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 comprising a compound A having a prescribed structure and at least one resin P selected from the group consisting of cyclized resins and precursors of cyclized resins; 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.

Description

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

[0001] The present invention relates to a resin composition, a cured product, a laminate, a method for manufacturing a cured product, a method for manufacturing a laminate, a method for manufacturing a semiconductor device, and a semiconductor device.

[0002] In modern times, resin materials manufactured from resin compositions containing resins are utilized in various fields. For example, cyclized resins such as polyimide are applied to a wide range of applications due to their excellent heat resistance and insulation properties. While not limited to these applications, examples of applications in semiconductor devices for packaging include their use as insulating films, encapsulating materials, or protective films. They are also used as base films and coverlays for flexible substrates.

[0003] For example, in the applications described above, cyclized resins such as polyimide are used in the form of precursors of cyclized resins, such as polyimide precursors, or resin compositions containing cyclized resins. Such resin compositions can be applied to a substrate, for example by coating, to form a photosensitive film, and then, if necessary, exposure, development, heating, etc., can be performed to form a cured product on the substrate. In the cured product, the precursors of cyclized resins, such as polyimide precursors, are converted into cyclized resins such as polyimide. Since the resin compositions can be applied by known coating methods, etc., they offer excellent manufacturing adaptability, such as a high degree of freedom in designing the shape, size, and application position of the resin composition when applied. In addition to the high performance of cyclized resins, the industrial application development of the above-mentioned resin compositions is increasingly expected from the viewpoint of such excellent manufacturing adaptability.

[0004] For example, Patent Document 1 describes a negative-type photosensitive resin composition comprising a resin containing a polyimide precursor, polyimide, or both thereof, a photopolymerization initiator, and a nitrogen-containing heterocyclic compound, wherein the polyimide precursor, polyimide, and nitrogen-containing heterocyclic compound each have a specific structure.

[0005] Japanese Patent Application Publication No. 2023-086715

[0006] When a cured product containing a cyclized resin such as polyimide is used in a manner of contacting a metal layer such as an insulating film, it is required to suppress the generation of voids (gaps) between the cured product and the metal layer over a long period of time. It is considered that the generation of voids leads to a decrease in the adhesion between the cured product and the metal layer and an increase in the electrical resistance of the metal layer. In addition, it is also required to suppress the generation of metal oxides between the cured product and the metal layer over a long period of time.

[0007] An object of the present invention is to provide a resin composition from which a cured product capable of suppressing the generation of voids and metal oxides between the cured product and a metal layer over a long period of time can be obtained, 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 including the method for producing the cured product, and a semiconductor device including the cured product.

[0008] Examples of typical embodiments of the present invention are shown below.

[0009] <1> A resin composition containing at least one resin P selected from the group consisting of a cyclized resin and a precursor of the cyclized resin, and a compound A represented by the following formula (1).

[0010]

[0011] In formula (1), R １１ to R １５ each independently represent a hydrogen atom or a substituent. At least two of R １１ to R １５ may be bonded to form a ring. X １１ represents a group represented by the following formula (G-1) or (G-2).

[0012]

[0013] In formulas (G-1) and (G-2), * represents a bonding site. In formula (G-2), R Ａ１１ represents a hydrogen atom or a substituent. <2> The resin composition according to <1>, wherein R １５ in the above formula (1) represents a hydrogen atom. <3> R １１ and R １４The resin composition according to <1> or <2>, wherein R represents a hydrogen atom. <4> In the above formula (1), R １２ and R １３ A resin composition according to any one of <1> to <3>, wherein at least one of the members represents a hydrogen atom. <5> A resin composition according to any one of <1> to <4>, wherein the molecular weight of compound A is 750 or less. <6> A resin composition according to any one of <1> to <5>, wherein the resin P is polyimide or a polyimide precursor. <7> A resin composition according to any one of <1> to <6>, satisfying at least one of the following (i) and (ii): (i) The resin P has a radical polymerizable group. (ii) In addition to the resin P and compound A, the resin composition contains a compound having a radical polymerizable group. <8> A resin composition according to any one of <1> to <7>, wherein the content of compound A is 0.005 to 30% by mass with respect to the total solid content of the resin composition. <9> A resin composition according to any one of <1> to <8>, used for forming an interlayer insulating film for a redistribution layer. <10> A cured product obtained by curing a resin composition according to any one of <1> to <8>. <11> A laminate comprising two or more layers made of the cured product according to <10>, with a metal layer between any of the layers made of the cured product. <12> A method for manufacturing a cured product, comprising a film forming step of applying a resin composition according to any one of <1> to <8> onto a substrate to form a film. <13> A method for manufacturing a cured product according to <12>, comprising an exposure step of selectively exposing the film and a developing step of developing the film using a developer to form a pattern. <14> A method for manufacturing a cured product according to <12> or <13>, comprising a heating step of heating the film at 50 to 450°C. <15> A method for manufacturing a laminate, comprising a method for manufacturing a cured product according to any one of <12> to <14>. <16> A method for manufacturing a semiconductor device, comprising a method for manufacturing a cured product according to any one of <12> to <14>. <17> A semiconductor device comprising the cured product according to <10>.

[0014] The present invention provides a resin composition that yields a cured product in which the generation of voids and metal oxides between the cured product and the metal layer is suppressed over a long period of time, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for manufacturing the cured product, a method for manufacturing the laminate, a method for manufacturing a semiconductor device including the method for manufacturing the cured product, and a semiconductor device containing the cured product.

[0015] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments explicitly stated. In this specification, numerical ranges represented by the symbol "~" mean a range that includes the numerical values ​​before and after "~" as the lower and upper limits, respectively. In this specification, the term "process" includes not only independent processes but also processes that are indistinguishable from other processes as long as the intended effect of the process is achieved. In the notation of groups (atomic groups) in this specification, notations that do not specify substituted or unsubstituted include both groups (atomic groups) with substituents and groups (atomic groups) without substituents. For example, "alkyl group" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of light used for exposure include the emission line spectrum of mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet (EUV) light, X-rays, electron beams, and other active light or radiation. In this specification, "(meth)acrylate" means both or either "acrylate" and "methacrylate," "(meth)acrylic" means both or either "acrylic" and "methacrylic," and "(meth)acryloyl" means both or either "acryloyl" and "methacryloyl." In this specification, Me in structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, total solids means the total mass of all components of the composition excluding the solvent. In this specification, solids concentration is the mass percentage of the components other than the solvent relative to the total mass of the composition. In this specification, 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, 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 connecting Guard Column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) in series as columns. Unless otherwise specified, these molecular weights shall be measured using NMP (N-methyl-2-pyrrolidone) as the eluent. However, if NMP is unsuitable as an eluent, such as in cases of low solubility, THF (tetrahydrofuran) may be used. Unless otherwise specified, detection in GPC measurements shall be performed using a UV (ultraviolet) wavelength 254 nm detector. In this specification, when the positional relationship of each layer constituting a laminate is described as "up" or "down," it is sufficient that there are other layers above or below the reference layer among the multiple layers of interest. That is, a third layer or element may be interposed between the reference layer and the other layers, and the reference layer and the other layers do not need to be in contact. Unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "up," or, if there is a resin composition layer, the direction from the substrate to the resin composition layer is referred to as "up," and the opposite direction is referred to as "down." Note that this setting of up and down directions is for convenience in this specification, and in actual embodiments, the "up" direction in this specification may differ from vertically upward. In this specification, unless otherwise specified, a composition may contain two or more compounds corresponding to each component contained in the composition. Also, 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, preferred embodiments are more preferred embodiments.

[0016] (Resin Composition) The resin composition of the present invention (hereinafter also simply referred to as "resin composition") is a resin composition comprising at least one resin P selected from the group consisting of cyclized resins and precursors of cyclized resins, and a compound A represented by the following formula (1).

[0017]

[0018] In formula (1), R １１ ~R １５ Each of these independently represents a hydrogen atom or a substituent. １１ ~R １５ At least two of them may be joined together to form a ring. １１ This represents a group represented by the following formula (G-1) or (G-2).

[0019]

[0020] In formulas (G-1) and (G-2), * represents a bonding site. In formula (G-2), R Ａ１１ represents a hydrogen atom or substituent.

[0021] In this specification, "at least one resin (resin P) selected from the group consisting of cyclized resins and precursors of cyclized resins" is also referred to as "specific resin".

[0022] The resin composition of the present invention is preferably used to form a photosensitive film subjected to exposure and development, and more preferably used to form a film subjected to exposure and development using a developer solution containing an organic solvent. The resin composition of the present invention can be used, for example, to form insulating films for semiconductor devices, interlayer insulating films for redistribution layers, stress buffer films, etc., and is preferably used to form interlayer insulating films for redistribution layers. Furthermore, the resin composition of the present invention may be a negative-type resin composition or a positive-type resin composition, but is preferably a negative-type resin composition. A negative-type resin composition refers to a resin composition that can be used to form a negative-type photosensitive film, and a positive-type resin composition refers to a resin composition that can be used to form a positive-type photosensitive film. A negative-type photosensitive film refers to a photosensitive film that can be used in negative-type development, and a positive-type photosensitive film refers to a photosensitive film that can be used in positive-type development. Negative-type development refers to development in which the unexposed areas are removed by development during exposure and development, and positive-type development refers to development in which the exposed areas are removed by development. The above-mentioned exposure method, developer, and developing method may be, for example, those described in the exposure process, developing process, and other descriptions in the description of the curing method described later. The resin composition of the present invention is preferably used to form a cured product in which at least a portion is in contact with a metal. Examples of metals include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals, with copper, aluminum, or alloys containing at least one of these being preferred. Copper or alloys containing copper are preferred.

[0023] The resin composition of the present invention provides a cured product in which the generation of voids and metal oxides between the cured product and the metal layer is suppressed over a long period of time. The mechanism by which the above effect is obtained is unknown, but it is presumed to be as follows. The compound represented by formula (1) contains a structure in which an aromatic ring and a heterocycle are fused. Here, it is thought that the heteroatom portion of the heterocycle is adsorbed onto the metal surface, such as metal wiring, thereby suppressing the migration of metal to the cured product. It is thought that by suppressing the migration of metal to the cured product, the generation of voids and metal oxides can be suppressed. Furthermore, because the compound represented by formula (1) has an aromatic ring and a heterocycle, it has excellent compatibility with specific resins. Therefore, it is less likely to precipitate during the formation of the cured product, and when applied to a metal, adsorption to the metal occurs in a nearly uniform state, so it is thought that the above effect of suppressing the generation of voids and metal oxides can be easily obtained.

[0024] The resin composition of the present invention will be described in detail below.

[0025] <Resin P (Specific Resin)> The resin composition of the present invention contains at least one resin P (specific resin) selected from the group consisting of cyclized resins and precursors of cyclized resins. The cyclized resin is preferably a resin that contains an imide ring structure or an oxazole ring structure in its main chain structure. In the present invention, "main chain" refers to the relatively longest bonding chain in the resin molecule, and "side chain" refers to the other bonding chains. Examples of cyclized resins include polyimide, polybenzoxazole, and polyamideimide. A precursor of a cyclized resin is a resin that undergoes a change in chemical structure due to external stimuli to become a cyclized resin. Resins that undergo a change in chemical structure due to heat to become a cyclized resin are preferred, and resins that undergo a ring-closing reaction due to heat to form a ring structure are more preferred. Examples of precursors of cyclized resins include polyimide precursors, polybenzoxazole precursors, and polyamideimide precursors.

[0026] In this specification, polyimide refers to a resin having repeating units containing imide structures within its molecular chain, and preferably a resin having repeating units containing imide ring structures within its molecular chain. Furthermore, if the polyimide is a linear resin, it is preferable that the polyimide is a resin having repeating units containing imide structures within its main chain, and more preferably a resin having repeating units containing imide ring structures within its main chain. In this specification, imide structure refers to a structure represented by *-C(=O)N(-*)C(=O)-*, where * represents a bonding site with another structure, preferably a bonding site with a carbon atom, and more preferably a bonding site with a quaternary carbon atom. In this specification, imide ring structure refers to a ring structure that includes all two carbon atoms and nitrogen atoms in the above imide structure as ring members. The imide ring structure is preferably a five-membered ring.

[0027] In this specification, a polyimide precursor refers to a resin that undergoes a change in chemical structure upon external stimulation to become a polyimide, preferably a resin that undergoes a change in chemical structure upon heat to become a polyimide, and more preferably a resin that undergoes a ring-closing reaction upon heat to form a ring structure to become a polyimide. Preferred embodiments of the formed polyimide are as described above.

[0028] In this specification, polybenzoxazole refers to a resin having repeating units containing a benzoxazole structure within its molecular chain. Furthermore, when the polybenzoxazole is a linear resin, it is preferable that the polybenzoxazole is a resin having repeating units containing a benzoxazole structure within its main chain. In the present invention, the benzoxazole structure refers to a structure represented by the following formula (PBO-1).

[0029]

[0030] In formula (PBO-1), * indicates a bonding site with another structure.

[0031] In this specification, a polybenzoxazole precursor refers to a resin that undergoes a chemical structure change upon external stimulation to become a polybenzoxazole, preferably a resin that undergoes a chemical structure change upon heat to become a polybenzoxazole, and more preferably a resin that undergoes a ring-closing reaction upon heat to form a ring structure to become a polybenzoxazole. The preferred embodiments of the formed polybenzoxazole are as described above.

[0032] In this specification, polyamide-imide refers to a resin having an amide structure in addition to an imide structure within its molecular chain, and is preferably a resin having repeating units containing an imide ring structure and an amide structure within its molecular chain. In this specification, an amide structure refers to a structure represented by *-C(=O)N(-#)-*, where * represents a bonding site with another structure, preferably a bonding site with a carbon atom, and more preferably a bonding site with a quaternary carbon atom. Also, # represents a bonding site with another structure, preferably a bonding site with a hydrogen atom or a carbon atom, and more preferably a bonding site with a hydrogen atom. In this specification, a polyamide-imide precursor refers to a resin that undergoes a change in chemical structure due to an external stimulus to become a polyamide-imide, preferably a resin that undergoes a change in chemical structure due to heat to become a polyamide-imide, and is more preferably a resin that undergoes a ring-closing reaction due to heat to form a ring structure to become a polyamide-imide. Preferred embodiments of the formed polyamide-imide are as described above.

[0033] The resin composition preferably contains, as a 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 polyimide or a polyimide precursor as the specific resin. Resin P is preferably polyimide or a polyimide precursor. The specific resin preferably has polymerizable groups, and more preferably contains radical polymerizable groups. If the specific resin has radical polymerizable groups, the resin composition of the present invention preferably contains a radical polymerization initiator, and more preferably contains a radical polymerization initiator and a radical crosslinking agent. Furthermore, a sensitizer may be included as needed. For example, a negative-type photosensitive film can be formed from such a resin composition. The specific resin may also have polarity-converting groups such as acid-degradable groups. If the specific resin has acid-degradable groups, the resin composition preferably contains a photoacid generator. For example, a chemically amplified positive-type or negative-type photosensitive film can be formed from such a resin composition.

[0034] [Polyimide Precursor] The polyimide precursor used in the present invention is not particularly limited in terms of type, but it is preferable that it contains repeating units represented by the following formula (2).

[0035]

[0036] In formula (2), A １ and A ２ Each is independently an oxygen atom or -NR ｚ - represents R １１１ represents a divalent organic group, R １１５ represents a tetravalent organic group, R １１３ and R １１４ Each of these independently represents a hydrogen atom or a monovalent organic group, R ｚ represents a hydrogen atom or a monovalent organic group.

[0037] A in equation (2) １ and A ２ Each is independently an oxygen atom or -NR ｚ R represents a negative sign, and an oxygen atom is preferred.ｚ R represents a hydrogen atom or a monovalent organic group, with a hydrogen atom being preferred. １１１ R represents a divalent organic group. Examples of divalent organic groups include linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups. Preferably, the group consists of 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 combination thereof, with groups containing an aromatic group having 6 to 20 carbon atoms being more preferred. The linear or branched aliphatic group may have hydrocarbon groups in the chain substituted with groups containing heteroatoms, and the cyclic aliphatic group and aromatic group may have hydrocarbon groups in the ring members substituted with groups containing heteroatoms. １１１ Examples include groups represented by -Ar- and -Ar-L-Ar-, with the group represented by -Ar-L-Ar- being preferred. However, Ar is independently an aromatic group, and L is a single bond or a C1-C10 aliphatic hydrocarbon group which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ２ The group consists of - or -NHCO-, or a combination of two or more of the above. The preferred ranges are as described above.

[0038] R １１１ It is preferable that it be derived from a diamine. Examples of diamines used in the production of polyimide precursors 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, R １１１ The diamine 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 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 hydrocarbon groups in the chain substituted with groups containing heteroatoms, and the cyclic aliphatic group and aromatic group may have hydrocarbon groups in the ring members substituted with groups containing heteroatoms. Examples of groups containing aromatic groups are listed below.

[0039]

[0040] In the formula, A 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 that may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -SO ２ Preferably, the group is -, -NHCO-, or a combination thereof, and may be a single bond or a C1-C3 alkylene group substituted with a fluorine atom, -O-, -C(=O)-, -S-, or -SO ２ It is more preferable that the group is selected from -CH ２ -, -O-, -S-, -SO ２ -, -C (CF ３ ) ２ -, or -C(CH ３ ) ２ It is even more preferable that it is -. In the formula, * represents a bonding site with another structure.

[0041] Diamines include, specifically, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane or 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 isophoronediamines; 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, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4 ,4'-diaminoparaterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 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 N, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, ester 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,Examples include 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)diphenylsulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 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'-hexafluorotidine, and 4,4'-diaminoquaterphenyl.

[0042] Furthermore, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferred.

