, and m is 0, 2, or 4.

[0271] In formula (T-1), from the viewpoint of the stability of the specific metal complex, R １１ is preferably a substituted or unsubstituted cyclopentadienyl ligand. １１ The cyclopentadienyl group, alkoxy group and phenoxy group in the formula (I) may be substituted, but an embodiment in which they are unsubstituted is also one of the preferred embodiments of the present invention.

[0272] 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. １２ The hydrocarbon group in may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but an aromatic hydrocarbon group is preferred. The aliphatic hydrocarbon group may be either 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. R １２ The substituent in R is preferably a monovalent substituent, such as a halogen atom. １２ When R is an aromatic hydrocarbon group, it may have an alkyl group as a substituent. １２ is preferably an unsubstituted phenylene group. １２ The phenylene group in is preferably a 1,2-phenylene group.

[0273] In formula (T-1), m is 2 or more, and R ２ If two or more are included,２ In formula (T-1), n ​​is 2 or more, and R ３ If two or more are included, ３ The structures may be the same or different.

[0274] In formula (T-2), X １ ~X ３ each independently represents -C(-*)= or -N=, and it is preferable that at least one represents -C(-*)=, and it is more preferable that at least two represent -C(-*)=.

[0275] Specific examples of the compound represented by formula (T-1) include, but are not limited to, the compound F-11 in the examples.

[0276] When an organotitanium compound is contained, its content 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 it is 10 parts by mass or less, the storage stability of the composition is improved.

[0277] When an organotitanium compound is contained, its content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 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 it is 10 parts by mass or less, the storage stability of the composition is superior.

[0278] [Antioxidant] By including an antioxidant as an additive, the elongation properties of the cured film and adhesion to metal materials can be improved. Examples of antioxidants include phenol compounds, phosphite ester compounds, and thioether compounds. Specific examples of antioxidants include the compounds described in paragraphs 0348 to 0357 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0279] The content of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. By adding an amount of 0.1 part by mass or more, it is easy to obtain the effect of improving elongation properties and adhesion to metal materials even in high-temperature, high-humidity environments, and by adding an amount of 10 parts by mass or less, the sensitivity of the resin composition is improved, for example, through interaction with the photosensitizer. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof be within the above range.

[0280] Other additives include compounds described in paragraphs 0249 to 0282 and 0316 to 0358 of WO 2022 / 145355, the disclosures of which are incorporated herein by reference.

[0281] <Characteristics of Resin Composition> The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. ２ / s~12,000mm ２ / s is preferred, and 2,000 mm ２ / s~10,000mm ２ / s is more preferable, and 2,500 mm ２ / s~8,000mm ２ Within the above range, it is easy to obtain a highly uniform coating film. ２ If the thickness is more than 12,000 mm / s, it is easy to apply the coating to a thickness required for an insulating film for rewiring, for example. ２ If the viscosity is less than 1 / s, a coating film with excellent surface condition can be obtained.

[0282] <Restrictions on Materials 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 it is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage. Furthermore, the lower limit of the water content of the resin composition is preferably 0.001% by mass or more, and can be 0.05% by mass or more, or can be 0.5% by mass or more, from the viewpoints of reducing the effort required for managing storage conditions, adhesion, developability, etc. Specific examples of the water content of the resin composition include 0.05% by mass, 0.2% by mass, and 1.4% by mass.

[0283] From the viewpoint of insulating properties, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Furthermore, from the viewpoint of reducing the effort required to reduce the metal content, mechanical properties, adhesion, etc., the lower limit of the metal content in the resin composition is preferably 0.001 mass ppm or more, and can also be 0.01 mass ppm or more. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, etc., but metals contained as complexes of organic compounds and metals are excluded. When multiple metals are contained, it is preferable that the total of these metals is within the above range. Specific examples of the metal content include 0.002 mass ppm, 0.05 mass ppm, 0.3 mass ppm, etc.

[0284] Furthermore, examples of methods for reducing metal impurities unintentionally contained in the resin composition of the present invention include selecting raw materials with a low metal content as 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.

[0285] 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 these, halogen atoms 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. Furthermore, from the viewpoint of reducing the effort required for reducing halogen ions, the lower limit of halogen ions in the resin composition can be set to 0.01 ppm by mass or more, and can also be set to 0.1 ppm by mass or more. Specific examples of the amount of halogen ions include 0.02 ppm by mass, 0.5 ppm by mass, and 2.5 ppm by mass. Examples of halogen atoms include fluorine atoms, iodine atoms, chlorine atoms, and bromine atoms. It is preferable that the total of fluorine atoms, iodine atoms, chlorine atoms, and bromine atoms, or the total of fluorine ions, iodine ions, chlorine ions, and bromine ions, respectively, is within the above-mentioned range. A preferred method for adjusting the content of halogen atoms is ion exchange treatment.

[0286] A conventionally known container 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 of six types of six resin layers, or a bottle with a seven-layer structure made of six types of resin. Examples of such containers include the container described in JP 2015-123351 A.