[0043] Furthermore, diamines having two or more alkylene glycol units as the main chain, as described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598, are also preferably used.

[0044] R １１１ From the viewpoint of the flexibility of the resulting organic film, it is preferable that it be represented as -Ar-L-Ar-. However, Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ２ - or -NHCO-, or a group consisting of two or more of the above. Ar is preferably a phenylene group, and L is a carbon-1 or carbon-2 aliphatic hydrocarbon group, -O-, -CO-, -S-, or -SO- which may be substituted with a fluorine atom. ２ - is preferred. Here, the aliphatic hydrocarbon group is preferably an alkylene group.

[0045] Also, R １１１ From the viewpoint of i-ray transmittance, it is preferable that the group is a divalent organic group represented by formula (51) or formula (61) below. In particular, from the viewpoint of i-ray transmittance and availability, it is more preferable that the group is a divalent organic group represented by formula (61).

[0046]

[0047] In formula (51), R ５０ ~R ５７ Each of these is independently a hydrogen atom, a fluorine atom, or a monovalent organic group, R ５０ ~R ５７ At least one of them is a fluorine atom, a methyl group, or a trifluoromethyl group, and * independently represents the bonding site with the nitrogen atom in formula (2). ５０ ~R ５７ Examples of monovalent organic groups include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and fluorinated alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

[0048]

[0049] In formula (61), R ５８ and R ５９ Each of these is independently a fluorine atom, a methyl group, or a trifluoromethyl group, and each of these 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 individually or in combination of two or more.

[0050] R １１１ The number of carbon atoms is preferably 4 or more, more preferably 4 to 50, and even more preferably 4 to 40. In formula (2), R １１１ The group may include a structure obtained by removing two or more hydrogen atoms from a structure represented by any of the following formulas (V-1) to (V-10). By including an organic group with a structure obtained by removing two or more hydrogen atoms from a structure represented by any of the following formulas (V-1) to (V-10), the chemical resistance and flatness of the cured product are improved.

[0051]

[0052] In formula (V-2), R Ｘ１ Each of these is independently a hydrogen atom, an alkyl group, or an alkyl halogen. In formula (V-3), R Ｘ２ and R Ｘ３ Each of these independently represents a hydrogen atom or a substituent, R Ｘ２ and R Ｘ３ They may bond to form a ring structure. In formula (V-8), R Ｘ５ Each of these is independently a hydrogen atom, an alkyl group, or an alkyl halogen.

[0053] In formula (V-2), R Ｘ１ Each of these is 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 is a group in which at least one hydrogen atom of the alkyl group is 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 Each of these is preferably a hydrogen atom. Ｘ２ and R Ｘ３ When R is bonded to form a ring structure, Ｘ２ and R Ｘ３ The structures formed by the bonding of these are single bonds, -O-, or -C(R) ２ It is preferable that it be -O- or -C(R) ２ It is more preferable that it be -, and even more preferable that it be -O-. R represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom. In formula (V-8), R Ｘ５ Each of these groups is preferably an alkyl group or a halogenated alkyl group, more preferably a C1-C4 alkyl group or a C1-C4 halogenated alkyl group, and even more preferably a methyl group or a trifluoromethyl group. A halogenated alkyl group is a group in which at least one hydrogen atom of the alkyl group is substituted with a halogen atom. The halogen atom is preferably F or Cl, and more preferably F.

[0054] R１１１ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-1), then R １１１ It is preferable that the group is represented by the following formula (V-1-2). In the following formula, * is R in formula (2). １１１ The 'n' represents the bonding site with the two nitrogen atoms to which it is bonded, and n1 represents an integer from 1 to 5. Furthermore, the hydrogen atoms in the structure below may be further substituted with a group represented by formula (RP-1) described later, or with known substituents such as hydrocarbon groups.

[0055]

[0056] R １１１ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-2), then R １１１ It is preferable that the group is 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 preferable that the group is represented by formula (V-2-4). In the following formula, L Ｘ１ represents a single bond or -O-, and * represents R in formula (2). １１１ This represents the bonding site with the two nitrogen atoms to which it is bonded. Also, R Ｘ１ The definition and preferred embodiments are as described above. Furthermore, the hydrogen atoms in these structures may be further substituted with a group represented by formula (RP-1), which will be described later, or with known substituents such as hydrocarbon groups.

[0057]

[0058] R １１１ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-3), then R １１１ It is preferable that the group is 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, it is preferable that the group is represented by formula (V-3-3). In the following formula, * is R in formula (2). １１１ This represents the bonding site with the two nitrogen atoms to which it is bonded. Also, R Ｘ２ and R Ｘ３The definition and preferred embodiments are as described above. Further, the hydrogen atoms in these structures may be further substituted with a group represented by the formula (RP-1) described later, or a known substituent such as a hydrocarbon group.

[0059]

[0060] R １１１ When R is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by the formula (V-4), R １１１ is preferably a group represented by the following formula (V-4-2) or formula (V-4-3). In the following formula, * represents the bonding site with the two nitrogen atoms to which R in the formula (2) is bonded, and n1 represents an integer of 0 to 5. Also, the embodiment where n1 is 0 is one of the preferred embodiments of the present invention. Further, the hydrogen atoms in the following structure may be further substituted with a group represented by the formula (RP-1) described later, or a known substituent such as a hydrocarbon group. Examples of the known substituent include an alkyl group, a halogenated alkyl group, a halogen atom, etc. １１１

[0061]

[0062] R １１１ When R is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by the formula (V-5), R １１１ is preferably a group represented by the following formula (V-5-2). In the following formula, * represents the bonding site with the two nitrogen atoms to which R in the formula (2) is bonded. Further, the hydrogen atoms in the formula (V-5-2) may be further substituted with a group represented by the formula (RP-1) described later, or a known substituent such as a hydrocarbon group. Examples of the known substituent include an alkyl group, a halogenated alkyl group, a halogen atom, etc. However, it is also preferable that none of the hydrogen atoms in the structure represented by (V-5-2) are substituted. １１１

[0063]

[0064]

[0065] R １１１ When R is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by the formula (V-6), R １１１is preferably a group represented by the following formula (V-6-2). In the following formula, * represents the bonding site with the two nitrogen atoms to which R in formula (2) is bonded. Further, the hydrogen atom in the following structure may be further substituted with a group represented by the formula (RP-1) described later, or a known substituent such as a hydrocarbon group. １１１ In the following structure, the hydrogen atom may be further substituted with a group represented by the formula (RP-1) described later, or a known substituent such as a hydrocarbon group.

[0065]

[0066] R １１１ When R is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-7), R １１１ is preferably a group represented by the following formula (V-7-2). In the following formula, * represents the bonding site with the two nitrogen atoms to which R in formula (2) is bonded. Further, the hydrogen atom in the following structure may be further substituted with a group represented by the formula (RP-1) described later, or a known substituent such as a hydrocarbon group. １１１ In the following structure, the hydrogen atom may be further substituted with a group represented by the formula (RP-1) described later, or a known substituent such as a hydrocarbon group.

[0067]

[0068] R １１１ When R is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-8), R １１１ is preferably a group represented by the following formula (V-8-2). In the following formula, * represents the bonding site with the two nitrogen atoms to which R in formula (2) is bonded. Further, the definition and preferred embodiment of R １１１ are as described above. Further, the hydrogen atom in the following structure may be further substituted with a group represented by the formula (RP-1) described later, or a known substituent such as a hydrocarbon group. Ｘ５ In the following structure, the hydrogen atom may be further substituted with a group represented by the formula (RP-1) described later, or a known substituent such as a hydrocarbon group.

[0069]

[0070] R １１１ When R is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-9), R １１１ is preferably a group represented by the following formula (V-9-2). In the following formula, * represents the bonding site with the two nitrogen atoms to which R in formula (2) is bonded. １１１This represents the bonding site with the two nitrogen atoms to which it is bonded. Furthermore, the hydrogen atoms in the structure below may be further substituted with a group represented by formula (RP-1) described later, or with known substituents such as hydrocarbon groups.

[0071]

[0072] R １１１ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-10), then R １１１ It is preferable that the group is represented by the following formula (V-10-2). In the following formula, * is R in formula (2). １１１ This represents the bonding site with the two nitrogen atoms to which it is bonded. Furthermore, the hydrogen atoms in the structure below may be further substituted with a group represented by formula (RP-1) described later, or with known substituents such as hydrocarbon groups.

[0073]

[0074] Other, R １１１ The base may be the one described in paragraphs 0042 to 0053 of Japanese Patent Publication No. 2023-003421. Also, R １１１ It is preferable that the structure does not contain an imide structure. Also, R １１１ It is preferable that the structure does not contain urethane bonds, urea bonds, and amide bonds. Furthermore, R １１１ It is preferable that the structure does not contain ester bonds. Among these, R １１１ It is preferable that the material does not contain imide structures, urethane bonds, urea bonds, and amide bonds, and more preferably that it does not contain imide structures, urethane bonds, urea bonds, amide bonds, and ester bonds.

[0075] R in equation (2) １１５ * represents a tetravalent organic group. A tetravalent organic group containing an aromatic ring is preferred, and a group represented by formula (5) or formula (6) below is more preferred. In formula (5) or formula (6), * independently represents a bonding site with another structure.

[0076]

[0077] In formula (5), R １１２The linking group is a single bond or a divalent linking group, and may be a single bond or a carbon-1 to carbon-10 aliphatic hydrocarbon group, -O-, -CO-, -S-, -SO- which may be substituted with a fluorine atom. ２ Preferably, the group is selected from -, -NHCO-, and combinations thereof, and is a C1- to C3 alkylene group, -O-, -CO-, -S-, and -SO- which may be single-bonded or substituted with a fluorine atom. ２ It is more preferable that the group is selected from -CH ２ -, -C (CF ３ ) ２ -, -C(CH ３ ) ２ -, -O-, -CO-, -S-, and -SO ２ It is even more preferable that the group is a divalent group selected from the group consisting of -.

[0078] R １１５ The number of carbon atoms is preferably 4 or more, more preferably 4 to 50, and even more preferably 4 to 40.

[0079] Among these, R １１５ The fact that the organic group contains a structure obtained by removing two or more hydrogen atoms from any of the above formulas (V-1) to (V-10) improves the chemical resistance and flatness of the cured product. Also, R １１５ By including an organic group containing a structure obtained by removing two or more hydrogen atoms from any of the structures represented by formulas (V-1) to (V-5), effects such as suppression of developing residue generation, lower dielectric constant of cured products, and reduction of thermal expansion coefficient can be obtained. By including an organic group containing a structure obtained by removing two or more hydrogen atoms from any of the structures represented by formulas (V-6) to (V-10), effects such as improved ultraviolet light transmittance, making it less likely for the cured product pattern to become tapered, and a wider tolerance for exposure amount can be obtained.

[0080] R １１５ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-1), then R １１５ It is preferable that the group is represented by the following formula (V-1-1). In the following formula, * is R in formula (2). １１５The 'n' represents the bonding sites with the four carbonyl groups to which it is bonded, and n1 represents an integer from 0 to 5, preferably an integer from 1 to 5. Furthermore, the hydrogen atoms in the structure below may be further substituted with a group represented by formula (RP-1) described later, or with known substituents such as hydrocarbon groups.

[0081]

[0082] R １１５ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-2), then R １１５ It is preferable that the group is 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 preferable that the group is represented by formula (V-2-2). In this specification, a bond intersecting the edge of a ring structure means that one of the hydrogen atoms in that ring structure is substituted. In the following formula, L Ｘ１ represents a single bond or -O-, and * represents R in formula (2). １１５ This represents the bonding sites with the four carbonyl groups to which it is bonded. Also, R Ｘ１ The definition and preferred embodiment of are as described above. Furthermore, the hydrogen atom in these structures is R in formula (2). １ Alternatively, it may be further substituted with known substituents such as hydrocarbon groups.

[0083]

[0084] R １１５ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-3), then R １１５ It is preferable that the group is 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, it is preferable that the group is represented by formula (V-3-2). In the following formula, * is R in formula (2). １１５ This represents the bonding sites with the four carbonyl groups to which it is bonded. Also, R Ｘ２ and R Ｘ３ The definition and preferred embodiments are as described above. Furthermore, the hydrogen atoms in these structures may be further substituted with a group represented by formula (RP-1), which will be described later, or with known substituents such as hydrocarbon groups.

[0085]

[0086] R １１５ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-4), then R １１５ It is preferable that the group is represented by the following formula (V-4-1). In the following formula (V-4-1), * is R in formula (2). １１５ The 'v' represents the bonding sites with the four carbonyl groups to which it is bonded, and n1 represents an integer from 0 to 5. Furthermore, the hydrogen atoms in formula (V-4-1) may be further substituted with known substituents such as the group represented by formula (RP-1) described later, or hydrocarbon groups. Examples of known substituents include alkyl groups, alkyl halides, and halogen atoms. However, it is also preferable that none of the hydrogen atoms in the structure represented by (V-4-1) are substituted.

[0087]

[0088] R １１５ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-5), then R １１５ It is preferable that the group is represented by the following formula (V-5-1). In the following formula, * is R in formula (2). １１５ This represents the bonding sites with the four carbonyl groups to which it is bonded. Furthermore, the hydrogen atoms in formula (V-5-1) may be further substituted with known substituents such as the group represented by formula (RP-1) described later, or hydrocarbon groups. Examples of known substituents include alkyl groups, alkyl halides, and halogen atoms. However, it is also preferable that none of the hydrogen atoms in the structure represented by (V-5-1) are substituted.

[0089]

[0090] R １１５ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-6), then R １１５ It is preferable that the group is represented by the following formula (V-6-1). In the following formula, * is R in formula (2). １１５This represents the bonding sites with the four carbonyl groups to which it is bonded. Furthermore, the hydrogen atoms in the structure below may be further substituted with a group represented by formula (RP-1) described later, or with known substituents such as hydrocarbon groups.

[0091]

[0092] R １１５ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-7), then R １１５ It is preferable that the group is represented by the following formula (V-7-1). In the following formula, * is R in formula (2). １１５ This represents the bonding sites with the four carbonyl groups to which it is bonded. Furthermore, the hydrogen atoms in the structure below may be further substituted with a group represented by formula (RP-1) described later, or with known substituents such as hydrocarbon groups.

[0093]

[0094] R １１５ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-8), then R １１５ It is preferable that the group is represented by the following formula (V-8-1). In the following formula, * is R in formula (2). １１５ This represents the bonding sites with the four carbonyl groups to which it is attached. Ｘ５ The definition and preferred embodiments are as described above. Furthermore, the hydrogen atoms in the following structure may be further substituted with a group represented by formula (RP-1) described later, or with known substituents such as hydrocarbon groups.

[0095]

[0096] R １１５ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-9), then R １１５ It is preferable that the group is represented by the following formula (V-9-1). In the following formula, * is R in formula (2). １１５ This represents the bonding sites with the four carbonyl groups to which it is bonded. Furthermore, the hydrogen atoms in the structure below may be further substituted with a group represented by formula (RP-1) described later, or with known substituents such as hydrocarbon groups.

[0097]

[0098] R １１５ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-10), then R １１５ It is preferable that the group is represented by the following formula (V-10-1). In the following formula, * is R in formula (2). １１５ This represents the bonding sites with the four carbonyl groups to which it is bonded. Furthermore, the hydrogen atoms in the structure below may be further substituted with known substituents such as the group represented by formula (RP-1) described later, or hydrocarbon groups.

[0099]

[0100] Other, R １１５ This may be a tetracarboxylic acid residue remaining after the removal of the anhydride group from the tetracarboxylic dianhydride described in paragraphs 0055 to 0057 of Japanese Patent Application Publication No. 2023-003421.

[0101] Also, R １１５ It is preferable that the structure does not contain an imide structure. Also, R １１５ Preferably, the structure does not contain urethane bonds, urea bonds, or amide bonds. In the present invention, urethane bonds are defined as *-O-C(=O)-NR Ｎ -* is a combination represented by R Ｎ R represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom. Ｎ The hydrogen atom or hydrocarbon group is preferred, the hydrogen atom or alkyl group is more preferred, and the hydrogen atom is even more preferred. In the present invention, the urea bond is *-NR Ｎ -C(=O)-NR Ｎ -* is a combination represented by R Ｎ Each of the symbols independently represents a hydrogen atom or a monovalent organic group, and each of the symbols * represents a bonding site with a carbon atom. Ｎ The preferred embodiment is as described above. Furthermore, R １１５ Preferably, the structure does not contain ester bonds. In the present invention, an ester bond is a bond represented by *-O-C(=O)-*. Among these, R １１５It is preferable that the material does not contain imide structures, urethane bonds, urea bonds, and amide bonds, and more preferably that it does not contain imide structures, urethane bonds, urea bonds, amide bonds, and ester bonds.

[0102] Also, R １１５ This is the structure represented by the following formula (X-3), or X in the structure represented by formula (X-3). ２ A hydrogen atom or L of the group represented by ３ The hydrogen atom of the group represented by may be replaced by the group represented by formula (RP-1) described later.

[0103]

[0104] In formula (X-3), X ２ Each of these independently represents a trivalent linking group, L ３ represents a divalent linking group, and * represents a bonding site with other structures. In formula (X-3), X ２ and L ３ A preferred embodiment is X in formula (X-2) described later. ２ and L ３ This is similar to the preferred embodiment.

[0105] R １１５ Specifically, examples include tetracarboxylic acid residues remaining after the removal of the anhydride group from tetracarboxylic dianhydride. Polyimide precursors are R １１５ The structure may contain only one tetracarboxylic dianhydride residue, or it may contain two or more. The tetracarboxylic dianhydride is preferably represented by the following formula (O).

[0106]

[0107] In formula (O), R １１５ R represents a tetravalent organic group. １１５ The preferred range of R in equation (2) is １１５ This is synonymous with the same thing, and the preferred range is also similar.