[0287] <Cured Product of Resin Composition> A cured product of the resin composition can be obtained by curing the resin composition of the present invention. The cured product of the present invention is a cured product obtained by curing the resin composition. The resin composition is preferably cured by heating, with a heating temperature of 120°C to 400°C being more preferred, 140°C to 380°C being even more preferred, and 170°C to 350°C being particularly preferred. The form of the cured product of the resin composition is not particularly limited, and can be selected depending on the application, such as a 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 depending on the application, such as forming a protective film on a wall surface, forming via holes for electrical conductivity, 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 rate when the resin composition of the present invention is cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage rate refers to the percentage of change in volume of the resin composition before and after curing, and can be calculated by the following formula: Shrinkage rate [%] = 100 - (volume after curing / volume before curing) x 100

[0288] <Characteristics of cured product of 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 more, more preferably 210°C or more, and even more preferably 230°C or more.

[0289] <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.

[0290] 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 filtering under pressure, the pressure to be applied is 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 filtering using a filter, a process of removing impurities using an adsorbent may be performed. Filter filtration and a process of removing impurities using an adsorbent may be combined. Known adsorbents can be used as the adsorbent. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. After filtering using a filter, the resin composition filled in a bottle may be subjected to a degassing process by placing it under reduced pressure.

[0291] (Method for producing a cured product) The method for producing a cured product of the present invention preferably includes a film-forming step in which a resin composition is applied to a substrate to form a film. The method for producing a cured product more preferably includes the film-forming step, an exposure step in which the film formed in the film-forming step is selectively exposed to light, and a development step in which the film exposed in the exposure step is developed using a developer to form a pattern. The method for producing a cured product particularly preferably includes the film-forming step, the exposure step, the development step, and at least one of a heating step in which the pattern obtained in the development step is heated and a post-development exposure step in which the pattern obtained in the development step is exposed to light. The method for producing a cured product also preferably includes the film-forming step and a step of heating the film. Details of each step are described below.

[0292] <Film Forming Step> The resin composition of the present invention can be used in a film forming step of applying the resin composition 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 to a substrate to form a film.

[0293] [Substrate] 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 metal and substrates on which a metal layer is formed by, for example, plating or vapor deposition), paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, mold substrates, and plasma display panel (PDP) electrode plates. Substrates are particularly preferably semiconductor production substrates, with silicon substrates, Cu substrates, and mold substrates being more preferred. These substrates may have a surface layer such as an adhesion layer or an oxide layer formed by hexamethyldisilazane (HMDS) or the like. 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. If it is rectangular, the length of the short side is preferably, for example, 100 to 1000 mm, more preferably 200 to 700 mm. As the substrate, for example, a plate-shaped, preferably a panel-shaped substrate (substrate) is used.

[0294] When a film is formed by applying a resin composition to the surface of a resin layer (for example, a layer made of a cured product) or the surface of a metal layer, the resin layer or the metal layer serves as the substrate.

[0295] Coating is preferred as a means for applying the resin composition to a substrate. Specific application methods 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 coating 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 method can be used in which a coating film formed by applying the coating composition to a temporary support in advance using the above-described application method is transferred onto the substrate. Regarding the transfer method, the preparation 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. A step of removing excess film from the edge of the substrate may also be performed. Examples of such a step include edge bead rinsing (EBR) and back rinsing. A pre-wetting step may also be employed in which the substrate is coated with various solvents before applying the resin composition to the substrate, improving the wettability of the substrate and then applying the resin composition.

[0296] <Drying Step> 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 carried out 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.

[0297] <Exposure Step> The film may be subjected to an exposure step in which the film is selectively exposed to light. The method for producing a cured product may include an exposure step in which the film formed in the film formation step is selectively exposed to light. Selective exposure means that a portion of the film is exposed to light. Furthermore, selective exposure forms exposed regions (exposed portions) and unexposed regions (unexposed portions) in the film. The exposure dose is not particularly limited as long as it can cure the resin composition of the present invention, but for example, it is 50 to 10,000 mJ / cm2 in terms of exposure energy at a wavelength of 365 nm. ２ is preferred, and 200 to 8,000 mJ / cm ２ is more preferred.

[0298] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

[0299] The exposure wavelengths, in relation to the light source, are: (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, and i-line); (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ２Examples of such light include excimer laser (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron beam, and (7) YAG laser second harmonic 532 nm and third harmonic 355 nm. 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 portion 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.

[0300] <Post-Exposure Bake Step> The film may be subjected to a heating step (post-exposure bake step) after exposure. That is, the method for producing a cured product of the present invention may include a post-exposure bake step in which the film exposed in the exposure step is heated. The post-exposure bake step can be carried out after the exposure step and before the development step. The heating temperature in the post-exposure bake step is preferably 50°C to 140°C, more preferably 60°C to 120°C. The heating time in the post-exposure bake step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes. The temperature rise rate in the post-exposure bake step from the temperature at the start of heating 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 also be changed as appropriate during heating. The heating means in the post-exposure bake step is not particularly limited, and known hot plates, ovens, infrared heaters, etc. may 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.

[0301] <Development step> The above-mentioned film after exposure may be subjected to a development step in which it is developed using 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 using a developer to form a pattern. By carrying out development, one of the exposed and unexposed parts of the film is removed to form a pattern. Here, development in which the unexposed parts of the film are removed in the development step is called negative development, and development in which the exposed parts of the film are removed in the development step is called positive development.

[0302] [Developer] The developer used in the development step may be an alkaline aqueous solution or a developer containing an organic solvent.

[0303] When the developer is an alkaline aqueous solution, examples of the basic compound that can be contained in the alkaline aqueous solution include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferred are 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, and more preferred is TMAH. The content of the basic compound in the developer is preferably from 0.01 to 10% by mass, more preferably from 0.1 to 5% by mass, and even more preferably from 0.3 to 3% by mass, based on the total mass of the developer.

[0304] When the developer contains an organic solvent, the organic solvent may be a compound described in paragraph

[0387] of WO 2021 / 112189, the contents of which are incorporated herein by reference. Suitable examples of alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol, and suitable examples of amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

[0305] When the developer contains an organic solvent, the organic solvent may be used alone or in combination. 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.

[0306] When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer 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. Alternatively, the content may be 100% by mass.

[0307] The developer may further contain other components, such as known surfactants and known defoaming agents.

[0308] [Method of Supplying Developer] The method of supplying the developer is not particularly limited as long as it can form the 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 the film formed on the substrate using a nozzle, and a method of continuously supplying the developer. The type of nozzle is not particularly limited, and examples 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 using a straight nozzle or a method of continuously supplying the developer using a spray nozzle is preferred, and from the viewpoint of the permeability of the developer to the image areas, a method of supplying using a spray nozzle is more preferred. In addition, a process may be adopted in which the developer is continuously supplied using a straight nozzle, the substrate is spun to remove the developer from the substrate, and after spin drying, the developer is continuously supplied again using a straight nozzle, and the substrate is spun to remove the developer from the substrate, or this process may be repeated multiple times. Methods of supplying the developer in the development process include a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept substantially stationary on the substrate, a process in which the developer is vibrated on the substrate using ultrasound or the like, and a combination thereof.

[0309] The development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

[0310] In the developing step, after the treatment with the developer, the pattern may be further washed (rinsed) with a rinse liquid. Alternatively, a method may be employed in which a rinse liquid is supplied before the developer in contact with the pattern is completely dried.

[0311] [Rinse Liquid] 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.

[0312] When the rinse solution 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 solution 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.

[0313] When the rinse solution contains an organic solvent, the organic solvent may be used alone or in combination of two or more. The organic solvent is preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, or PGME, more preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, or PGME, and even more preferably cyclohexanone or PGMEA.

[0314] 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, and may also account for 100% by mass of the total mass of the rinse solution.

[0315] The rinse liquid may further contain other components, such as known surfactants and known defoaming agents.

[0316] [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, methods of supplying the rinse liquid using a shower nozzle, straight nozzle, spray nozzle, etc. are available, and a method of continuously supplying using a spray nozzle is preferred, and from the viewpoint of the permeability of the rinse liquid into the image areas, a method of supplying using a spray nozzle is more preferred. The type of nozzle is not particularly limited, and examples include a straight nozzle, shower nozzle, spray nozzle, etc. That is, the rinsing step is preferably a step of supplying or continuously supplying the rinse liquid to the exposed film using a straight nozzle, and more preferably a step of supplying the rinse liquid using 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.

[0317] The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinsing liquid during rinsing is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

[0318] <Heating Step> The pattern obtained by the development step (or the pattern after rinsing, if a rinsing step is performed) 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 in which the pattern obtained by the development step is heated. Furthermore, the method for producing a cured product of the present invention may include a heating step in which a pattern obtained by another method without performing a development step, or a film obtained by a film formation step, is heated. In the heating step, a resin such as a polyimide precursor is cyclized to form a resin such as a polyimide. Furthermore, crosslinking of unreacted crosslinkable groups in the specific resin or in a 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, even more preferably 160 to 250°C, and particularly preferably 160 to 230°C.

[0319] 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 a base or the like generated from the base generator due to heating.

[0320] 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. In addition, in the case of an oven capable of rapid heating, it is preferable to increase the temperature from the temperature at the start of heating to the maximum heating temperature at a temperature increase rate of 1 to 8°C / sec, more preferably 2 to 7°C / sec, and even more preferably 3 to 6°C / sec.

[0321] 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 the start of the process of heating up to the maximum heating temperature. For example, when the resin composition of the present invention is applied to a substrate and then dried, the temperature is the temperature of the film (layer) after this drying, and it is preferable to raise the temperature from, for example, a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition.

[0322] The heating time (heating time at the maximum heating temperature) is preferably from 5 to 360 minutes, more preferably from 10 to 300 minutes, and even more preferably from 15 to 240 minutes.

[0323] In particular, when forming a multilayer laminate, from the viewpoint of interlayer adhesion, 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 lower, more preferably 250° C. or lower, and even more preferably 240° C. or lower.

[0324] 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's 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 step 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, cooling may be performed after heating. In this case, the cooling rate is preferably from 1 to 5°C / min.

[0325] The heating step is preferably carried out in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, or by carrying out the heating step under reduced pressure, in order to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less. The heating means used in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, and an infrared oven.

[0326] <Post-development exposure step> The pattern obtained in 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 obtained in 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 in which the pattern obtained in the development step is exposed to light. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step. The post-development exposure step can promote, for example, a reaction in which cyclization of a polyimide precursor or the like progresses due to exposure of a photobase generator, or a reaction in which elimination of an acid-decomposable group progresses due to exposure of a photoacid generator. In the post-development exposure step, it is sufficient that at least a portion 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 50 to 20,000 mJ / cm in terms of exposure energy at a wavelength to which the photosensitive compound has sensitivity. ２ is preferred, and 100 to 15,000 mJ / cm ２ 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.

[0327] <Metal Layer Forming Step> The pattern obtained by the developing step (preferably subjected to at least one of a heating step and a post-development exposure step) may be subjected to a metal layer forming step of forming a metal layer 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 developing step (preferably subjected to at least one of a heating step and a post-development exposure step).