[0108] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA). 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-diphenylsulfidetetracarboxylic acid dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3',4,4'-diphenylmethanetetracarboxylic acid dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4'-benzophenonetetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,4,5,7-naphthalenetetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride Examples include aqueous compounds, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydride, 1,4,5,6-naphthalenetetracarboxylic acid dianhydride, 2,2',3,3'-diphenyltetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 1,2,4,5-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, and alkyl and alkoxy derivatives of these compounds having 1 to 6 carbon atoms.

[0109] Furthermore, the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598 are also preferred examples.

[0110] Among these, R in equation (2) １１５ and R １１１However, it is preferable that all of them contain a ring structure, and it is more preferable that all of them contain an aromatic ring structure. Also, R in formula (2) １１５ and R １１１ However, it is preferable that each of these groups is an organic group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by any of the above formulas (V-1) to (V-10), and more preferably an organic group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by any of the above formulas (V-1) to (V-4). Preferred embodiments of these groups are as described above.

[0111] In equation (2), R １１１ and R １１５ It is also possible that at least one of them has an OH group. More specifically, R １１１ Examples include residues of bisaminophenol derivatives.

[0112] [Base represented by formula (RP-1)] In formula (2), R １１１ and R １１５ At least one of them may include a group represented by formula (RP-1).

[0113]

[0114] 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, and * represents R in formula (2). １１５ or R １１１ This represents the bonding site with other structures.

[0115] In formula (RP-1), L １ Preferably, the group is represented by the following formula (L-2).

[0116]

[0117] In formula (L-2), Z ２ -O-, -NR Ｎ -, -C(=O)O- or -C(=O)NR Ｎ - represents R Ｎ represents a hydrogen atom or a monovalent organic group, and when a1 is 1, L ｘ represents a single bond or a divalent linking group, and when a1 is 2 or more, Lｘ represents a1+1 valent linking group, a1 represents an integer greater than or equal to 1, and * represents R in equation (2). １１５ or R １１１ This indicates a bonding site with other structures inside, and # represents A in formula (RP-1). １ This represents the connection point.

[0118] In formula (L-2), Z ２ It is preferable that is -O- or -C(=O)O-. Also, Z ２ ga-NR Ｎ - If R Ｎ A hydrogen atom or a hydrocarbon group is preferred, a hydrogen atom, an alkyl group or a phenyl group is more preferred, and a hydrogen atom is even more preferred. In formula (L-2), when a1 is 1, L ｘ It 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. In formula (L-2), when a1 is 2 or more, L ｘ It 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 is the same as a1 in formula (RP-1).

[0119] In formula (RP-1), A １ represents a polymerizable group. The preferred embodiment of the polymerizable group is as described above for the preferred embodiment of the polymerizable group possessed by the specific resin.

[0120] Among these, A １ The group is preferably a vinylphenyl group, a (meth)acryloxy group, a vinyl ether group, a maleimide group, an allyl group, or a group containing these, and more preferably a maleimide group, a (meth)acryloxy group, a (meth)acrylamide group, or a vinylphenyl group. In particular, the (meth)acryloxy group is preferred from the viewpoint of reactivity. Furthermore, the maleimide group or a vinylphenyl group is preferred from the viewpoint of reducing the dielectric loss tangent of the cured product. In particular, A in formula (RP-1) included in formula (2) １At 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 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.

[0121] Among these, A in equation (RP-1) １ is a vinylphenyl group, L １ It is preferable that the group is represented by formula (L-2-1).

[0122]

[0123] In formula (L-2-1), L Ｘ２ represents a hydrocarbon group, a1 represents an integer of 1 or more, and * represents R in formula (2). １１５ or R １１１ This indicates a bonding site with other structures inside, and # represents A in formula (RP-1). １ This represents the bonding site with. In formula (L-2-1), L Ｘ２ An aliphatic saturated hydrocarbon group is preferred. When a1 is 1, L Ｘ２ An alkylene group is preferred, an alkylene group having 1 to 10 carbon atoms is more preferred, an alkylene group having 1 to 4 carbon atoms is even more preferred, and a methylene group is particularly preferred. In formula (L-2-1), a1 is the same as a1 in formula (RP-1).

[0124] Also, A in equation (RP-1) １ The maleimide group is L １ is a group represented by formula (L-2), where L in formula (L-2) ＸIt is preferable that the group is an aromatic group or an aliphatic saturated hydrocarbon group having four or more carbon atoms. The aromatic group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, but an aromatic hydrocarbon group is preferred. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having six to ten carbon atoms, and more preferably an aromatic hydrocarbon group having six carbon atoms. Examples of heteroatoms in the aromatic heterocyclic group include oxygen atoms, nitrogen atoms, sulfur atoms, etc. The number of heteroatoms in the aromatic heterocyclic group is preferably one or two. Furthermore, the aromatic heterocyclic group is preferably a five-membered ring or a six-membered ring containing the above heteroatoms. In addition, other aromatic heterocyclic groups or other aromatic hydrocarbon ring groups may be fused to the aromatic heterocyclic group. The aliphatic saturated hydrocarbon group having four or more carbon atoms may have a linear, branched, cyclic, or combination thereof structure. The number of carbon atoms in the aliphatic saturated hydrocarbon group having four or more carbon atoms is preferably four to 20, and more preferably five to 10.

[0125] In formula (RP-1), a1 is preferably an integer between 1 and 4, and more preferably an integer between 1 and 2. Furthermore, the embodiment in which a1 is 1 is also one of the preferred embodiments of the present invention.

[0126] Furthermore, it is preferable that the number of ester bonds in formula (RP-1) is 1 or 0.

[0127] R in equation (2) １１３ and R １１４ Each of these independently represents a hydrogen atom or a monovalent organic group. Preferably, the monovalent organic group includes a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkylene oxy group. Also, R １１３ and R １１４ It is preferable that at least one of them contains a polymerizable group, and more preferably that both contain a polymerizable group. １１３ and R １１４It is also preferable that at least one of the components contains two or more polymerizable groups. The polymerizable groups are groups that can undergo crosslinking reactions by the action of heat, radicals, etc., and radical polymerizable groups are preferred. Specific examples of polymerizable groups include groups having an ethylenically unsaturated bond, alkoxymethyl groups, hydroxymethyl groups, acyloxymethyl groups, epoxy groups, oxetanyl groups, benzoxazolyl groups, blocked isocyanate groups, and amino groups. As radical polymerizable groups of the polyimide precursor, groups having an ethylenically unsaturated bond are preferred. Examples of groups having an ethylenically unsaturated bond include vinyl groups, allyl groups, isoallyl groups, 2-methylallyl groups, groups having an aromatic ring directly bonded to a vinyl group (for example, vinylphenyl groups), (meth)acrylamide groups, (meth)acryloyloxy groups, and groups represented by the following formula (III), with groups represented by the following formula (III) being preferred.

[0128]

[0129] In equation (III), R ２００ R represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, with a hydrogen atom or a methyl group being preferred. In formula (III), * represents a bonding site with other structures. In formula (III), R ２０１ This is an alkylene group having 2 to 12 carbon atoms, -CH ２ CH(OH)CH ２ - represents a cycloalkylene group or a polyalkylene oxy group. Preferred R ２０１ Examples include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, as well as 1,2-butanediyl, 1,3-butanediyl, and -CH ２ CH(OH)CH ２ -Polyalkylene oxy groups are examples, including alkylene groups such as ethylene groups and propylene groups, and -CH ２ CH(OH)CH ２-, cyclohexyl groups, polyalkylene oxy groups are more preferred, alkylene groups such as ethylene groups and propylene groups, or polyalkylene oxy groups are even more preferred. In the present invention, a polyalkylene oxy group refers to a group in which two or more alkylene oxy groups are directly bonded. The alkylene groups in the multiple alkylene oxy groups contained in the polyalkylene oxy group may be the same or different. When the polyalkylene oxy group contains multiple types of alkylene oxy groups with different alkylene groups, the arrangement of the alkylene oxy groups in the polyalkylene oxy group may be random, have blocks, or have patterns such as alternating arrangements. The number of carbon atoms in the alkylene group (including the number of carbon atoms of the substituents if the alkylene group has substituents) 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 substituents. Preferred substituents include alkyl groups, aryl groups, halogen atoms, etc. The number of alkylene oxy groups contained in the polyalkylene oxy group (number of repeating polyalkylene oxy 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 polyalkylene oxy group is preferably a polyethylene oxy group, a polypropylene oxy group, a polytrimethylene oxy group, a polytetramethylene oxy group, or a group in which multiple ethylene oxy groups and multiple propylene oxy groups are bonded, more preferably a polyethylene oxy group or a polypropylene oxy group, and even more preferably a polyethylene oxy group. In the group in which multiple ethylene oxy groups and multiple propylene oxy groups are bonded, the ethylene oxy groups and propylene oxy groups may be arranged randomly, in blocks, or in alternating patterns. The preferred configurations for the number of repeating ethylene oxy groups in these groups are as described above.

[0130] In equation (2), R １１３If R is a hydrogen atom, １１４ If the atom is a hydrogen atom, the polyimide precursor may form a pair 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.

[0131] In equation (2), R １１３ and R １１４ At least one of the groups may be a polarity-converting group such as an acid-degradable group. The acid-degradable group is not particularly limited as long as it decomposes under the action of acid to produce alkali-soluble groups such as phenolic hydroxyl groups and carboxyl groups, but acetal groups, ketal groups, silyl groups, silyl ether groups, and tertiary alkyl ester groups are preferred, and from the viewpoint of exposure sensitivity, acetal groups or ketal groups are more preferred. Specific examples of acid-degradable groups include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group, tert-butoxycarbonylmethyl group, and trimethylsilyl ether group. From the viewpoint of exposure sensitivity, ethoxyethyl groups or tetrahydrofuranyl groups are preferred.

[0132] The polyimide precursor may also preferably contain fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0133] Furthermore, to improve adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples include using bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane as the diamine.

[0134] The repeating unit represented by formula (2) is preferably the 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 the repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A) in the polyimide precursor, it becomes possible to further widen the exposure latitude. Formula (2-A)

[0135]

[0136] In formula (2-A), A １ and A ２ represents an oxygen atom, R １１１ and R １１２ Each of these independently represents a divalent organic group, R １１３ and R １１４ Each of these independently represents a hydrogen atom or a monovalent organic group, R １１３ and R １１４ Preferably, at least one of the groups is a polymerizable group, and both are polymerizable groups.

[0137] A １ A ２ , R １１１ , R １１３ and R １１４ These are, independently of A in equation (2), １ A ２ , R １１１ , R １１３ and R １１４ This is synonymous with the following, and the preferred range is also similar. １１２ R in equation (5) is １１２ This is synonymous with the same thing, and the preferred range is also similar.

[0138] The polyimide precursor may contain one type of repeating unit represented by formula (2), or it may contain two or more types. It may also contain structural isomers of the repeating unit represented by formula (2). In addition to the repeating unit of formula (2), the polyimide precursor may also contain other types of repeating units.

[0139] One embodiment of the polyimide precursor in the present invention is one in which the content of repeating units represented by formula (2) is 50 mol% or more of the total repeating units. The above 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 above total content is not particularly limited, and all repeating units in the polyimide precursor except for the terminals may be repeating units represented by formula (2).

[0140] 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 dispersion of the above polyimide precursor is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no particular upper limit for the molecular weight dispersion of the polyimide precursor, but for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and even more preferably 6.0 or lower. In this specification, molecular weight dispersion is a value calculated by weight-average molecular weight / number-average molecular weight. When a resin composition contains multiple types of polyimide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polyimide precursors are within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated by treating the multiple types of polyimide precursors as a single resin are, respectively, within the above ranges.

[0141] When the specific resin is a polyimide precursor, the imidation rate (also called the "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 and insulating properties of the resulting organic film. The lower limit of the above imidation rate may be 0% or more, 5% or more, or 10% or more. The imidation rate refers to the ratio (%) of the molar amount of the imide ring structure to the total molar amount of the amic acid structure, amic acid ester structure, and imide ring structure.

[0142] [Polyimide] The polyimide used in the present invention may be an alkali-soluble polyimide, or a polyimide soluble in a developer mainly composed of an organic solvent. In this specification, alkali-soluble polyimide means a polyimide that dissolves at 23°C in 100 g of a 2.38% by mass aqueous solution of tetramethylammonium, and from the viewpoint of pattern formation, it is preferable that the polyimide dissolves at a rate of 0.5 g or more, and more preferably at a rate of 1.0 g or more. The upper limit of the above dissolution amount is not particularly limited, but it is preferably 100 g or less. From the viewpoint of film strength and insulating properties of the resulting organic film, the polyimide is preferably a polyimide having multiple imide structures in its main chain.

[0143] -Fluorine Atoms- From the viewpoint of the film strength of the resulting organic film, it is also preferable for the polyimide to have fluorine atoms. Fluorine atoms are, for example, in the R of the repeating unit represented by formula (4) described later. １３２ , or R in the repeating unit represented by formula (4) described later. １３１ Preferably, it is included in the repeating unit R represented by formula (4) described later. １３２ , or R in the repeating unit represented by formula (4) described later. １３１ It is more preferable that it be included as an alkyl fluoride. The amount of fluorine atoms relative to the total mass of the polyimide is preferably 5% by mass or more, and more preferably 20% by mass or less.

[0144] -Silicon atoms- From the viewpoint of the film strength of the resulting organic film, it is also preferable for the polyimide to have silicon atoms. For example, silicon atoms are R in the repeating unit represented by formula (4) described later. １３１ Preferably, it is included in the repeating unit R represented by formula (4) described later. １３１ It is more preferable that the silicon atoms or the organically modified (poly)siloxane structure described later be included. The silicon atoms or the organically modified (poly)siloxane structure may be included in the side chains of the polyimide, but it is preferable that they be included in the main chain of the polyimide. The amount of silicon atoms relative to the total mass of the polyimide is preferably 1% by mass or more, and preferably 20% by mass or less.

[0145] - Ethylene-unsaturated bond - From the viewpoint of the film strength of the resulting organic film, it is preferable that the polyimide has an ethylenically unsaturated bond. The polyimide may have an ethylenically unsaturated bond at the end of the main chain or in the side chains, but it is preferable that it has one in the side chains. It is preferable that the above ethylenically unsaturated bond has radical polymerizability. The ethylenically unsaturated bond is R in the repeating unit represented by formula (4) described later. １３２ or R １３１ Preferably, it is included in R １３２ or R １３１ It is more preferable that it be included as a group having an ethylenically unsaturated bond. Among these, the ethylenically unsaturated bond is R in the repeating unit represented by formula (4) described later. １３１ Preferably, it is included in R １３１ It is more preferable that the group be included as a group having an ethylenically unsaturated bond. Examples of groups having an ethylenically unsaturated bond include vinyl groups, allyl groups, vinylphenyl groups, and other groups having a vinyl group that is directly bonded to an aromatic ring and may be substituted, (meth)acrylamide groups, (meth)acryloyloxy groups, the group represented by the above formula (RP-1), and the group represented by the following formula (IV).

[0146]

[0147] In formula (IV), R ２０represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, with a hydrogen atom or a methyl group being preferred.

[0148] In formula (IV), R ２１ This is an alkylene group having 2 to 12 carbon atoms, -O-CH ２ CH(OH)CH ２ The characters represent -, -C(=O)O-, -O(C=O)NH-, a (poly)alkylene oxy group having 2 to 30 carbon atoms (the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and particularly preferably 2 or 3; the repeating number of the alkylene oxy group preferably has 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3), or a group formed by combining two or more of these. The alkylene group having 2 to 12 carbon atoms may be linear, branched, cyclic, or 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.

[0149] Among these, R ２１ It is preferable that the group is represented by any of the following formulas (R1) to (R3), and more preferably by the group represented by formula (R1).

[0150]

[0151] In formulas (R1) to (R3), L represents a single bond, or an alkylene group having 2 to 12 carbon atoms, a (poly)alkylene oxy group having 2 to 30 carbon atoms, or a group having two or more of these bonded together; X represents an oxygen atom or a sulfur atom; * represents a bonding site with another structure; and ● represents R in formula (IV). ２１ This represents the bonding site with the oxygen atom to which it is bonded. In formulas (R1) to (R3), a preferred embodiment of L is an alkylene group having 2 to 12 carbon atoms, or a (poly)alkylene oxy group having 2 to 30 carbon atoms, as shown in formula (IV) R ２１The preferred embodiment is the same as that of an alkylene group having 2 to 12 carbon atoms, or a (poly)alkylene oxy group having 2 to 30 carbon atoms. In formula (R1), X is preferably an oxygen atom. In formulas (R1) to (R3), * is the same as * in formula (IV), and the preferred embodiment is the same. The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl 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 carboxyl group with a compound having a hydroxyl 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 hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenically unsaturated bond (e.g., glycidyl methacrylate).

[0152] In formula (IV), * represents a binding site with another structure, and is preferably a binding site with the polyimide main chain.

[0153] The amount of ethylenically unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.0005 to 0.05 mol / g.

[0154] -Polymerizable groups other than those having ethylenically unsaturated bonds- Polyimide may have polymerizable groups other than those having ethylenically unsaturated bonds. Examples of polymerizable groups other than those having ethylenically unsaturated bonds include epoxy groups, cyclic ether groups such as oxetanyl groups, alkoxymethyl groups such as methoxymethyl groups, and methylol groups. Polymerizable groups other than those having ethylenically unsaturated bonds include, for example, R in the repeating unit represented by formula (4) described later. １３１ It is preferable that it be included in the following. The amount of polymerizable groups other than those having ethylenically unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0155] -Polarity-Converting Group- Polyimides may have polarity-converting groups such as acid-degradable groups. Acid-degradable groups in polyimides are R in formula (2) above. １１３ and R １１４ The acid-degradable group is the same as described above, and the preferred embodiment is also the same. The polarity-converting group is, for example, R in the repeating unit represented by formula (4) described later. １３１ , R １３２ It is found at the ends of polyimides, etc.