[0328] The metal layer is not particularly limited, and existing metal species can be used. Examples include 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.

[0329] 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. Patent No. 7,888,181 B2, and U.S. Patent No. 9,177,926 B2 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 specifically, examples include patterning methods that combine sputtering, photolithography, and etching, and patterning methods that combine photolithography and electroplating. Preferred plating methods include electroplating using a copper sulfate or copper cyanide plating solution.

[0330] The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm, at the thickest part.

[0331] <Applications> Fields to which the method for producing a cured product 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 sealing films, substrate materials (base films, coverlays, and interlayer insulating films for flexible printed circuit boards), and the etching of insulating films for packaging applications such as those described above. For these applications, reference can be made to, for example, Science & Technology Co., Ltd.'s "High Performance Polyimide and Application Technology" (April 2008), edited by Masaaki Kakimoto, CMC Technical Library "Fundamentals and Development of Polyimide Materials" (November 2011), and Japan Polyimide and Aromatic Polymer Research Association's "Latest Polyimide Fundamentals and Applications" (NTS, August 2010).

[0332] The method for producing the cured product of the present invention, or the cured product of the present invention, can also be used for producing printing plates such as offset printing plates or screen printing plates, for etching molded parts, for producing protective lacquers and dielectric layers in electronics, especially microelectronics, etc.

[0333] (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 each made of the cured product, and may be a laminate including three or more layers. At least one of the two or more layers each made of the cured product contained in the laminate 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.

[0334] That is, 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.

[0335] The laminate of the present invention preferably includes two or more layers made of a cured product and a metal layer between any 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 a layer made of a cured product between multiple cured product production processes. A preferred embodiment of the metal layer-forming step is as described above. Examples of the laminate include a laminate having at least a layer structure in which three layers are stacked in this order: a layer made of a first cured product, a metal layer, and a layer made of a second cured product. It is preferred that both the layer made of the first cured product and the layer made of the second cured product are 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.

[0336] <Lamination Step> The method for producing a laminate of the present invention preferably includes a lamination step. The lamination step is a series of steps including performing at least one of (a) a film formation step (layer formation step), (b) an exposure step, (c) a development step, and (d) a heating step and a post-development exposure step again on the surface of the pattern (resin layer) or the metal layer in this order. However, at least one of (a) the film formation step and (d) the heating step and the post-development exposure step may be repeated. Furthermore, after at least one of (d) the heating step and the post-development exposure step, (e) a metal layer formation step may be included. It goes without saying that the lamination step may further include the above-mentioned drying step or the like as appropriate.

[0337] When a further lamination step is performed after the lamination step, a surface activation treatment step may be further performed after the exposure step, the heating step, or the metal layer forming step. An example of the surface activation treatment is a plasma treatment. Details of the surface activation treatment will be described later.

[0338] The lamination step is preferably performed 2 to 20 times, more preferably 2 to 9 times. For example, a structure having 2 to 20 resin layers, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferred, and a structure having 2 to 9 resin layers is even more preferred. Each of the layers may be the same or different in composition, shape, film thickness, etc.

[0339] In the present invention, a particularly preferred embodiment is one in which, after providing a metal layer, a cured product (resin layer) of the resin composition of the present invention is further formed so as to cover the metal layer.Specific examples include an embodiment in which the steps of (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 are repeated in this order, or an embodiment in which the steps of (a) film formation step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step are repeated in this order.By alternately performing the lamination step of laminating the resin composition layer (resin layer) of the present invention and the metal layer formation step, the resin composition layer (resin layer) of the present invention and the metal layer can be alternately laminated.

[0340] (Surface Activation Treatment Step) The method for producing a laminate of the present invention preferably includes a surface activation treatment step in which at least a portion of the metal layer and the resin composition layer are surface-activated. The surface activation treatment step is usually performed after the metal layer formation step, but after the development step (preferably after at least one of the heating step and the post-development exposure step), the resin composition layer may be surface-activated before the metal layer formation step. The surface activation treatment may be performed only on at least a portion of the metal layer, or only on at least a portion of the resin composition layer after exposure, or may be performed 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 to be formed. In this way, by performing the surface activation treatment on the surface of the metal layer, adhesion with the resin composition layer (film) provided on the surface can be improved. The surface activation treatment is also preferably performed on part or all of the resin composition layer (resin layer) after exposure. In this way, by performing the surface activation treatment on the surface of the resin composition layer, adhesion with the metal layer or resin layer provided on the surface that has been surface-activated can be improved. In particular, when negative development is performed, when the resin composition layer is cured, it is less susceptible to damage due to 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 International Publication No. 2021 / 112189. The contents of this specification are incorporated herein.

[0341] (Semiconductor device and manufacturing method thereof) The present invention also discloses a semiconductor device comprising the cured product or laminate of the present invention. The present invention also discloses a manufacturing method for a semiconductor device comprising the manufacturing method for the cured product or the manufacturing method for the laminate of the present invention. Specific examples of semiconductor devices using the resin composition of the present invention to form an interlayer insulating film for a rewiring layer can be found in paragraphs 0213 to 0218 and FIG. 1 of JP 2016-027357 A, the contents of which are incorporated herein by reference.