[0156] - Acid Value - When polyimide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of polyimide is preferably 30 mg KOH / g or more, more preferably 50 mg KOH / g or more, and even more preferably 70 mg KOH / g or more. The above acid value is preferably 500 mg KOH / g or less, more preferably 400 mg KOH / g or less, and even more preferably 200 mg KOH / g or less. When polyimide is subjected to development using a developer mainly composed of an organic solvent (for example, "solvent development"), the acid value of polyimide is preferably 1 to 35 mg KOH / g, more preferably 2 to 30 mg KOH / g, and even more preferably 5 to 20 mg KOH / g. The above 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 groups contained in polyimides are preferably acid groups with a pKa of 0 to 10, and more preferably acid groups with a pKa of 3 to 8. pKa is the negative common logarithm of the equilibrium constant Ka, considering the dissociation reaction in which hydrogen ions are released from an acid. In this specification, unless otherwise specified, pKa is the value calculated by ACD / ChemSketch®. The value of pKa may also be referenced from the value published in the "Revised 5th Edition Chemical Handbook Basic Edition" edited by the Chemical Society of Japan. When the acid group is a polyvalent acid such as phosphoric acid, the above pKa is the first dissociation constant. As such acid groups, polyimides preferably contain at least one selected from the group consisting of carboxyl groups and phenolic hydroxyl groups, and more preferably contain phenolic hydroxyl groups.

[0157] -Phenolenic Hydroxyl Group- From the viewpoint of ensuring an appropriate development rate with an alkaline developer, it is preferable that the polyimide has a phenolic hydroxyl group. The polyimide may have a phenolic hydroxyl group at the end of the main chain or in the side chain. The phenolic hydroxyl group is, for example, R in the repeating unit represented by formula (4) described later. １３２ or R １３１ It is preferable that it be included in [the polyimide]. The amount of phenolic hydroxyl groups relative to the total mass of polyimide is preferably 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.

[0158] 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 repeating units represented by the following formula (4).

[0159]

[0160] In formula (4), R １３１ represents a divalent organic group, R １３２ R represents a tetravalent organic group. If it has a polymerizable group, the polymerizable group is R １３１ and R １３２ It may be located at least one of the two, or it may be located at the end of the polyimide as shown in formula (4-1) or formula (4-2) below. Formula (4-1)

[0161]

[0162] In formula (4-1), R １３３ This is a polymerizable group, and the other groups are equivalent to those in formula (4). Formula (4-2)

[0163]

[0164] 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 is equivalent to formula (4).

[0165] Examples of polymerizable groups include groups containing the ethylenically unsaturated bond described above, or crosslinkable groups other than those having the ethylenically unsaturated bond described above. １３１ R represents a divalent organic group. As an example of a divalent organic group, R in formula (2) is １１１ Similar examples are given, and the preferred range is also similar. Among these, preferred divalent organic groups include groups that include structures obtained by removing two or more hydrogen atoms from any of the above-mentioned structures represented by formulas (V-1) to (V-10), and more preferably structures that are obtained by removing two or more hydrogen atoms from any of the above-mentioned structures represented by formulas (V-1) to (V-10), and that have a group represented by formula (RP-1) as a substituent in these structures. １３１ Examples include diamine residues remaining after the removal of the amino group of a diamine. Examples of diamines include aliphatic, cyclic aliphatic, or aromatic diamines. A specific example is R in formula (2) of the polyimide precursor. １１１ Examples include:

[0166] R １３１ It is preferable that the diamine residue has at least two alkylene glycol units in its main chain, as this more effectively suppresses warping during firing. More preferably, it is a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in a single molecule, and even more preferably, it is the above-mentioned diamine residue that does not contain an aromatic ring.

[0167] Examples of diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in a single molecule include, but are not limited to, Jeffermin® KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (all trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.

[0168] R１３２ R represents a tetravalent organic group. As an example of a tetravalent organic group, R in formula (2) is １１５ Similar examples are given, and the preferred range is also similar. For example, R １１５ The four bonders of the tetravalent organic group, as exemplified, bond with the four -C(=O)- parts in formula (4) to form a fused ring.

[0169] R １３２ Examples include tetracarboxylic acid residues remaining after the removal of the anhydride group from tetracarboxylic dianhydride. A specific example is R in formula (2) of the polyimide precursor. １１５ Examples include: From the standpoint of the strength of the organic film, R １３２ It is preferable that it is an aromatic diamine residue having 1 to 4 aromatic rings.

[0170] R １３１ and R １３２ It is also preferable that at least one of them has an OH group. More specifically, R １３１ As examples, 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) are listed as preferred examples, R １３２ As such, (DAA-1) to (DAA-5) above can be cited as more preferred examples.

[0171] It is also preferable that the polyimide contains fluorine atoms in its structure. The fluorine atom content in the polyimide is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0172] To improve adhesion to the substrate, the polyimide may be copolymerized with aliphatic groups having a siloxane structure. Specifically, examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0173] To improve the storage stability of the resin composition, it is preferable that the main chain ends of the polyimide are encapsulated with end-capturing agents such as monoamines, acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds. Of these, the use of monoamines is more preferable, 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 Examples include -5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may be used, and multiple different end groups may be introduced by reacting multiple end encapsulants.

[0174] The sentence "-Imidization rate (ring closure rate)- The imidization rate (also called the "ring closure rate") of 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 above imidization rate is not particularly limited and may be 100% or less. The above imidization rate is measured by, for example, the method described below." should be deleted and replaced with "The imidization rate refers to the ratio of the imide ring structure to the sum of the amic acid structure, amic acid ester structure, and imide ring structure."

[0175] Polyimide is a material in which all repeating units are R １３１ and R １３２ The combination of R may include the repeating unit represented by the above formula (4), which is the same. １３１ and R １３２ The polyimide may contain repeating units represented by formula (4) above, which include two or more different combinations of elements. In addition to the repeating units represented by formula (4) above, the polyimide may also contain other types of repeating units. Examples of other types of repeating units include the repeating units represented by formula (2) above.

[0176] Polyimides can be synthesized by obtaining polyimide precursors using methods such as: reacting tetracarboxylic dianhydride with a diamine (partially substituted with a monoamine end-captive) at low temperatures; reacting tetracarboxylic dianhydride (partially substituted with an acid anhydride, monoacid chloride compound, or monoactive ester compound end-captive) with a diamine at low temperatures; obtaining a diester from tetracarboxylic dianhydride with an alcohol, and then reacting it with a diamine (partially substituted with a monoamine end-captive) in the presence of a condensing agent; obtaining a diester from tetracarboxylic dianhydride with an alcohol, and then acid-chloridizing the remaining dicarboxylic acid and reacting it with a diamine (partially substituted with a monoamine end-captive); completely imidizing the precursor using a known imidation reaction method; stopping the imidation reaction midway to introduce a partial imide structure; or introducing a partial imide structure by blending a fully imidized polymer with its polyimide precursor. Other known methods for synthesizing polyimides can also be applied.

[0177] 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 flexural resistance of the film after curing can be improved. In order to obtain an organic film with excellent mechanical properties (e.g., elongation at break), 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 degree of dispersion of the molecular weight of the above polyimide is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no specific upper limit for the degree of dispersion of the molecular weight of polyimide, but for example, it is 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 polyimide as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one type of polyimide are within the above range. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated when the multiple types of polyimide are treated as a single resin are each within the above range.

[0178] [Polybenzoxazole precursors] Examples of polybenzoxazole precursors include the compounds described in paragraphs 0073-0095 of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0179] [Polybenzoxazoles] Examples of polybenzoxazoles include the compounds described in paragraphs 0096-0103 of International Publication No. 2022 / 145355. The foregoing description is incorporated herein by reference.

[0180] [Polyamide-imide precursors] Examples of polyamide-imide precursors include the compounds described in paragraphs 0104-0119 of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0181] Furthermore, if the specific resin is a polyamide-imide precursor, then R in formula (2) １１５The structure is represented by the following formula (X-2), or X in the structure represented by formula (X-2). ２ A hydrogen atom or L of the group represented by ３ The hydrogen atom of the group represented by is also substituted by the group represented by formula (RP-1). In the above embodiment, A in formula (2) １ A ２ , R １１１ , R １１３ and R １１４ The preferred embodiment is as described above.

[0182]

[0183] In formula (X-2), X ２ Each of these independently represents a trivalent linking group, L ３ represents a divalent linking group, and * represents a bonding site with other structures.

[0184] In formula (X-2), X ２ Examples include linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups, or groups formed by linking two or more of these by single bonds or linking groups. Preferably, these are linear aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, aromatic groups having 6 to 20 carbon atoms, or groups formed by combining two or more of these by single bonds or linking groups. More preferably, these are aromatic groups having 6 to 20 carbon atoms, or groups formed by combining two or more aromatic groups having 6 to 20 carbon atoms by single bonds or linking groups. Examples of the linking groups include -O-, -S-, -C(=O)-, and -S(=O). ２-, alkylene groups, halogenated alkylene groups, arylene groups, or linking groups comprising two or more of these are preferred, and -O-, -S-, alkylene groups, halogenated alkylene groups, arylene groups, or linking groups comprising two or more of these are more preferred. As for the alkylene group, alkylene groups having 1 to 20 carbon atoms are preferred, alkylene groups having 1 to 10 carbon atoms are more preferred, and alkylene groups having 1 to 4 carbon atoms are even more preferred. As for the halogenated alkylene group, halogenated alkylene groups having 1 to 20 carbon atoms are preferred, halogenated alkylene groups having 1 to 10 carbon atoms are more preferred, and halogenated alkylene groups having 1 to 4 carbon atoms are even more preferred. In addition, examples of halogen atoms in the halogenated alkylene group include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being preferred. The above halogenated alkylene group may have hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferable that all of the hydrogen atoms are substituted with halogen atoms. Examples of preferred halogenated alkylene groups include the (ditrifluoromethyl)methylene group. The above 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.

[0185] Also, X ２ It is preferable that the product is derived from a tricarboxylic acid compound in which at least one carboxyl group is halogenated. Chlorination is preferred as the halogenation. In the present invention, a compound having three carboxyl groups is referred to as a tricarboxylic acid compound. Two of the three carboxyl groups of the tricarboxylic acid compound may be acid anhydrides. Examples of tricarboxylic acid compounds that may be halogenated include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds. Only one of these tricarboxylic acid compounds may be used, or two or more may be used.

[0186] X ２ It is preferable that the structure does not contain an imide structure. Also, X ２It is preferable that the structure does not contain urethane bonds, urea bonds, and amide bonds. Furthermore, X ２ It is preferable that the structure does not contain ester bonds. Among these, X ２ It is preferable that the material does not contain imide structures, urethane bonds, urea bonds, and amide bonds, and more preferably that it does not contain imide structures, urethane bonds, urea bonds, amide bonds, and ester bonds.

[0187] Specifically, preferred tricarboxylic acid compounds include 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 formed by combining two or more of these groups by single bonds or linking groups. More preferred tricarboxylic acid compounds include an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms by single bonds or linking groups.

[0188] Furthermore, specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalentricarboxylic acid, and phthalic acid (or phthalic anhydride) and benzoic acid with a single bond, -O-, -CH ２ -, -C(CH ３ ) ２ -, -C (CF ３ ) ２ -, -SO ２ - Or, compounds linked by a phenylene group, etc. These compounds may be compounds in which two carboxyl groups have been converted to anhydrides (e.g., trimellitic anhydride), or compounds in which at least one carboxyl group has been halogenated (e.g., trimellitic anhydride chloride).

[0189] In formula (X-2), L ３Examples of these groups include linear or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, or groups formed by linking two or more of these groups by single bonds or linking groups. Preferably, these groups include linear aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, aromatic groups having 6 to 20 carbon atoms, or groups formed by combining two or more of these groups by single bonds or linking groups. More preferably, these groups include aromatic groups having 6 to 20 carbon atoms, or groups formed by combining two or more aromatic groups having 6 to 20 carbon atoms by single bonds or linking groups. Examples of the linking groups include -O-, -S-, -C(=O)-, and -S(=O). ２ -, alkylene groups, halogenated alkylene groups, arylene groups, or linking groups comprising two or more of these are preferred, and -O-, -S-, alkylene groups, halogenated alkylene groups, arylene groups, or linking groups comprising two or more of these are more preferred. As for the alkylene group, alkylene groups having 1 to 20 carbon atoms are preferred, alkylene groups having 1 to 10 carbon atoms are more preferred, and alkylene groups having 1 to 4 carbon atoms are even more preferred. As for the halogenated alkylene group, halogenated alkylene groups having 1 to 20 carbon atoms are preferred, halogenated alkylene groups having 1 to 10 carbon atoms are more preferred, and halogenated alkylene groups having 1 to 4 carbon atoms are even more preferred. In addition, examples of halogen atoms in the halogenated alkylene group include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being preferred. The above halogenated alkylene group may have hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferable that all of the hydrogen atoms are substituted with halogen atoms. Examples of preferred halogenated alkylene groups include the (ditrifluoromethyl)methylene group. The above 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.

[0190] [Polyamideimides] Examples of polyamideimides include the compounds described in paragraphs 0120-0133 of International Publication No. 2022 / 145355. The foregoing description is incorporated herein by reference.

[0191] [Method for Producing Polyimide Precursor, etc.] Polyimide and the like are produced, for example, by the method described in paragraphs 0134 to 0136 of International Publication No. 2022 / 145355. The above description is incorporated herein. Further, synthesis may be carried out by referring to other known methods.

[0192] [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, still 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. Also, 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, still 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 kind of the specific resin or may contain two or more kinds thereof. When two or more kinds are contained, the total amount is preferably within the above range.

[0193] 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 the specific resin, but it is preferable to contain two or more kinds of the specific resin. When the resin composition of the present invention contains two or more kinds of the specific resin, for example, it is preferably a polyimide precursor and contains two or more kinds of polyimide precursors having different structures derived from dianhydrides (R in the above formula (2)). １１５

[0194] <Other Resins> The resin composition of the present invention may contain the specified resin described above and other resins different from the specified resin (hereinafter also simply referred to as "other resins"). 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, polyester resins, etc. For example, by further adding (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, in place of the polymerizable compound described later, or in addition to the polymerizable compound described later, a resin with a high polymerizability value and a weight-average molecular weight of 20,000 or less (for example, the molar amount of polymerizable groups per 1 g of resin is 1 × 10) may be used. －３ By adding (meth)acrylic resin (in a quantity of mol / g or more) to the resin composition, the coatability of the resin composition, the solvent resistance of the pattern (cured product), and other properties can be improved.

[0195] 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, still more preferably 1% by mass or more, even more preferably 2% by mass or more, still 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, still more preferably 70% by mass or less, even more preferably 60% by mass or less, still more preferably 50% by mass or less, based on the total solid content of the resin composition. As a preferred embodiment of the resin composition of the present invention, an embodiment in which the content of the other resin is a low content can also be adopted. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, even more preferably 5% by mass or less, and still more preferably 1% by mass or less, based on the total solid content of the resin composition. The lower limit of the above content is not particularly limited, and it may be 0% by mass or more. The resin composition of the present invention may contain only one kind of other resin or two or more kinds of other resins. When two or more kinds are contained, the total amount is preferably within the above range.

[0196] <Compound A> The resin composition of the present invention contains a compound A represented by the following formula (1).

[0197]

[0198] In formula (1), R １１ ~R １５ each independently represents a hydrogen atom or a substituent. At least two of R １１ ~R １５ may be bonded to form a ring. X １１ represents a group represented by the following formula (G-1) or (G-2).

[0199]

[0200] In formulas (G-1) and (G-2), * represents a bonding site. In formula (G-2), R Ａ１１represents a hydrogen atom or substituent.

[0201] [X １１ ] Because compound A is strongly bonded to the metal surface at the heteroatom portion of its heterocycle, X in formula (1) １１ The group represented by formula (G-2) is (-N(R Ａ１１ When representing )-), R Ａ１１ R is preferably a substituent that is decomposed by heat or light and converted into a hydrogen atom, or represents a hydrogen atom, and more preferably represents a hydrogen atom. Ａ１１ When R represents a substituent that is decomposed by heat or light and converted into a hydrogen atom, the H of -NH- and the metal atoms on the surface of the metal layer exchange to form covalent or ionic bonds, effectively suppressing the generation of voids and metal oxides between the hardened product and the metal layer. Examples of substituents that are decomposed by heat or light and converted into a hydrogen atom include substituents bonded by a carbamate structure and substituents bonded by a carbamoyl structure. Specifically, examples include t-butoxycarbonyl groups and N,N-dimethylaminocarbonyl groups. Ａ１１ When represents a substituent, it may be a hydrocarbon group other than a substituent that is decomposed by the above heat or light and converted to a hydrogen atom. The above hydrocarbon group may be an alkyl group, and is preferably a methyl group. １１ It is preferable that represents the group (-O-) represented by formula (G-1).

[0202] A certain compound X is R Ａ１１ It has R Ａ１１ Whether or not the R of compound X is converted into hydrogen atoms by the action of heat can be determined by the following method. Ａ１１ Let compound Y be the compound in which the atoms are converted to hydrogen atoms. Compound X is prepared as a 0.1 mol / L solution or suspension and heated at 1 atmosphere and 50-230°C for 10 minutes each １ If compound Y is quantified by methods such as 1H-NMR, and compound Y is generated at a molar ratio of 0.01% or more relative to compound X before heating within 24 hours, then the R of compound X is determined to be present. Ａ１１ It is determined that this substituent is converted to a hydrogen atom by the action of heat.

[0203] A certain compound X is R Ａ１１ It has R Ａ１１ Whether or not the R of compound X is converted into a hydrogen atom by the action of light can be determined by the following method. Ａ１１ Let compound Y be the compound in which the atoms are converted to hydrogen atoms. Compound X is prepared as a 0.1 mol / L solution or suspension and exposed to light with a wavelength of 190 to 800 nm at an illuminance of 0.1 to 25 W / cm² under conditions of -100 to 50°C at 1 atm. ２ Under these conditions, irradiate every 10 minutes １ If compound Y is quantified by methods such as H-NMR, and compound Y is generated at a molar ratio of 0.01% or more relative to compound X before exposure within 24 hours, then the R of compound X is determined to be present. Ａ１１ It is determined that this is a substituent that is converted to a hydrogen atom by the action of light.

[0204] [R １１ ~R １５ ] R in equation (1) １１ ~R １５ Each of these independently represents a hydrogen atom or a substituent. When compound A is adsorbed on a metal surface at the heteroatom portion of its heterocycle, it is desirable that there are no sterically hindering substituents in adjacent positions. Therefore, R in formula (1) １１ ~R １４Preferably, each of these is independently a hydrogen atom, a C1-C12 alkyl group, a C2-C12 alkenyl group, a C2-C12 alkynyl group, a C6-C10 aryl group, a C5-C10 heteroaryl group, a halide group (halogen atom), a hydroxyl group, an alkoxy group, a substituent bonded by an ester structure, a substituent bonded by a carbamate structure, a substituent bonded by a carbamoyl structure, a C0-C8 amino group, a nitro group, a nitroso group, a substituent bonded by an amide structure, a cyano group, a thiol group, a substituent bonded by a sulfide structure, a substituent bonded by a sulfoxide structure, a substituent bonded by a sulfonyl structure, a substituent bonded by a carbonyl structure, a substituent bonded by an imine structure, or a substituent bonded by a thiocarbonyl structure, and preferably a hydrogen atom, a C1-C4 alkyl group It is more preferable that the substituent is an alkyl group, a C2-C4 alkenyl group, a C2-C4 alkynyl group, a C6-C8 aryl group, a C5-C7 heteroaryl group, a halide group, a hydroxyl group, an alkoxy group, a substituent bonded by an ester structure, a substituent bonded by a carbamate structure, a substituent bonded by a carbamoyl structure, an amino group having C0-C4, a substituent bonded by an amide structure, a substituent bonded by a carbonyl structure, or a substituent bonded by an imine structure. It is even more preferable that the substituent is a hydrogen atom, a methyl group, an ethyl group, an ethynyl group, a phenyl group, a hydroxyl group, a methoxy group, an ethoxy group, or an amino group without substituents. It is particularly preferable that the substituent is a hydrogen atom, a methyl group, an ethyl group, an ethynyl group, a phenyl group, a hydroxyl group, a methoxy group, or an ethoxy group, and most preferably a hydrogen atom.

[0205] Furthermore, because compound A does not inhibit the radical curing of resin P, R in formula (1) １１ ~R １４The substituent is preferably a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a halide group, an alkoxy group, a substituent bonded by an ester structure, a substituent bonded by a carbamate structure, a substituent bonded by a carbamoyl structure, a cyano group, a sulfoxide group, a sulfonyl group, a substituent bonded by a carbonyl structure, or a substituent bonded by an imine structure; more preferably a hydrogen atom, an alkyl group, an alkoxy group, or a substituent bonded by a carbonyl structure; and most preferably a hydrogen atom.

[0206] R in equation (1) １１ and R １４ It is preferable that R in formula (1) represents a hydrogen atom. １２ and R １３ It is preferable that at least one of them represents a hydrogen atom. １１ and R １４ represents a hydrogen atom, and R １２ and R １３ It is particularly preferable that at least one of them represents a hydrogen atom.

[0207] Because compound A is strongly bonded to the metal surface at the heteroatom portion of its heterocycle, R １５ It is preferable, and more preferable, that this represents a substituent that is decomposed by heat or light and converted into a hydrogen atom, or a hydrogen atom.

[0208] R in equation (1) １１ ~R １５ At least two of them may be joined together to form a ring. １１ ~R １５ When two adjacent elements of these elements combine to form a ring, the resulting ring structure may be either an aliphatic ring or an aromatic ring. Furthermore, the resulting ring structure may include an acetal structure. In formula (1), R １１ ~R １５ It is preferable that at least two of them do not combine.

[0209] [Molecular Weight] For the reasons that compound A can easily move within the resin composition or the cured product obtained by curing the resin composition, readily bond with the metal surface, and effectively suppress the generation of voids and metal oxides between the cured product and the metal layer, the molecular weight of compound A is preferably 2000 or less, more preferably 750 or less, even more preferably 300 or less, and most preferably 145 or less. Furthermore, the lower limit of the molecular weight of compound A is preferably 100 or more, and more preferably 130 or more.

[0210] [pKa] The pKa of compound A is preferably 4 or higher, more preferably 6 or higher, and even more preferably 8 or higher. The pKa of the conjugate acid of compound A is preferably 10 or lower, more preferably 8 or lower, and even more preferably 6 or lower. In this specification, unless otherwise specified, pKa values ​​are calculated using ACD / ChemSketch®.

[0211] [Synthesis Method] Compound A can be synthesized, for example, by the method described in the examples below. It may also be synthesized using other known synthesis methods, and the synthesis method is not particularly limited.

[0212] [Specific Examples] Specific examples of compound A are not particularly limited, but include, for example, the compounds described in the examples described later.

[0213] [Content] The content of compound A is not particularly limited, but is preferably 0.005 to 30% by mass relative to the total solid content of the resin composition of the present invention. The lower limit of the content of compound A is more preferably 0.01% by mass or more, even more preferably 0.02% by mass or more, particularly preferably 0.05% by mass or more, and most preferably 0.1% by mass or more. The upper limit of the content of compound A is more preferably 15% by mass or less, even more preferably 5% by mass or less, and particularly preferably 1% by mass or less. Furthermore, when the content of the specific resin is 100 parts by mass, the content of compound A is not particularly limited, but is preferably 0.005 to 30 parts by mass, more preferably 0.01 to 15 parts by mass, even more preferably 0.02 to 5 parts by mass, and particularly preferably 0.1 to 3 parts by mass. Compound A may be used alone, or two or more may be used in combination. When two or more are used in combination, it is preferable that their total amount is within the above range.

[0214] The resin composition of the present invention preferably satisfies at least one of the following conditions (i) and (ii): (i) The resin P has radical polymerizable groups. (ii) The resin composition contains, in addition to the resin P and compound A, a compound having radical polymerizable groups.

[0215] <Polymerizable Compounds> The resin composition of the present invention preferably contains polymerizable compounds. Examples of polymerizable compounds include compounds having radical polymerizable groups (radical crosslinking agents) or other crosslinking agents.

[0216] [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 above-mentioned groups containing an ethylenically unsaturated bond include vinyl group, allyl group, vinylphenyl group, (meth)acryloyl group, maleimide group, and (meth)acrylamide group. Among these, (meth)acryloyl group, (meth)acrylamide group, and vinylphenyl group are preferred, and from the viewpoint of reactivity, the (meth)acryloyl group is more preferred.

[0217] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, and more preferably a compound having two or more. The radical crosslinking agent may also have three or more ethylenically unsaturated bonds. As for the compound having two or more ethylenically unsaturated bonds, it is preferable that it has 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. From the viewpoint of the film strength of the resulting pattern (cured product), it is also preferable that the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds.

[0218] 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.

[0219] Specific examples of radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably esters of unsaturated carboxylic acids with polyhydric alcohol compounds, and amides of unsaturated carboxylic acids with polyhydric amine compounds. Addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, or sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxys, and dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids are also suitably used. Addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having leaving substituents such as halogeno groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also suitable. 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. For specific examples, refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0220] 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 International Publication No. 2021 / 112189. This information is incorporated herein by reference.

[0221] Other preferred radical crosslinking agents include the radical polymerizable compounds described in paragraphs 0204-0208 of International Publication No. 2021 / 112189. This information is incorporated herein by reference.

[0222] Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), and structures in which the (meth)acryloyl groups of these are linked via ethylene glycol residues or propylene glycol residues. These oligomer types can also be used.

[0223] Commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate having four ethylene oxy chains; SR-209, 231, and 239, difunctional methacrylates having four ethylene oxy chains (all manufactured by Sartomer Co., Ltd.); DPCA-60, a hexafunctional acrylate having six pentylene oxy chains; and TPA-330, a trifunctional acrylate having three isobutylene oxy chains (both manufactured by Nippon Kayaku Co., Ltd.); and urethane oligomers. Examples include UAS-10, UAB-140 (both manufactured by Nippon Paper Industries), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (all manufactured by Kyoeisha Chemical Co., Ltd.), and Bremmer PME400 (manufactured by NOF Corporation).

[0224] As the radical crosslinking agent, urethane acrylates as described in Japanese Patent Publication No. Sho 48-041708, Japanese Patent Laid-Open No. Sho 51-037193, Japanese Patent Publication No. Hei 02-032293, and Japanese Patent Publication No. Hei 02-016765, and urethane compounds having an ethylene oxide-based skeleton as described in Japanese Patent Publication No. Sho 58-049860, Japanese Patent Publication No. Sho 56-017654, Japanese Patent Publication No. Sho 62-039417, and Japanese Patent Publication No. Sho 62-039418 are also suitable. As the radical crosslinking agent, compounds having an amino structure or a sulfide structure in the molecule as described in Japanese Patent Laid-Open No. Sho 63-277653, Japanese Patent Laid-Open No. Sho 63-260909, and Japanese Patent Laid-Open No. Hei 01-105238 can also be used.

[0225] The radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphoric acid 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 having an acid group by reacting an unreacted hydroxy group of the aliphatic polyhydroxy compound with an aliphatic carboxylic anhydride. Particularly preferred is a radical crosslinking agent having an acid group by reacting an unreacted hydroxy group of an aliphatic polyhydroxy compound with an aliphatic carboxylic anhydride, and the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include M-510, M-520, etc. as polybasic acid-modified acrylo oligomers manufactured by Toagosei Co., Ltd.

[0226] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH / g, and more preferably 1 to 100 mgKOH / g. If the acid value of the radical crosslinking agent is within the above range, it has excellent handling properties in production and excellent developability. Also, the polymerizability is good. The above acid value is measured in accordance with the description of JIS K 0070:1992.

[0227] As a radical crosslinking agent, a radical crosslinking agent having at least one selected from the group consisting of urea bonds and urethane bonds (hereinafter also referred to as "crosslinking agent U") is also preferred. When the resin composition contains crosslinking agent U, chemical resistance, resolution, etc. may be improved. The mechanism by which the above effects are obtained is unknown, but for example, it is thought that when curing by heating, etc., a part of the crosslinking agent U is thermally decomposed, generating amines, etc., and these amines, etc. promote the cyclization of precursors of cyclized resins such as polyimide precursors. In addition, crosslinking agent U has high compatibility with compound A having an amide structure or an ester structure, and by using crosslinking agent U in the resin composition of the present invention, it is also possible to improve the coatability of the composition. Crosslinking agent U may have only one urea bond or urethane bond, may have one or more urea bonds and one or more urethane bonds, may have two or more urea bonds without a urethane bond, or may have two or more urethane bonds without a urea bond. The total number of urea bonds and urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2. If the crosslinking agent U does not have urethane bonds, the number of urea bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2. If the crosslinking agent U does not have urea bonds, the number of urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0228] The radical polymerizable groups in the crosslinking agent U are not particularly limited, but include vinyl groups, allyl groups, (meth)acryloyl groups, (meth)acryloxy groups, (meth)acrylamide groups, vinylphenyl groups, maleimide groups, etc., with (meth)acryloxy groups, (meth)acrylamide groups, vinylphenyl groups, or maleimide groups being preferred, and (meth)acryloxy groups being more preferred. When the crosslinking agent U has two or more radical polymerizable groups, the structures of each radical polymerizable group may be the same or different. The number of radical polymerizable groups in the crosslinking agent U may be only one, or two or more, preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4. The radical polymerizability value (mass of compound per mole of radical polymerizable groups) in the crosslinking agent U is preferably 150 to 400 g / mol. From the viewpoint of chemical resistance of the cured product, the lower limit of the radical polymerization value is more preferably 200 g / mol or more, even more preferably 210 g / mol or more, even more preferably 220 g / mol or more, even more preferably 230 g / mol or more, even more preferably 240 g / mol or more, and particularly preferably 250 g / mol or more. From the viewpoint of developability, the upper limit of the radical polymerization value is more preferably 350 g / mol or less, even more preferably 330 g / mol or less, and particularly preferably 300 g / mol or less. In particular, the polymerization value of the crosslinking agent U is preferably 210 to 400 g / mol, and more preferably 220 to 400 g / mol.

[0229] The crosslinking agent U preferably has a structure represented by the following formula (U-1).

[0230]

[0231] In formula (U-1), R Ｕ１ A is a hydrogen atom or a monovalent organic group, and A is -O- or -NR Ｎ - and R Ｎ is a hydrogen atom or a monovalent organic group, Z Ｕ１ is an m-valent organic group, Z Ｕ２is an n+1 valent organic group, X is a radical polymerizable group, n is an integer greater than or equal to 1, and m is an integer greater than or equal to 1.

[0232] R Ｕ１ R is preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group, and more preferably a hydrogen atom. Ｎ The element is preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group, and more preferably a hydrogen atom. Ｕ１ These are hydrocarbon groups, -O-, -C(=O)-, -S-, -S(=O) ２ -, -NR Ｎ - or a group in which two or more of these are bonded together is preferred, and is a hydrocarbon group, or a hydrocarbon group and -O-, -C(=O)-, -S-, -S(=O) ２ -, and -NR Ｎ A group bonded with at least one group selected from the group consisting of - is more preferable. The hydrocarbon group is preferably a hydrocarbon group having 20 or fewer carbon atoms, more preferably a hydrocarbon group having 18 or fewer carbon atoms, and even more preferably a hydrocarbon group having 16 or fewer carbon atoms. Examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by the bonding of these. Ｎ Z represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom or a methyl group. Ｕ２ These are hydrocarbon groups, -O-, -C(=O)-, -S-, -S(=O) ２ -, -NR Ｎ - or a group in which two or more of these are bonded together is preferred, and is a hydrocarbon group, or a hydrocarbon group and -O-, -C(=O)-, -S-, -S(=O) ２ -, and -NR Ｎ A group bonded to at least one group selected from the group consisting of - is more preferable. The hydrocarbon group is Z Ｕ１Similar to those listed above, preferred embodiments are also listed. X is not particularly limited, but examples include vinyl group, allyl group, (meth)acryloyl group, (meth)acryloxy group, (meth)acrylamide group, vinylphenyl group, maleimide group, etc., with (meth)acryloxy group, (meth)acrylamide group, vinylphenyl group, or maleimide group being preferred, and (meth)acryloxy group being more preferred. n is preferably an integer from 1 to 10, more preferably an integer from 1 to 4, even more preferably 1 or 2, and particularly preferably 1. m is preferably an integer from 1 to 10, more preferably an integer from 1 to 4, and even more preferably 1 or 2.

[0233] The crosslinking agent U may also preferably have at least one of a hydroxyl group, an alkylene oxy group, an amide group, and a cyano group. From the viewpoint of the chemical resistance of the resulting cured film, the hydroxyl group may be an alcoholic hydroxyl group or a phenolic hydroxyl group, but it is preferable that it be an alcoholic hydroxyl group. From the viewpoint of the chemical resistance of the resulting cured film, the alkylene oxy group is preferably an alkylene oxy group having 2 to 20 carbon atoms, more preferably an alkylene oxy group having 2 to 10 carbon atoms, even more preferably an alkylene oxy group having 2 to 4 carbon atoms, even more preferably an ethylene group or a propylene group, and particularly preferably an ethylene group. The alkylene oxy group may also be included in the crosslinking agent U as a polyalkylene oxy group. In this case, the number of repeating alkylene oxy groups is preferably 2 to 10, and more preferably 2 to 6. The amide group is -C(=O)-NR Ｎ This refers to a combination represented by -. Ｎ As stated above, when the crosslinking agent U has an amide group, the crosslinking agent U is, for example, R-C(=O)-NR Ｎ - A group represented by *, or *-C(=O)-NR ＮIt can be included as a group represented by -R. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group. The crosslinking agent U may have two or more structures selected from the group consisting of a hydroxyl group, an alkylene oxy group (however, if it constitutes a polyalkylene oxy group, it may be a polyalkylene oxy group), an amide group and a cyano group in its molecule, but it is also preferable to have only one in the molecule. The above hydroxyl group, alkylene oxy group, amide group and cyano group may be located at any position of the crosslinking agent U, but from the viewpoint of chemical resistance, it is also preferable that the crosslinking agent U has at least one selected from the group consisting of the above hydroxyl group, alkylene oxy group, amide group and cyano group and at least one radical polymerizable group contained in the crosslinking agent U linked by a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-1"). In particular, when the crosslinking agent U contains only one radical polymerizable group, it is preferable that the radical polymerizable group contained in the crosslinking agent U and at least one selected from the group consisting of a hydroxyl group, an alkylene oxy group, an amide group, and a cyano group are linked by a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-2"). When the crosslinking agent U contains an alkylene oxy group (however, if it constitutes a polyalkylene oxy group, it is a polyalkylene oxy group) and has the above-mentioned linking group L2-1 or linking group L2-2, the structure on the side opposite to linking group L2-1 or linking group L2-2 of the alkylene oxy group (however, if it constitutes a polyalkylene oxy group, it is a polyalkylene oxy group) is not particularly limited, but a hydrocarbon group, a radical polymerizable group, or a group represented by a combination thereof is preferred. As the above-mentioned hydrocarbon group, a hydrocarbon group having 20 or fewer carbon atoms is preferred, a hydrocarbon group having 18 or fewer carbon atoms is more preferred, and a hydrocarbon group having 16 or fewer carbon atoms is even more preferred. Examples of the hydrocarbon groups mentioned above include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by combinations thereof. Furthermore, the preferred embodiment of the radical polymerizable group is the same as the preferred embodiment of the radical polymerizable group in the crosslinking agent U described above.When the crosslinking agent U contains an amide group and has the linking group L2-1 or L2-2, the structure on the side of the amide group opposite to linking group L2-1 or L2-2 is not particularly limited, but a hydrocarbon group, a radical polymerizable group, or a group represented by a combination thereof is preferred. As the hydrocarbon group, a hydrocarbon group having 20 or fewer carbon atoms is preferred, a hydrocarbon group having 18 or fewer carbon atoms is more preferred, and a hydrocarbon group having 16 or fewer carbon atoms is even more preferred. As the hydrocarbon group, examples include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by a combination thereof. The preferred embodiment of the radical polymerizable group is the same as the preferred embodiment of the radical polymerizable group in the crosslinking agent U described above. In addition, in the above embodiment, the carbon atom side of the amide group may be bonded to linking group L2-1 or L2-2, or the nitrogen atom side of the amide group may be bonded to linking group L2-1 or L2-2. Among these, from the viewpoint of adhesion to the substrate, chemical resistance, and suppression of Cu voids, it is preferable that the crosslinking agent U has a hydroxyl group.