[0342] The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

[0343] <Polymer synthesis> [Synthesis Example P-1: Synthesis of resin (P-1) (precursor of cyclized resin)] Resin (P-1) was synthesized according to the method described in paragraph

[0397] of WO 2022 / 044998, except that the molar ratio of 4,4'-oxydiphthalic dianhydride (ODPA) to bisphthalic dianhydride (BPDA) used was 60:40. The weight average molecular weight (Mw) was 28,000. １ The structure of resin (P-1) was confirmed by H-NMR to be the structure represented by the following formula (P-1). In the following formula (P-1), m and n represent the molar ratio of the respective repeating units contained, with m:n = 60:40. In addition, by changing the equivalent weight of the diamine used, resins (P-1) with Mw of 15,000, 20,000, 30,000, 40,000, and 50,000 were also synthesized. In the above and following synthesis examples, unless otherwise specified, the weight average molecular weight and number average molecular weight were measured by the following methods. GPC measurements were performed using a high-speed GPC system HLC-8420GPC (manufactured by Tosoh Corporation) with a TSK guard column Super AW-H (4.6 mm × 35 mm) and two TSKgel Super AWM-H (4.6 mm × 150 mm) columns connected in series. A 0.01 mol / L solution of lithium bromide in NMP (N-methyl-2-pyrrolidone) was used as the eluent.

[0344] [Synthesis Example P-2: Synthesis of Resin (P-2) (Precursor to Cyclized Resin)] Resin (P-2) was synthesized in the same manner as in Synthesis Example P-1, except that the molar ratio of 4,4'-oxydiphthalic dianhydride (ODPA) to bisphthalic dianhydride (BPDA) used was 75:25. The weight average molecular weight (Mw) was 22,000. Furthermore, by changing the equivalent weight of the diamine used, a resin (P-2) with an Mw of 30,000 was also synthesized. In the following formula (P-2), m and n represent the molar ratio of each repeating unit, with m:n = 75:25. １ By H-NMR, it was confirmed that the structure of resin (P-2) was a structure represented by the following formula (P-2).

[0345] Synthesis Example P-3: Synthesis of Resin (P-3) (Precursor to Cyclized Resin) 21.2 g of 4,4'-oxydiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, and 250 mL of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at 60°C for 4 hours to synthesize a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to -10°C, and 17.0 g of thionyl chloride was added over 60 minutes while maintaining the temperature at -10±5°C. After dilution with 50 mL of N-methylpyrrolidone, a solution of 12.6 g of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture over 60 minutes at -10±5°C, and the mixture was stirred at room temperature for 2 hours. Thereafter, 10.0 g of ethanol was added and the mixture was stirred at room temperature for 1 hour. Next, 6,000 g of water was added to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The precipitate (solid polyimide precursor) after stirring was collected by filtration and dissolved in 500 g of tetrahydrofuran. 6,000 g of water (poor solvent) was added to the resulting solution to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The precipitate after stirring was again filtered and dried at 45°C under reduced pressure for 3 days. 46.6 g of the dried powder was dissolved in 419.6 g of tetrahydrofuran, and then 2.3 g of triethylamine was added and the mixture was stirred at room temperature for 35 minutes. Then, 3,000 g of ethanol was added, and the precipitate was collected by filtration. The resulting precipitate was dissolved in 281.8 g of tetrahydrofuran. 17.1 g of water and 46.6 g of ion exchange resin UP6040 (AmberTec) were added thereto and stirred for 4 hours. Thereafter, the ion exchange resin was removed by filtration, and the resulting polymer solution was added to 5,600 g of water to obtain a precipitate. The precipitate was collected by filtration and dried under reduced pressure at 45 ° C. for 24 hours to obtain 45.1 g of resin (P-3). １ By H-NMR, it was confirmed that the structure of resin (P-3) was the structure represented by the following formula (P-3): The weight average molecular weight (Mw) was 30,000.

[0346] [Synthesis Examples P-4 to P-16: Synthesis of Resins (P-4 to P-16) (Precursors of Cyclized Resins)] Resins (P-4) to (P-16) represented by any of the following formulas (P-4) to (P-16) were synthesized in the same manner as in Synthesis Example 3, except that the compounds used were changed appropriately. The Mw of resins (P-4) to (P-16) was all 30,000.

[0347] Synthesis Example P-20: Synthesis of Resin (P-20) (Cyclated Resin) Synthesis Example AA-1: 48.65 g (225 mmol) of 3,3'-dihydroxybenzidine and 375 mL of dimethylformamide were mixed in a flask. Under ice cooling, 98.21 g (450 mmol) of di-t-butyl dicarbonate was added dropwise. After 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 were precipitated, and the precipitated solid was collected by suction filtration. The obtained white solid was purified by recrystallization at 60°C using 1000 mL of acetone. 125 g (yield 85.6%) of the following intermediate AA-1a was obtained. The structure of AA-1a is shown below. １ This was confirmed by H-NMR spectrum. １ H-NMR (BRUKER, AVANCE NEO 400): δ(ppm,DMSO-d6)8.04-7.94(s,2H), 7.75-7.64(d,2H), 7.56-7.42(m,8H), 7.27-7.20(d,2H), 7.19-7.12(d,2H), 6.79-6.64(2H), 5.89-5.77(2H), 5.30-5.15(6H), 1.49-1.43(s,18H)