[0234] The crosslinking agent U preferably contains an aromatic group from the viewpoint of compatibility with specific resins. The aromatic group preferably directly bonds with a urea bond or urethane bond contained in the crosslinking agent U. If the crosslinking agent U contains two or more urea bonds or urethane bonds, it is preferable that one of the urea bonds or urethane bonds directly bonds with the aromatic group. The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, and these may form a fused ring structure, but it is preferable that it be an aromatic hydrocarbon group. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and even more preferably a group obtained by removing two or more hydrogen atoms from a benzene ring structure. The aromatic heterocyclic group is preferably an aromatic heterocyclic group having 5 or 6 membered rings. Examples of aromatic heterocyclic groups include pyrrole, imidazole, triazole, tetrazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, and the like. These rings may be fused with other rings, such as indole and benzimidazole. Preferred heteroatoms in the aromatic heterocyclic group are nitrogen, oxygen, or sulfur atoms. The aromatic group is preferably included in a linking group that connects two or more radical polymerizable groups and contains a urea bond or a urethane bond, or in a linking group that connects at least one selected from the group consisting of the hydroxyl group, alkylene oxy group, amide group, and cyano group with at least one radical polymerizable group contained in the crosslinking agent U.

[0235] The number of atoms (chain length) between the urea bond or urethane bond and the radical polymerizable group in the crosslinking agent U is not particularly limited, but is preferably 30 or less, more preferably 2 to 20, and even more preferably 2 to 10. If the crosslinking agent U contains a total of 2 or more urea bonds or urethane bonds, or contains 2 or more radical polymerizable groups, or contains 2 or more urea bonds or urethane bonds and 2 or more radical polymerizable groups, the minimum number of atoms (chain length) between the urea bond or urethane bond and the radical polymerizable group should be within the above range. In this specification, "number of atoms (chain length) between the urea bond or urethane bond and the polymerizable group" refers to the shortest (minimum number of atoms) linking atomic chains on the path connecting two atoms or groups of atoms to be linked. For example, in the structure represented by the following formula, the number of atoms (chain length) between the urea bond and the radical polymerizable group (methacryloyloxy group) is 2.

[0236]

[0237] [Axis of Symmetry] It is also preferable that the crosslinking agent U is a compound with a structure that does not have an axis of symmetry. The absence of an axis of symmetry in the crosslinking agent U means that it does not have an axis that, when the entire compound is rotated, produces molecules identical to the original molecules, and is therefore an asymmetric compound. Furthermore, when the structural formula of the crosslinking agent U is written on paper, the absence of an axis of symmetry in the crosslinking agent U means that the structural formula of the crosslinking agent U cannot be written in a form that has an axis of symmetry. It is believed that the absence of an axis of symmetry in the crosslinking agent U suppresses aggregation of the crosslinking agents U within the composition film.

[0238] [Molecular Weight] The molecular weight of the crosslinking agent U is preferably 100 to 2,000, more preferably 150 to 1,500, and even more preferably 200 to 900.

[0239] The method for producing the crosslinking agent U is not particularly limited, but for example, it can be obtained by reacting a radical polymerizable compound with a compound having an isocyanate group with a compound having at least one of a hydroxyl group or an amino group.

[0240] Specific examples of crosslinking agent U are shown below, but crosslinking agent U is not limited to these examples.

[0241]

[0242]

[0243]

[0244] From the viewpoint of pattern resolution and film stretchability, it is preferable to use a bifunctional methacrylate or acrylate in 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, and 1,6-methyl-1,5-pentanediol diacrylate. Xanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, ethylene oxide (EO) adduct diacrylate of bisphenol A, ethylene oxide (EO) adduct dimethacrylate of bisphenol A, propylene oxide (PO) adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid EO-modified dimethacrylate, and other bifunctional acrylates and bifunctional methacrylates having urethane bonds can be used. Two or more of these can be mixed and used as needed. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate in which the formula weight of the polyethylene glycol chain is about 200. From the viewpoint of suppressing warping of the pattern (cured product), a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent in the resin composition of the present invention.Preferably used as 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. To suppress volatilization before exposure, compounds with a boiling point of 100°C or higher under normal pressure are also preferred as monofunctional radical crosslinking agents. Other examples of bifunctional or more functional radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0245] If a radical crosslinking agent is included, the content of the radical crosslinking agent is preferably more than 0% by mass and 60% by mass or less, relative to 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.

[0246] A single radical crosslinking agent may be used alone, or two or more may be used in combination. When two or more agents are used in combination, it is preferable that their total amount be within the above range.

[0247] [Other Crosslinking Agents] The resin composition of the present invention may also preferably contain other crosslinking agents different from the radical crosslinking agents described above. Other crosslinking agents refer to crosslinking agents other than the radical crosslinking agents described above, and are preferably compounds having multiple groups in their molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products upon exposure to a photoacid generator or a photobase generator, and are preferably compounds having multiple groups in their molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products by the action of an acid or a base. Examples of other crosslinking agents include the compounds described in paragraphs 0179 to 0207 of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0248] The content of other crosslinking agents 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. The other crosslinking agents may be present as one type or as two or more types. If two or more other crosslinking agents are present, it is preferable that their total amount is within the above range.

[0249] [Polymerization Initiator] The resin composition of the present invention preferably contains a polymerization initiator. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable to include a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular restrictions on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible region is preferred. Alternatively, it may be an activator that acts with a photoexcited sensitizer to generate active radicals.

[0250] The photoradical polymerization initiator is present in an amount of at least about 50 L / mol with a wavelength in the range of about 240 to 800 nm (preferably 330 to 500 nm). －１ ・cm －１It is preferable that the compound contains at least one compound having a molar extinction coefficient. The molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure it using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0251] Any known compound can be used as a 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 oxides, oxime compounds such as hexaarylbiimidazole and 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, organoboron compounds, and iron arene complexes. For further details, please refer to paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015 / 199219, which are incorporated herein by reference. Furthermore, examples include paragraphs 0065 to 0111 of Japanese Patent Publication No. 2014-130173, the compounds described in Japanese Patent No. 6301489, the peroxide-based photopolymerization initiators described in MATERIAL STAGE 37-60p, vol. 19, No. 3, 2019, the photopolymerization initiators described in International Publication No. 2018 / 221177, the photopolymerization initiators described in International Publication No. 2018 / 110179, the photopolymerization initiators described in Japanese Patent Publication No. 2019-043864, the photopolymerization initiators described in Japanese Patent Publication No. 2019-044030, and the peroxide-based initiators described in Japanese Patent Publication No. 2019-167313, the contents of which are incorporated herein by reference.

[0252] Examples of ketone compounds include the compounds described in paragraph 0087 of Japanese Patent Publication No. 2015-087611, the contents of which are incorporated herein by reference. Among commercially available products, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

[0253] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used as photoradical polymerization initiators. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Publication No. 10-291969 and an acylphosphine oxide-based initiator described in Japanese Patent Publication No. 4225898 can be used, and this is incorporated herein by reference.

[0254] As α-hydroxyketone initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, 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) can be used.

[0255] As α-aminoketone initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.

[0256] As aminoacetophenone initiators, acylphosphine oxide initiators, and metallocene compounds, for example, compounds described in paragraphs 0161 to 0163 of International Publication No. 2021 / 112189 can also be suitably used. This is incorporated herein by reference.

[0257] More preferably, oxime compounds are used as photoradical polymerization initiators. Using oxime compounds makes it possible to more effectively improve the exposure latitude. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.

[0258] Specific examples of oxime compounds include the compounds described in Japanese Patent Publication No. 2001-233842, Japanese Patent Publication No. 2000-080068, Japanese Patent Publication No. 2006-342166, the compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), the compounds described in J. C. S. Perkin II (1979, pp. 156-162), and Journal of Photopolymer Science and Examples include compounds described in Technology (1995, pp. 202-232), compounds described in Japanese Patent Publication No. 2000-066385, compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Publication No. 2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, compounds described in Japanese Patent Publication No. 2017-198865, compounds described in paragraphs 0025-0038 of International Publication No. 2017 / 164127, compounds described in International Publication No. 2013 / 167515, and others, the contents of which are incorporated herein by reference.

[0259] Preferred oxime compounds include, for example, compounds with the following structures, as well as 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-phenylpropane-1-one, 2-(benzoyloxy(imino))-1-phenylpropane-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropane-1-one. In resin compositions, it is particularly preferable to use oxime compounds as photoradical polymerization initiators. Oxime compounds used as photoradical polymerization initiators have a >C=N-O-C(=O)- linking group in their molecule.

[0260]

[0261] Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (all manufactured by BASF), ADEKA optomer N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in Japanese Patent Publication No. 2012-014052), TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA Arclus NCI-730, NCI-831, and ADEKA Arclus NCI-930 (manufactured by ADEKA Corporation), DFI-091 (manufactured by Daito Chemix Co., Ltd.), and SpeedCure PDO (SARTOMER Examples include those manufactured by ARKEMA. Additionally, oxime compounds with the following structures can also be used.

[0262]

[0263] As photoradical polymerization initiators, for example, oxime compounds having a fluorene ring as described in paragraphs 0169-0171 of International Publication No. 2021 / 112189, oxime compounds having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring, and oxime compounds having a fluorine atom can be used. Also, oxime compounds having a nitro group as described in paragraphs 0208-0210 of International Publication No. 2021 / 020359, oxime compounds having a benzofuran skeleton, and oxime compounds in which a substituent having a hydroxyl group is attached to the carbazole skeleton can be used. These contents are incorporated herein by reference.

[0264] Among these, the photopolymerization initiator preferably contains a compound represented by the following formula (P-1).

[0265]

[0266] In addition, compounds described in paragraphs 0113 to 0117 of Japanese Patent Publication No. 2023-058585 may be used as photopolymerization initiators. This description is incorporated into the present specification.

[0267] If the resin composition contains a photopolymerization initiator, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass, based on the total solid content of the resin composition. The resin composition may contain only one type of photopolymerization initiator or two or more types. If two or more types of photopolymerization initiators are contained, it is preferable that the total amount is within the above range. In addition, since photopolymerization initiators may also function as thermal polymerization initiators, crosslinking by the photopolymerization initiator may be further advanced by heating with an oven or hot plate, etc.

[0268] [Sensitizer] The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and enters an electronically excited state. When the sensitizer enters an electronically excited state, it comes into contact with thermal radical polymerization initiators, photoradical polymerization initiators, etc., causing electron transfer, energy transfer, and heat generation. As a result, the thermal radical polymerization initiators and photoradical polymerization initiators undergo chemical changes and decompose, generating radicals, acids, or bases. Suitable sensitizers include compounds such as benzophenone, Michla's ketone, coumarin, pyrazole azo, anilino azo, triphenylmethane, anthraquinone, anthracene, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo compounds. Examples of sensitizers include the compounds described in paragraph 0202 of International Publication No. 2023 / 190064.

[0269] If the resin composition contains a sensitizer, the sensitizer content is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass, based on the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more types.

[0270] [Chain Transfer Agents] The resin compositions of the present invention may contain chain transfer agents. Chain transfer agents are defined, for example, on pages 683-684 of the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, Japan, 2005). Examples of chain transfer agents include -S-S- and -SO2 molecules. ２ Compounds containing -S-, -N-O-, SH, PH, SiH, and GeH, as well as dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthanthate compounds having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation chain Transfer) polymerization, are used. These can generate radicals by donating hydrogen to low-activity radicals, or by being oxidized and then deprotonated. Thiol compounds are particularly preferred.

[0271] Furthermore, the chain transfer agent may be a compound described in paragraphs 0152-0153 of International Publication No. 2015 / 199219, which is incorporated herein by reference.

[0272] If 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, based on 100 parts by mass of the total solid content of the resin composition. There may be only one type of chain transfer agent, or there may be two or more types. If there are two or more types of chain transfer agents, it is preferable that their total content is within the above range.

[0273] Furthermore, a preferred embodiment of the present invention is that the resin composition of the present invention contains two or more polymerization initiators as polymerization initiators. Specifically, the resin composition of the present invention may contain a photopolymerization initiator and a thermal polymerization initiator described later.

[0274] By including a photopolymerization initiator and a thermal polymerization initiator described later, pattern formation by exposure becomes possible, and radical polymerization also proceeds more easily during curing by the heating process described later, which may improve performance such as chemical resistance. When including a photopolymerization initiator and a thermal polymerization initiator described later, the content ratio of the thermal polymerization initiator is preferably 20 to 70% by mass, and more preferably 30 to 60% by mass, relative to the total content of the photopolymerization initiator and the thermal polymerization initiator.

[0275] The inclusion of a photoradical polymerization initiator and a photoacid generator may improve performance such as resolution. When a photopolymerization initiator and a photoacid generator are included, the content ratio of the photoacid generator is preferably 20 to 70% by mass, and more preferably 30 to 60% by mass, relative to the total content of the photopolymerization initiator and the photoacid generator.

[0276] [Thermal Polymerization Initiators] Examples of thermal polymerization initiators include thermal radical polymerization initiators. Thermal radical polymerization initiators are compounds that generate radicals using thermal energy, thereby initiating or promoting the polymerization reaction of polymerizable compounds. By adding thermal radical polymerization initiators, the polymerization reaction of resins and polymerizable compounds can be advanced, thereby further improving solvent resistance.

[0277] Examples of thermal radical polymerization initiators include the compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554, the details of which are incorporated herein by reference.

[0278] If a thermal polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.5 to 15% by mass, based on the total solid content of the resin composition. Only one thermal polymerization initiator may be included, or two or more may be included. If two or more thermal polymerization initiators are included, the total amount is preferably within the above range.

[0279] <Base Generator> The resin composition of the present invention may contain a base generator. Here, a base generator is a compound that can generate a base by physical or chemical action. Preferred base generators include thermal base generators and photobase generators. In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition contains a base generator. By containing a thermal base generator in the resin composition, the cyclization reaction of the precursor can be promoted by heating, for example, resulting in good mechanical properties and chemical resistance of the cured product, and thus good performance as an interlayer insulating film for redistribution layers contained in semiconductor packages, for example. The base generator may be an ionic base generator or a nonionic base generator. Examples of bases 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. Known base-generating agents include, for example, carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, amineimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, α-lactone ring derivative compounds, amineimide compounds, phthalimide derivative compounds, and acyloxyimino compounds. Specific examples of nonionic base-generating agents include the compounds described in paragraphs 0249-0275 of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0280] Examples of base-generating agents include, but are not limited to, the following compounds.

[0281]

[0282]

[0283] 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.

[0284] Specific preferred compounds for ionic base generators include, for example, the compounds described in paragraphs 0148-0163 of International Publication No. 2018 / 038002.

[0285] Specific examples of ammonium salts include, but are not limited to, the following compounds.

[0286]

[0287] Specific examples of iminium salts include, but are not limited to, the following compounds.

[0288]

[0289] Furthermore, as a base-generating agent, it is preferable that the amino group is protected by a t-butoxycarbonyl group, from the viewpoint of storage stability and base generation by deprotection during curing.

[0290] 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, diethanol Luamine, 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-butanol bis(3-aminopropyl) Examples include, but are not limited to, ethers, 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 its derivative is protected by a t-butoxycarbonyl group.

[0291] When the resin composition contains a base generating agent, the amount of base generating agent is preferably 0.1 to 50 parts by mass per 100 parts by mass of 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 generating agents can be used. When two or more types are used, it is preferable that the total amount is within the above range.

[0292] <Solvent> The resin composition of the present invention preferably contains a solvent. Any known solvent can be used. An organic solvent is preferred. Examples of organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0293] 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, alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl esters of 3-alkyloxypropionates (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-A Suitable examples include alkyl esters of alkyloxypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.).

[0294] Suitable ethers include, for example, 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 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.

[0295] Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucocenone, and dihydrolevoglucocenone.

[0296] Suitable cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0297] As an example of a sulfoxide, dimethyl sulfoxide is a suitable choice.

[0298] Suitable amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0299] Suitable ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0300] 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, methylphenylcarbinol, n-amyl alcohol, methylamyl alcohol, and diacetone alcohol.

[0301] From the viewpoint of improving the properties of the coated surface, it is also preferable to use a mixture of two or more solvents.