[0348] 75.0 g (115.6 mmol) of (AA-1a) and 500 mL of methylene chloride were mixed in a 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 collected 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 following structure is １ This was confirmed by H-NMR spectrum. １ H-NMR (BRUKER, AVANCE NEO 400): δ(ppm,DMSO-d6)7.53-7.45(s,8H), 7.05-6.98(d,2H), 6.92-6.85(d,2H), 6.79-6.63(4H), 5.89-5.78(d,2H), 5.29-5.22(d,2H), 5.20-5.13(s,4H), 4.92-4.64(4H)

[0349] Synthesis Example AT-1 AT-1 was obtained in the same manner as in Synthesis Example AA-1, except that 3,3'-dihydroxybenzidine was replaced with p-methoxyphenol. The structure of AT-1 is shown below. １ The identity was confirmed by H-NMR spectrum. 1H-NMR (BRUKER, AVANCE NEO 400): δ (ppm, DMSO-d6) 7.52-7.42 (d, 2H), 7.42-7.32 (d, 2H), 6.80-6.63 (3H), 6.54-6.43 (d, 2H), 5.92-5.77 (1H), 5.30-5.19 (1H), 4.95-4.89 (s, 2H), 4.68-4.54 (2H). 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, 5.14 g (24.2 mmol) of m-tolidine, 10.86 g (24.2 mmol) of AA-1, and 1.30 g (5.76 mmol) of AT-1 were dissolved in 100 g of NMP and added dropwise to the solution over 1 hour at a temperature of 0 to 10°C. After stirring at 25°C for 60 minutes, 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, and after stirring for 15 minutes, 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, filtered, and dried under reduced pressure at 40°C for 10 hours. Subsequently, the dried resin was dissolved in 250 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, and the ion exchange resin was removed by filtration. The polyimide resin was then 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 cyclized resin (P-20). The weight average molecular weight of the obtained cyclized resin (P-20) was 30,000. The cyclized resin (P-20) is a resin having a repeating unit represented by the following formula (P-20). The structure of the repeating unit is: １ Determined from H-NMR spectrum.

[0350] Synthesis Example P-21: Synthesis of Resin (P-21) (Cyclated Resin) 33.6 g (64.5 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 6.23 g (28.8 mmol) of 4,4'-diamino-3,3'-dihydroxybiphenyl, 6.11 g (28.8 mmol) of m-tolidine, and 0.76 g (7.0 mmol) of 4-aminophenol were dissolved in 200 mL of NMP and stirred at 200°C for 3 hours under a nitrogen atmosphere to obtain a polyimide. Next, 0.1 g of TEMPO and 50.4 g (324 mmol) of MOI (2-isocyanatoethyl methacrylate) were added at room temperature, and the mixture was heated to 60°C. After that, 0.1 g of Neostan U-600 (Nitto Kasei Co., Ltd., inorganic bismuth) was added and stirred for 3 hours. To the obtained polyimide solution, 630 mL of THF was added, and the mixture was added dropwise to 2500 mL of methanol to precipitate the polymer. The polymer collected by filtration was dried under reduced pressure at 40°C for 1 day to obtain polyimide (P-21) as a powder. The weight average molecular weight of the obtained cyclized resin (P-21) was 30,000. The cyclized resin (P-21) is a resin having a repeating unit represented by the following formula (P-21). The structure of the repeating unit is: １ Determined from H-NMR spectrum.

[0351] [Synthesis Examples P-17 to 19, 22 to 23: Synthesis of Resins (P-17) to (P-19), (P-22) to (P-23) (Cyclated Resins)] Resins (P-17) and (P-19) having a structure represented by either of the following formulas (P-17) and (P-19) were synthesized by the same method as in Synthesis Example P-20, except that the compounds used were changed appropriately. Furthermore, resins (P-18) and (P-22) to (P-23) having a structure represented by either of the following formulas (P-18) and (P-22) to (P-23) were synthesized by the same method as in Synthesis Example P-21, except that the compounds used were changed appropriately. The Mw of resins (P-17) to (P-19) and (P-22) to (P-23) was all 30,000.

[0352] Examples and Comparative Examples In each example, the components listed in the table below were mixed to obtain a resin composition. In each comparative example, the components listed in the table below were mixed to obtain a comparative composition. Specifically, the content of each component listed in the table was the amount (parts by mass) listed in the "Parts by Mass" column of each column in the table. The amount of solvent used was such that the solid content concentration of the composition would be the "Solid Content Concentration (% by mass)" in the table, and each solvent was mixed at the mixing ratio (mass ratio) listed in the "Ratio" column. The obtained resin composition and comparative composition were pressure-filtered using a polytetrafluoroethylene filter with a pore size of 0.8 μm. In the table, "-" indicates that the composition did not contain the corresponding component.

[0353]

[0354]

[0355]

[0356]

[0357]

[0358]

[0359]

[0360] [Resins] P-1 to P-23: Resins (P-1) to (P-23) synthesized above

[0361] [Polymerizable compounds] M-1: NK Ester 4G (manufactured by Shin-Nakamura Chemical Co., Ltd.) M-2: Compound having the following structure M-3: NK Ester A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.) M-4: Viscoat #802 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) M-5: NK Ester TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) M-6: NK Ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0362] [Polymerization initiator] I-1: Compound having the following structure I-2: Compound having the following structure I-3: Compound having the following structure

[0363] [Specific compounds] A-1 to A-10: Compounds having the following structures

[0364] [Synthesis of specific compounds] - Synthesis of compound A-1 - Compound A-1 was synthesized with reference to ACS Catal. 2023, 13, 5795. １ It was confirmed that the H NMR was consistent with the values ​​reported in the literature. Compounds A-2 to A-10 were also synthesized by a similar method. The molar absorption coefficients at a wavelength of 365 nm of the above-mentioned compounds I-1 to I-3 and A-1 to A-10 are shown in the table below. The molar absorption coefficient was measured by the following method. 12.5 mg of the compound was weighed and dissolved in 100 mL of acetonitrile to prepare a 0.125 g / L solution of the compound. 2 mL of this solution was taken and diluted to 25 mL with acetonitrile to prepare a 0.01 g / L solution of the compound. The absorbance of this solution at a wavelength of 365 nm was measured using a spectrophotometer (UH-4150, manufactured by Hitachi High-Tech Corporation), and the molar absorption coefficient ε was calculated from the following formula: Formula: Molar absorption coefficient ε (L mol －１ ・cm －１ )=A / (C×l) (A: absorbance, C: concentration (mol / L), l: optical path length (cm))

[0365]

[0366] [Base Generator] AR-1 to AR-5: Compounds having the following structure

[0367] [Polymerization inhibitors] B-1: 2-nitroso-1-naphthol B-2: 4-methoxyphenol B-3: 1,4-benzoquinone B-4: hydroquinone B-5: 2,6-di-tert-butyl-p-cresol

[0368] [Silane coupling agents] C-1: Compound having the following structure C-2: Compound having the following structure C-3: Compound having the following structure C-4: Compound having the following structure C-5: X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.) C-6: KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0369] [Antioxidants] D-1: Compound having the following structure D-2: IRGANOX 3114 (manufactured by BASF) D-3: IRGANOX 1330 (manufactured by BASF) D-4: IRGANOX 1010 (manufactured by BASF) D-5: IRGANOX MD 1024 (manufactured by BASF)

[0370] [Migration inhibitors] E-1: 8-azaadenine E-2: 5-aminotetrazole E-3: benzotriazole E-4: tetrazole

[0371] [Additives] F-1: N-phenyldiethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.) F-2: Compound having the following structure F-3: 7-(diethylamino)coumarin-3-carboxylate ethyl (manufactured by Tokyo Chemical Industry Co., Ltd.) F-4: 1,3-dicyclohexylurea (manufactured by Tokyo Chemical Industry Co., Ltd.) F-5: Benzoyl peroxide (manufactured by Tokyo Chemical Industry Co., Ltd.) F-6: Methyl acetoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) F-7: Ethyl acetoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) F-8: Tetraisopropyl titanate (manufactured by Tokyo Chemical Industry Co., Ltd.) F-9: Compound having the following structure F-10: Compound having the following structure F-11: Compound having the following structure F-12: Ester of 2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-1,1'-spirobi(1H-indene)-5,5',6,6',7,7'hexanol and 1,2-naphthoquinone-(2)-diazo-5-sulfonic acid (NQD (naphthoquinone diazide)) F-13: Compound having the following structure F-14: Compound having the following structure F-15: Compound having the following structure F-16: Compound having the following structure

[0372] [Solvents] S-1: N-methyl-2-pyrrolidone S-2: Ethyl lactate S-3: γ-butyrolactone S-4: Dimethyl sulfoxide S-5: γ-valerolactone S-6: 3-methoxy-N,N-dimethylpropanamide S-7: 3-butoxy-N,N-dimethylpropanamide

[0373] <Evaluation> [Resolution Evaluation] The resin composition or comparative composition prepared in each Example or Comparative Example was applied in the form of a layer by spin coating to the surface of a thin copper layer of a resin substrate having a thin copper layer formed on its surface, and dried at 110°C for 5 minutes to form a resin composition layer having a thickness of 4 μm after film formation. The obtained resin composition layer was then subjected to a spin coating of 200 to 1500 mJ / cm using an i-line stepper (Canon: FPA-3000i5, NA=0.5, σ=0.7) using a square via mask having a pattern formed in 0.5 μm increments from 0.5 to 10 μm. ２ in the range of 50 mJ / cm ２ The film was exposed to each exposure dose in increments. Subsequently, the film was developed with the developer listed in the "Developer" column of the table until the unexposed areas were removed, rinsed with PGMEA for 30 seconds, and then heated at a temperature increase rate of 10°C / min under a nitrogen atmosphere, and heated at the temperature listed in the "Cure Temperature (°C)" column of the table for the time listed in the "Cure Time (min)" column. In addition, in the examples listed as "IR" in the "Cure Temperature (°C)" column, the resin film obtained in each example was heated at a temperature increase rate of 10°C / min under a nitrogen atmosphere using an infrared lamp heating device (manufactured by Advance Riko Co., Ltd., RTP-6), and after reaching 230°C, the temperature was maintained for 180 minutes to obtain a cured product. In the developer column of the table, "CP" indicates cyclopentanone, and "CP / GBL" indicates a solvent obtained by mixing cyclopentanone and γ-butyrolactone in a mass ratio of 90:10. The minimum opening mask diameter of the obtained cured product was determined by observing the cross section of the opening pattern portion with a scanning microscope S-4800 (manufactured by Hitachi High-Technologies Corporation) and evaluated according to the following evaluation criteria. The minimum opening mask diameter was defined as the smallest mask diameter among those in which an opening pattern was formed with at least one exposure dose in a range in which the remaining film ratio before and after development (%, film thickness after development / film thickness before development x 100) was 95% or more among the above-mentioned exposure doses. In addition, at 400 mJ / cm ２The residual film ratio (%, film thickness after development / film thickness before development x 100) was calculated from the film thickness before and after development when exposed to light at 100°C. A residual film ratio of less than 80% is not preferable for forming a rewiring layer, regardless of the aperture mask size. (Evaluation criteria) A: The minimum aperture mask diameter was 3 μm or less, and the residual film ratio after development was 90% or more. B: The minimum aperture mask diameter was more than 3 μm and 4 μm or less, and the residual film ratio after development was 90% or more. C: The minimum aperture mask diameter was more than 4 μm and 5 μm or less, and the residual film ratio after development was 90% or more. D: The minimum aperture mask diameter was more than 5 μm, or the residual film ratio after development was less than 80%.