[0302] 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, and propylene glycol methyl ether acetate, levoglucocenone, and dihydrolevoglucocenone, or a mixed solvent composed of two or more of these, is preferred. The combination of dimethyl sulfoxide and γ-butyrolactone, the combination of dimethyl sulfoxide and γ-valerolactone, the combination of 3-methoxy-N,N-dimethylpropionamide and γ-butyrolactone, the combination of 3-methoxy-N,N-dimethylpropionamide, γ-butyrolactone and dimethyl sulfoxide, or the combination of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred. Another preferred embodiment of the present invention is to further add toluene to these combined solvents in an amount of about 1 to 10% by mass relative to the total mass of the solvent. In particular, from the viewpoint of storage stability of the resin composition, an embodiment containing γ-valerolactone as the solvent is also a preferred embodiment of the present invention. In such embodiments, 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. Furthermore, the upper limit of the above content is not particularly limited and may be 100% by mass. The above content can be determined by considering the solubility of specific resins and other components contained in the resin composition. Furthermore, when dimethyl sulfoxide and γ-valerolactone are used in combination, it is preferable to contain 60 to 90% by mass of γ-valerolactone and 10 to 40% by mass of dimethyl sulfoxide relative to the total mass of the solvent, more preferably 70 to 90% by mass of γ-valerolactone and 10 to 30% by mass of dimethyl sulfoxide, and even more preferably 75 to 85% by mass of γ-valerolactone and 15 to 25% by mass of dimethyl sulfoxide.

[0303] 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. The inclusion of ethyl lactate provides excellent film-forming properties. This is thought to be because ethyl lactate has low hydrophilicity, and its inclusion suppresses the precipitation of the resin due to moisture in the residual solvent during drying of the composition. 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 above content is not particularly limited and may be 100% by mass or less. Furthermore, in the above embodiment, the content of one or more solvents selected from the group consisting of γ-butyrolactone and N-methyl-2-pyrrolidone, relative to 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 80 to 99.9% by mass, more preferably 90 to 99.5% by mass, and even more preferably 90 to 99.0% by mass. Furthermore, in the above 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 presumed to be because dimethyl sulfoxide has high polarity, which suppresses aggregation in the resin composition. When dimethyl sulfoxide is included, the content of dimethyl sulfoxide relative to the total mass of the solvent is preferably 10 to 40% by mass, more preferably 15 to 35% by mass, and even more preferably 20 to 30% by mass.

[0304] From the viewpoint of coatability, the solvent content is preferably such that the total solid content concentration of the resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, even more preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass. The solvent content can be adjusted according to the desired thickness of the coating film and the application method. If two or more solvents are included, it is preferable that their total is within the above range.

[0305] <Metal Adhesion Enhancers> The resin composition of the present invention preferably contains a metal adhesion enhancer from the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc. Examples of metal adhesion enhancers include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, amino compounds, and the like.

[0306] [Silane Coupling Agents] Examples of silane coupling agents include the compounds described in paragraph 0316 of International Publication No. 2021 / 112189 and the compounds described in paragraphs 0067 to 0078 of Japanese Patent Application Publication No. 2018-173573, 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 Japanese Patent Application Publication No. 2011-128358. The following compounds are also preferable as silane coupling agents. In the following formulas, Me represents a methyl group and Et represents an ethyl group. R below represents a structure derived from a blocking agent in a blocked isocyanate group. The blocking agent can be selected according to the elimination temperature, but examples include alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, and active methylene compounds. For example, from the viewpoint of wanting to set the elimination temperature to 160 to 180°C, caprolactam is preferred. Examples of commercially available compounds of this type include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0307]

[0308]

[0309] 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 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-isocyanatetopropyltriethoxysilane, and 3-trimethoxysilylpropyl succinic anhydride. These can be used individually or in combination of two or more. Furthermore, oligomeric compounds having multiple alkoxysilyl groups can also be used as silane coupling agents. Examples of such oligomeric compounds include compounds containing repeating units represented by the following formula (S-1).

[0310]

[0311] In formula (S-1), R Ｓ１ represents a monovalent organic group, R Ｓ２ R represents a hydrogen atom, a hydroxyl group, or an alkoxy group, and n represents an integer between 0 and 2. Ｓ１It is preferable that the structure includes polymerizable groups. Examples of polymerizable groups include groups having ethylenically unsaturated bonds, epoxy groups, oxetanyl groups, benzoxazolyl groups, blocked isocyanate groups, amino groups, etc. Examples of groups having ethylenically unsaturated bonds include vinyl groups, allyl groups, isoallyl groups, 2-methylallyl groups, groups having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl group), (meth)acrylamide groups, (meth)acryloyloxy groups, etc., with vinylphenyl groups, (meth)acrylamide groups, or (meth)acryloyloxy groups being preferred, vinylphenyl groups or (meth)acryloyloxy groups being more preferred, and (meth)acryloyloxy groups being even more preferred. Ｓ２ n is preferably an alkoxy group, and more preferably a methoxy group or an ethoxy group. n represents an integer from 0 to 2, and is preferably 1. Here, the structures of the repeating units represented by multiple formulas (S-1) contained in the oligomer-type compound may all be the same. Here, it is preferable that n is 1 or 2 in at least one of the repeating units represented by multiple formulas (S-1) contained in the oligomer-type compound, more preferably that n is 1 or 2 in at least two, and even more preferably that n is 1 in at least two. Commercial products can be used as such oligomer-type compounds, and an example of a commercial product is KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0312] [Aluminum-based adhesive aids] Examples of aluminum-based adhesive aids include aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), and ethyl acetate aluminum diisopropylate.

[0313] Other metal adhesion modifiers that can be used include the compounds described in paragraphs 0046 to 0049 of Japanese Patent Publication No. 2014-186186 and the sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Publication No. 2013-072935, the details of which are incorporated herein by reference.

[0314] The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. A value above the lower limit ensures good adhesion between the pattern and the metal layer, while a value below the upper limit ensures good heat resistance and mechanical properties of the pattern. Only one type of metal adhesion improver may be used, or two or more types may be used. If two or more types are used, it is preferable that their total value is within the above range.

[0315] <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, the migration of metal ions originating from the metal layer (or metal wiring) into the film can be effectively suppressed. Compounds corresponding to compound A described above are not considered migration inhibitors as referred to herein.

[0316] While there are no particular limitations on the migration inhibitors, examples include compounds having heterocyclic rings (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, and 6H-pyran ring, triazine ring), thioureas and compounds having sulfanyl groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

[0317] As migration inhibitors, ion trapping agents that capture anions such as halogen ions can also be used.

[0318] Other migration inhibitors that can be used include the rust inhibitor described in paragraph 0094 of Japanese Patent Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Publication No. 2009-283711, the compounds described in paragraph 0052 of Japanese Patent Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Publication No. 2012-194520, and the compounds described in paragraph 0166 of International Publication No. 2015 / 199219, the details of which are incorporated herein by reference.

[0319] Specific examples of migration inhibitors include the following compounds.

[0320]

[0321] 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% by mass, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass, based on the total solid content of the resin composition.

[0322] There may be only one type of migration inhibitor, or there may be two or more types. If there are two or more types of migration inhibitors, it is preferable that their total number is within the above range.

[0323] <Light Absorbers> The resin composition of the present invention may also preferably contain a compound (light absorber) whose absorbance at the exposure wavelength decreases upon exposure. Examples of light absorbers include the compounds described in paragraphs 0159 to 0183 of International Publication No. 2022 / 202647 and the compounds described in paragraphs 0088 to 0108 of Japanese Patent Application Publication No. 2019-206689. These contents are incorporated herein by reference.

[0324] Furthermore, it is preferable to include a compound with the following structure as a light absorber.

[0325]

[0326] 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% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 5% by mass.

[0327] <Polymerization Inhibitor> The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

[0328] Specific examples of polymerization inhibitors include the compounds described in paragraph 0310 of International Publication No. 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]nona-2-ene-N,N-dioxide, and the like. This information is incorporated herein by reference.

[0329] If the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass, based on the total solid content of the resin composition.

[0330] There may be only one polymerization inhibitor or two or more. If there are two or more polymerization inhibitors, it is preferable that their total number is within the above range.

[0331] <Other Additives> The resin composition of the present invention may optionally contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, photoacid generators, anti-aggregation agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliary agents (e.g., defoamers, flame retardants, etc.), to the extent that the effects of the present invention are obtained. By appropriately including these components, properties such as film properties can be adjusted. These components can be described, for example, in paragraphs 0183 onwards of Japanese Patent Application Publication No. 2012-003225 (paragraph 0237 of the corresponding U.S. Patent Application Publication No. 2013 / 0034812), paragraphs 0101 to 0104, 0107 to 0109 of Japanese Patent Application Publication No. 2008-250074, and the contents of these are incorporated herein. When these additives are incorporated, it is preferable that their total content be 3% by mass or less of the solid content of the resin composition of the present invention.

[0332] [Surfactants] Various surfactants can be used as surfactants, such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0333] By incorporating a surfactant into the resin composition of the present invention, the liquid properties (especially the fluidity) of the prepared coating liquid composition are further improved, and the uniformity of the coating thickness and the liquid-saving properties can be further enhanced. Specifically, when forming a film using a coating liquid containing a surfactant, the interfacial tension between the surface to be coated and the coating liquid decreases, improving the wettability to the surface to be coated and improving the coatability to the surface to be coated. Therefore, it is possible to more favorably form a uniform film with less thickness variation.

[0334] Examples of fluorinated surfactants include the compounds described in paragraph 0328 of International Publication No. 2021 / 112189, which are incorporated herein by reference. Fluorinated polymer compounds can also be preferably used as fluorinated surfactants, which include repeating units derived from a (meth)acrylate compound having a fluorine atom and repeating units derived from a (meth)acrylate compound having two or more (preferably five or more) alkylene oxy groups (preferably ethylene oxy groups, propylene oxy groups). Examples include the following compounds.

[0335]

[0336] 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 a fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in its side chain can also be used. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of Japanese Patent Application Publication No. 2010-164965, the contents of which are incorporated herein by reference. Examples of commercially available products include Megafac RS-101, RS-102, RS-718K, etc., manufactured by DIC Corporation.

[0337] The fluorine content in the fluorinated surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. Fluorinated surfactants with a fluorine content within this range are effective in terms of uniformity of coating film thickness and liquid saving, and also have good solubility in the composition.

[0338] Examples of silicone-based surfactants, hydrocarbon-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants include the compounds described in paragraphs 0329-0334 of International Publication No. 2021 / 112189, respectively, which are incorporated herein by reference.

[0339] One type of surfactant may be used, or two or more types may be used in combination. The surfactant content is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, relative to the total solid content of the composition.

[0340] [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.

[0341] The average particle diameter 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 diameter of the inorganic particles is the primary particle diameter and also the volume-average particle diameter. The volume-average particle diameter can be measured, for example, by dynamic light scattering using 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, X-ray transmission, or laser diffraction / scattering.

[0342] [Organotitanium Compounds] By including organotitanium compounds in the resin composition, a resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

[0343] Suitable organotitanium compounds include those in which an organic group is bonded to a titanium atom via covalent or ionic bonds. Specific examples of organotitanium compounds are shown in I) to VII) below: I) Titanium chelate compounds: Titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability for the resin composition and yield a good curing pattern. Specific examples include titanium bis(triethanolamine)diisopropoxide, titanium di(n-butoxide)bis(2,4-pentanedione), titanium diisopropoxidebis(2,4-pentanedione), titanium diisopropoxidebis(tetramethylheptanedione), titanium diisopropoxidebis(ethylacetoacetate), etc. II) Tetraalkoxy titanium 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 tetrastearaloxide, titanium tetrakis[bis{2,2-(alyloxymethyl)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-pyrrole-1-yl)phenyl)titanium, etc. IV) Monoalkoxy titanium compounds: For example, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc. V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc.VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate. VII) Titanate coupling agents: For example, isopropyltridodecylbenzenesulfonyl titanate.

[0344] In particular, from the viewpoint of better chemical resistance, the organotitanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds. Titanium diisopropoxide bis(ethyl acetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium are preferred.

[0345] Furthermore, it is preferable to include a compound represented by the following formula (T-1) as an organotitanium compound, or in place of an organotitanium compound.

[0346]

[0347] In equation (T-1), M is titanium, zirconium, or hafnium, l1 is an integer from 0 to 2, l2 is 0 or 1, l1 + l2 × 2 is an integer from 0 to 2, m is an integer from 0 to 4, n is an integer from 0 to 2, l1 + l2 + m + n × 2 = 4, R １１ Each of these is independently a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenoxy group, R １２ R is a substituted or unsubstituted hydrocarbon group, ２ Each of these is an independent group containing a structure represented by the following formula (T-2), and R ３ Each of these is an independent group containing a structure represented by the following formula (T-2), and X Ａ Each of these is independently either an oxygen atom or a sulfur atom.

[0348]

[0349] In formula (T-2), X １ ~X ３Each of these independently represents -C(-*)= or -N=, where * represents a bonding site with another structure, and # represents a bonding site with a metal atom.

[0350] 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, in formula (T-1), it is also preferable that l1 and l2 are 0 and m is 0, 2, or 4.

[0351] In formula (T-1), from the viewpoint of the stability of the specific metal complex, R １１ A substituted or unsubstituted cyclopentadienyl ligand is preferred. Also, R １１ The cyclopentadienyl group, alkoxy group, and phenoxy group in the compound may be substituted, but an unsubstituted configuration is also a preferred embodiment of the present invention.

[0352] In formula (T-1), R １２ R 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. １２ The substituents in are preferably monovalent substituents, such as halogen atoms. １２ If is an aromatic hydrocarbon group, it may have an alkyl group as a substituent. Among these, in formula (T-1), R １２ It is preferable that R is an unsubstituted phenylene group. １２The phenylene group in this is preferably a 1,2-phenylene group.

[0353] In equation (T-1), m is 2 or greater, and R ２ If there are two or more of them, then the two or more R ２ The structures of each may be the same or different. In equation (T-1), n ​​is 2 or greater, and R ３ If there are two or more of them, then the two or more R ３ The structures of each may be the same or different.

[0354] In formula (T-2), X １ ~X ３ Each of these independently represents -C(-*)= or -N=, preferably at least one represents -C(-*)=, and more preferably at least two represent -C(-*)=.

[0355] Specific examples of compounds represented by formula (T-1) include, but are not limited to, the compound corresponding to F-11 in the examples.

[0356] When an organic titanium compound is included, its content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the specific resin. When the content is 0.05 parts by mass or more, the heat resistance and chemical resistance of the resulting cured pattern are better, and when it is 10 parts by mass or less, the storage stability of the composition is better.

[0357] When an organic titanium compound is included, its content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin. When the content is 0.05 parts by mass or more, the heat resistance and chemical resistance of the resulting cured pattern are better, and when it is 10 parts by mass or less, the storage stability of the composition is better.

[0358] [Antioxidants] By including antioxidants as additives, the elongation properties of the cured film and its 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 0348-0357 of International Publication No. 2021 / 112189, which are incorporated herein by reference.

[0359] The antioxidant content is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. By adding 0.1 parts by mass or more, it is easier to obtain the effect of improving elongation characteristics and adhesion to metal materials even in high temperature and high humidity environments, and by adding 10 parts by mass or less, the sensitivity of the resin composition is improved, for example, through interaction with the photosensitive agent. 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 their total amount is within the above range. Other additives include compounds described in paragraphs 0249 to 0282 and 0316 to 0358 of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0360] <Characteristics of the Resin Composition> The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of coating film thickness, 1,000 mm ２ / s~12,000mm ２ / s is preferred, and 2,000 mm ２ / s~10,000mm ２ / s is more preferable, 2,500 mm ２ / s~8,000mm ２ / s is even more preferable. Within the above range, it becomes easier to obtain a highly uniform coating film. 1,000 mm ２ If the temperature is 1 / s or higher, it is easy to coat the film with the required thickness, for example, as an insulating film for rewiring, and 12,000 mm ２ If the rate is less than or equal to / s, a coating with excellent properties can be obtained on the coated surface.

[0361] <Restrictions on the substances contained in the 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. Furthermore, the lower limit of the water content of the resin composition of the present invention is preferably 0.001% by mass or more, can be 0.05% by mass or more, and can be 0.5% by mass or more, from the viewpoint of reducing the effort required to manage storage conditions, adhesion, developability, etc. Specific examples of the water content of the resin composition of the present invention include, for example, 0.05% by mass, 0.2% by mass, and 1.4% by mass. Methods for maintaining the water content include adjusting the humidity in the storage conditions and reducing the porosity of the storage container during storage.

[0362] From the viewpoint of insulating properties and reliability, the metal content of the resin composition of the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Furthermore, from the viewpoint of reducing the effort required to reduce the metal content, mechanical properties, and adhesion, the lower limit of the metal content in the resin composition of the present invention can be 0.001 ppm by mass or more, and can also be 0.01 ppm by mass or more. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, manganese, aluminum, titanium, cobalt, zinc, and tin, but excludes metals included as complexes of organic compounds and metals. If multiple metals are included, it is preferable that the sum of these metals is within the above range. Specific examples of the metal content in the resin composition of the present invention include, for example, 0.002 ppm by mass, 0.05 ppm by mass, and 0.3 ppm by mass.

[0363] Furthermore, methods for reducing metal impurities unintentionally included in the resin composition of the present invention include selecting raw materials with a low metal content as the raw materials constituting the resin composition of the present invention, performing filter filtration on the raw materials constituting the resin composition of the present invention, and performing distillation under conditions in which contamination is suppressed as much as possible by lining the inside of the apparatus with polytetrafluoroethylene or the like.