[0374] From the above results, it can be seen that the resin composition of the present invention has excellent resolution in the obtained cured product. The comparative compositions of Comparative Examples 1 to 4 do not contain the specific compound. It can be seen that when such compositions are used, the obtained cured product has poor resolution.

[0375] Example 201 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. The resulting layer was dried at 100°C for 5 minutes to form a 20 μm-thick photosensitive film, which was then exposed using a stepper (Nikon Corporation, NSR1505 i6). The exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-and-space pattern and a line width of 10 μm). After the exposure, the film was developed with cyclopentanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern. The temperature was then increased at a rate of 10°C / min in a nitrogen atmosphere, reaching 230°C, and maintained at 230°C for 180 minutes to form an interlayer insulating film for a redistribution layer. This interlayer insulating film for a redistribution layer had excellent insulating properties. Furthermore, a semiconductor device was manufactured using this interlayer insulating film for a redistribution layer, and it was confirmed to operate without any problems.

Claims

1. A resin and a compound represented by the following formula (A1-1), (A1-2), or (A1-3), having a molar absorption coefficient of 1×10 at a wavelength of 365 nm. ３ L.mol －１ ・cm －１ A resin composition comprising: Compound A1: In formula (A1-1), formula (A1-2), and formula (A1-3), R １ is an aromatic ring, and R ２ ~R ４ is an organic group, and R ２ ~R ４ may be the same or different, and R ５ ~R １０ is a hydrogen atom or an organic group, and R ５ ~R １０ may be the same or different, and R １ ~R １０ may be bonded to each other to form a ring structure.

2. In formula (A1-1), formula (A1-2), and formula (A1-3), R １ The resin composition according to claim 1 , wherein is a phenyl group which may have a substituent.

3. A resin composition comprising a resin and a compound A2 represented by the following formula (A2-1), (A2-2), or (A2-3): In formula (A2-1), formula (A2-2), and formula (A2-3), R １ is an unsubstituted phenyl group, and R ２ ~R ４ is an organic group, and R ２ ~R ４ may be the same or different, and R ５ ~R １０ is a hydrogen atom or an organic group, and R ５ ~R １０ may be the same or different, and R １ ~R １０ may be bonded to each other to form a ring structure.

4. The resin composition according to any one of claims 1 to 3, wherein the resin is at least one resin selected from the group consisting of cyclized resins and precursors thereof.

5. The above R ２ The resin composition according to any one of claims 1 to 3, wherein each of the following formulas (R2-1) or (R2-2) is a structure represented by: In formula (R2-1) and formula (R2-2), R ２２ is an organic group, and * is the bonding site with the oxygen atom.

6. The above R ３ and the R ４ The resin composition according to any one of claims 1 to 3, wherein each of the alkyl groups may be bonded to each other.

7. The above R ５ ~R １０ The resin composition according to any one of claims 1 to 3, wherein all of are hydrogen atoms.

8. The resin composition according to claim 1 or 2, wherein the compound A1 is a compound represented by the following formula (A1-4): In formula (A1-4), R １ is an aromatic ring, and R ２３ is an alkyl group, an aryl group, or an alkoxy group, and R ３ and R ４ is a hydrogen atom or an organic group, and R ３ and R ４ may be bonded to each other to form a ring structure.

9. The resin composition according to claim 3, wherein the compound A2 is a compound represented by the following formula (A2-4): In formula (A2-4), R １ is an unsubstituted phenyl group, and R ２３ is an alkyl group, an aryl group, or an alkoxy group, and R ３ and R ４ is a hydrogen atom or an organic group, and R ３ and R ４ may be bonded to each other to form a ring structure.

10. The resin composition according to any one of claims 1 to 3, wherein the resin is a polyimide or a polyimide precursor.

11. The resin composition according to any one of claims 1 to 3, wherein the resin has a radically polymerizable group.

12. The resin composition according to any one of claims 1 to 3, which is used to form an interlayer insulating film for a rewiring layer.

13. A cured product obtained by curing the resin composition according to any one of claims 1 to 3.

14. A laminate comprising two or more layers of the cured product according to claim 13, and a metal layer between any of the layers of the cured product.

15. A method for producing a cured product, comprising a film-forming step of applying the resin composition according to any one of claims 1 to 3 onto a substrate to form a film.

16. The method for producing a cured product according to claim 15, 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.

17. The method for producing a cured product according to claim 15, further comprising a heating step of heating the film at 50 to 450°C.

18. A method for producing a laminate, comprising the method for producing the cured product according to claim 15.

19. A method for manufacturing a semiconductor device, comprising the method for manufacturing the cured product according to claim 15.

20. A semiconductor device comprising the cured product of claim 13.

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