[0364] Considering its application as a semiconductor material, the halogen atom content of the resin composition of the present invention 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 preventing wiring corrosion. In particular, the amount of halogen atoms present in the form of halogen ions is 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 to reduce halogen ions, the lower limit of halogen ions in the resin composition of the present invention can be 0.01 ppm by mass or more, or 0.1 ppm by mass or more. Specific examples of halogen ion amounts in the resin composition of the present invention include, for example, 0.02 ppm by mass, 0.5 ppm by mass, and 2.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferable that the total amount of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above ranges. A preferred method for adjusting the halogen atom content is ion exchange treatment.

[0365] Conventional containers can be used as containers for the resin composition of the present invention. To suppress the incorporation of impurities into the raw materials and the resin composition of the present invention, it is also preferable to use multilayer bottles with an inner wall constructed of six types of resin in six layers, or bottles with a seven-layer structure of six types of resin. Examples of such containers include the container described in Japanese Patent Application Publication No. 2015-123351.

[0366] <Cured product of the resin composition> A cured product of the resin composition of the present invention 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 curing of the resin composition is preferably done by heating, with a heating temperature of 120°C to 400°C being more preferably, 140°C to 380°C being even more preferably, 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 according to the application, such as in the form of a film, rod, sphere, or pellet. In the present invention, the cured product is preferably in the form of a film. By pattern processing of the resin composition, the shape of the cured product can also be selected according to the application, such as forming a protective film on the wall surface, forming via holes for conductivity, adjusting impedance, capacitance or internal stress, or providing a heat dissipation function. 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 change in volume of the resin composition before and after curing, and can be calculated using the following formula: Shrinkage rate [%] = 100 - (Volume after curing ÷ Volume before curing) × 100

[0367] <Characteristics of the Cured Resin Composition> The imidization reaction rate of the cured 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 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 resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and even more preferably 230°C or higher.

[0368] <Preparation of Resin Composition> The resin composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited and can be carried out by conventionally known methods. Mixing methods 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, and more preferably 15 to 25°C.

[0369] For the purpose of removing foreign matter such as dirt and fine particles from the resin composition of the present invention, filtration using a filter is preferable. The filter pore size is preferably, for example, 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. If the filter material is polyethylene, it is more preferably HDPE (high-density polyethylene). The filter may be one that has been pre-washed with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or in parallel. When multiple types of filters are used, filters with different pore sizes or materials may be combined. As an example of a connection configuration, 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. Furthermore, various materials may be filtered multiple times. When filtering multiple times, circulating filtration may be used. Furthermore, filtration may be performed under pressure. When filtration is performed under pressure, the pressure applied is preferably, for example, 0.01 MPa to 1.0 MPa, more preferably 0.03 MPa to 0.9 MPa, even more preferably 0.05 MPa to 0.7 MPa, and even more preferably 0.05 MPa to 0.5 MPa. In addition to filtration using a filter, impurity removal treatment using an adsorbent may also be performed. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, known adsorbents can be used. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. After filtration using a filter, the resin composition filled into bottles may be subjected to a degassing step by placing it under reduced pressure.

[0370] (Method for Manufacturing Cured Products) The method for manufacturing cured products of the present invention preferably includes a film-forming step of applying a resin composition onto a substrate to form a film. The method for manufacturing cured products more preferably includes the film-forming step, an exposure step of selectively exposing the film formed in the film-forming step, and a developing step of developing the film exposed in the exposure step using a developer to form a pattern. The method for manufacturing cured products particularly preferably includes the film-forming step, the exposure step, the developing step, and at least one of a heating step of heating the pattern obtained in the developing step and a post-development exposure step of exposing the pattern obtained in the developing step. Furthermore, the method for manufacturing cured products may also preferably include the film-forming step and a step of heating the film. Details of each step will be described below.

[0371] <Membrane Formation Process> The resin composition of the present invention can be used in a membrane formation process in which it is applied to a substrate to form a film. The method for producing a cured product of the present invention preferably includes a membrane formation process in which the resin composition is applied to a substrate to form a film.

[0372] [Substrate] The type of substrate can be appropriately determined according to the application and is not particularly limited. Examples of substrates include semiconductor manufacturing substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon; quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, reflective films; metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metal, and substrates in which a metal layer is formed by, for example, plating or vapor deposition); paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, molded substrates, and electrode plates for plasma display panels (PDPs). Semiconductor manufacturing substrates are particularly preferred, and silicon substrates, Cu substrates, and molded substrates are more preferred. These substrates may have layers such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) on their surface. The shape of the substrate is not particularly limited and may be circular or rectangular. If the substrate is circular, for example, a diameter of 100 to 450 mm is preferred, and 200 to 450 mm is more preferred. If it is rectangular, for example, the length of the shorter side is preferred to be 100 to 1000 mm, and 200 to 700 mm is more preferred. As the substrate, for example, a plate-shaped, preferably panel-shaped, substrate (substrate) is used.

[0373] When a resin composition is applied to the surface of a resin layer (for example, a layer made of cured material) or a metal layer to form a film, the resin layer or metal layer serves as the substrate.

[0374] Coating is a preferred method for applying the resin composition onto 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 are 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 the coating conditions according to the application method, a film of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected depending on the shape of the substrate; for circular substrates such as wafers, spin coating, spray coating, and inkjet coating are preferred, while for rectangular substrates, slit coating, spray coating, and inkjet coating 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. Furthermore, a method can be applied in which a coating film, which has been previously applied and formed on a temporary support using the above application method, is transferred onto the substrate. Regarding the transfer method, the manufacturing methods described in paragraphs 0023, 0036-0051 of Japanese Patent Application Publication No. 2006-023696 and paragraphs 0096-0108 of Japanese Patent Application Publication No. 2006-047592 can be suitably used. In addition, a step of removing excess film at the edges of the substrate may be performed. Examples of such steps include edge bead rinsing (EBR) and back rinsing. A pre-wetting step may be employed in which the substrate is coated with various solvents to improve the wettability of the substrate before applying the resin composition to the substrate, and then the resin composition is applied.

[0375] <Drying Step> After the film formation step (layer formation step), the film may be subjected to a drying step (drying step) to remove the solvent. That is, the method for producing a cured product of the present invention may include a drying step to dry the film formed in the film formation step. The drying step is preferably performed after the film formation step and before the exposure step. The drying temperature of the film in the drying step is preferably 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. Drying may also be performed under reduced pressure. The drying time is exemplified as 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.

[0376] <Exposure Process> The above film may be subjected to an exposure process in which the film is selectively exposed. The method for manufacturing the cured product may include an exposure process in which the film formed by the film formation process is selectively exposed. Selective exposure means exposing a part of the film. By selective exposure, exposed areas (exposed parts) and unexposed areas (unexposed parts) are formed in the film. The amount of exposure is not particularly limited as long as the resin composition of the present invention can be cured, but for example, it may be 50 to 10,000 mJ / cm in terms of exposure energy at a wavelength of 365 nm. ２ Preferably, 200 to 8,000 mJ / cm² ２ This is preferable.

[0377] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, with 240 to 550 nm being preferred.

[0378] In relation to the light source, the exposure wavelength can be found in: (1) semiconductor lasers (wavelengths 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-line (wavelength 436nm), h-line (wavelength 405nm), i-line (wavelength 365nm), broad (three wavelengths: g, h, i), (4) excimer lasers, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F ２Examples of exposures include (5) excimer laser (wavelength 157 nm), (6) extreme ultraviolet light; EUV (wavelength 13.6 nm), (7) YAG laser with 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 the i-line is more preferred from the viewpoint of exposure sensitivity. The exposure method is not particularly limited, and any method in which at least a part of the film made of the resin composition of the present invention is exposed is acceptable, but examples include exposure using a photomask and exposure by laser direct imaging.

[0379] <Post-exposure heating step> The above film may be subjected to a heating step after exposure (post-exposure heating step). That is, the method for producing a cured product of the present invention may include a post-exposure heating step in which the film exposed in the exposure step is heated. The post-exposure heating step can be performed after the exposure step and before the development step. The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, and more preferably 60°C to 120°C. The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, and more preferably 1 minute to 10 minutes. The heating rate in the post-exposure heating step is preferably 1 to 12°C / min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. The heating rate may also be changed as appropriate during heating. The heating means in the post-exposure heating step is not particularly limited, and known hot plates, ovens, infrared heaters, etc., can be used. Furthermore, it is preferable to carry out the heating process in a low-oxygen atmosphere by flowing inert gases such as nitrogen, helium, or argon through the system.

[0380] <Development Process> The film after exposure may be subjected to a development process in which a pattern is formed by developing it with a developer. That is, the method for manufacturing a cured product of the present invention may include a development process in which a pattern is formed by developing the film exposed in the exposure process with a developer. By developing, one of the exposed and unexposed parts of the film is removed, and a pattern is formed. Here, development in which the unexposed part of the film is removed by the development process is called negative development, and development in which the exposed part of the film is removed by the development process is called positive development.

[0381] [Developer] Developers used in the developing process include alkaline aqueous solutions or developers containing organic solvents.

[0382] When the developer is an alkaline aqueous solution, the basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferably, TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine are preferred, and TMAH is more preferred. The content of basic compounds in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass, based on the total mass of the developer.

[0383] If the developer contains an organic solvent, the organic solvent may be one of the compounds described in paragraph 0387 of International Publication No. 2021 / 112189. This is incorporated herein by reference. Suitable alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutylcarbinol, triethylene glycol, etc., and suitable amides include N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc.

[0384] When the developer contains an organic solvent, one or more organic solvents can be used in mixture form. 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.

[0385] 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 above content may be 100% by mass.

[0386] The developing solution may further contain other components. Examples of other components include known surfactants and known defoaming agents.

[0387] [Method of supplying developer] There are no particular restrictions on the method of supplying the developer as long as a desired pattern can be formed. These include immersing a substrate on which a film has been formed in the developer, paddle development in which the developer is supplied to the film formed on the substrate using a nozzle, or a method of continuously supplying the developer. There are no particular restrictions on the type of nozzle, and examples include straight nozzles, shower nozzles, spray nozzles, etc. From the viewpoint of developer penetration, removal of non-image areas, and manufacturing efficiency, a method of supplying the developer with a straight nozzle or a method of continuously supplying it with a spray nozzle is preferred, and from the viewpoint of developer penetration into the image area, a method of supplying with a spray nozzle is more preferred. In addition, a step may be adopted in which the developer is continuously supplied with a straight nozzle, the substrate is spun to remove the developer from the substrate, and after spin drying, the developer is supplied again with a straight nozzle, and the substrate is spun to remove the developer from the substrate. This step may be repeated multiple times. Examples of methods of supplying the developer in the development process include a step in which the developer is continuously supplied to the substrate, a step in which the developer is kept in a nearly stationary state on the substrate, a step in which the developer is vibrated on the substrate with ultrasound, etc., and a step that combines these.

[0388] The development time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the developer solution during development is not particularly specified, but is preferably 10 to 45°C, and more preferably 18 to 30°C.

[0389] In the developing process, after processing with the developer, the pattern may be further washed (rinsed) with a rinsing solution. Alternatively, methods such as supplying the rinsing solution before the developer in contact with the pattern dries completely may be employed.

[0390] [Rinsing Solution] If the developer is an alkaline aqueous solution, water can be used as the rinsing solution. If the developer contains an organic solvent, a solvent different from the solvent contained in the developer (for example, water, or an organic solvent different from the organic solvent contained in the developer) can be used as the rinsing solution.

[0391] When the rinsing solution contains an organic solvent, the organic solvent can be the same as the organic solvent exemplified above when the developer contains an organic solvent. Preferably, the organic solvent in the rinsing solution is different from the organic solvent in the developer, and more preferably, it is an organic solvent with lower pattern solubility than the organic solvent in the developer.

[0392] If the rinsing solution contains an organic solvent, one or more organic solvents may be used in mixture form. Preferred organic solvents are cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA (propylene glycol 1-monomethyl ether 2-acetate), and PGME (1-methyl-2-propanol). Cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME are more preferred, and cyclohexanone and PGMEA are even more preferred.

[0393] When the rinsing solution contains an organic solvent, the amount of the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, relative to the total mass of the rinsing solution. Alternatively, the amount of the organic solvent may be 100% by mass, relative to the total mass of the rinsing solution.

[0394] The rinse solution may further contain other components. Examples of other components include known surfactants and known defoaming agents.

[0395] [Method of supplying rinsing solution] There are no particular restrictions on the method of supplying the rinsing solution as long as a desired pattern can be formed. These include immersing the substrate in the rinsing solution, supplying the rinsing solution to the substrate by pouring the solution, supplying the rinsing solution to the substrate with a shower, and continuously supplying the rinsing solution onto the substrate using means such as a straight nozzle. From the viewpoint of the penetration of the rinsing solution, the removal of non-image areas, and manufacturing efficiency, there are methods of supplying the rinsing solution with a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuous supply with a spray nozzle is preferred, and from the viewpoint of the penetration of the rinsing solution into the image area, the method of supplying with a spray nozzle is more preferred. There are no particular restrictions on the type of nozzle, and examples include straight nozzles, shower nozzles, spray nozzles, etc. That is, the rinsing process is preferably a process of supplying the rinsing solution to the film after exposure using a straight nozzle or continuously supplying it, and it is more preferable to supply the rinsing solution using a spray nozzle. Possible methods for supplying the rinsing solution in the rinsing process include a process in which the rinsing solution is continuously supplied to the substrate, a process in which the rinsing solution is kept in a nearly stationary state on the substrate, a process in which the rinsing solution is vibrated on the substrate using ultrasound or the like, and a process that combines these methods.

[0396] The rinsing time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the rinsing solution during rinsing is not particularly specified, but is preferably 10 to 45°C, and more preferably 18 to 30°C.

[0397] <Heating Step> The pattern obtained by the developing 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 developing 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 developing 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 developing step, or a film obtained by a film formation step is heated. In the heating step, precursors of cyclized resins such as polyimide precursors are cyclized to become cyclized resins such as polyimide. In addition, crosslinking of unreacted crosslinkable groups in specific resins or crosslinking agents other than specific resins 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.

[0398] The heating step is preferably a step in which the heating promotes the cyclization reaction of the polyimide precursor within the pattern by the action of bases generated from the base generating agent.

[0399] In the heating process, heating is preferably carried out at a heating rate of 1 to 12°C / minute from the initial heating temperature to the maximum heating temperature. More preferably, the heating rate is 2 to 10°C / minute, and even more preferably 3 to 10°C / minute. By setting the heating rate to 1°C / minute or more, it is possible to prevent excessive volatilization of acid or solvent while ensuring productivity, and by setting the heating rate to 12°C / minute 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 carry out heating at a heating rate of 1 to 8°C / second from the initial heating temperature to the maximum heating temperature, more preferably 2 to 7°C / second, and even more preferably 3 to 6°C / second.

[0400] The starting temperature for 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 starting temperature for heating refers to the temperature at which the process of heating to the maximum heating temperature is initiated. For example, when the resin composition of the present invention is applied to a substrate and then dried, this is the temperature of the film (layer) after drying, and it is preferable to start the heating process from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition.

[0401] The heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

[0402] 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 especially preferably 120°C or higher. The upper limit of the above heating temperature is preferably 350°C or lower, more preferably 250°C or lower, and even more preferably 240°C or lower.

[0403] Heating may be carried out in stages. For example, the process may involve raising the temperature from 25°C to 120°C at a rate of 3°C / min, holding at 120°C for 60 minutes, raising the temperature from 120°C to 180°C at a rate of 2°C / min, and holding at 180°C for 120 minutes. It is also preferable to treat while irradiating with ultraviolet light, as described in U.S. Patent No. 9,159,547. Such pretreatment steps can improve the properties of the film. The pretreatment step is preferably carried out for a short time of about 10 seconds to 2 hours, and more preferably for 15 seconds to 30 minutes. The pretreatment may consist of two or more steps; for example, the first pretreatment step may be carried out in the range of 100 to 150°C, followed by the second pretreatment step in the range of 150 to 200°C. Furthermore, cooling may be performed after heating, and in this case, the cooling rate is preferably 1 to 5°C / min.

[0404] The heating process is preferably carried out in a low-oxygen atmosphere, such as by flowing an inert gas like nitrogen, helium, or argon, or under reduced pressure, from the viewpoint of preventing the decomposition of specific resins. The oxygen concentration is preferably 50 ppm (by volume) or less, and more preferably 20 ppm (by volume) or less. The heating means in the heating process is not particularly limited, but examples include hot plates, infrared furnaces, electric ovens, hot air ovens, and infrared ovens.

[0405] <Post-development exposure step> The pattern obtained in the development step (or the pattern after rinsing, if a rinsing step is performed) may be subjected to a post-development exposure step in which the pattern after the development step is exposed, either in place of the heating step 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. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or it may include only one of the heating step and the post-development exposure step. In the post-development exposure step, for example, reactions such as the cyclization of polyimide precursors etc. by photosensitivity of a photobase generator, or the elimination of acid-degradable groups by photosensitivity of a photoacid generator can be promoted. In the post-development exposure step, it is sufficient for at least a part of the pattern obtained in the development step to be exposed, but it is preferable for the entire pattern to be exposed. The amount of exposure in the post-development exposure step is 50 to 20,000 mJ / cm in terms of exposure energy at the wavelength to which the photosensitive compound is sensitive. ２ Preferably, 100 to 15,000 mJ / cm² ２ This is more preferable. The post-development exposure step can be performed, for example, using the light source in the exposure step described above, and it is preferable to use broadband light.

[0406] <Metal Layer Formation Process> The pattern obtained by the development process (preferably one that has been subjected to at least one of the heating process and the post-development exposure process) may be subjected to a metal layer formation process in which a metal layer is formed on the pattern. That is, the method for producing a cured product of the present invention preferably includes a metal layer formation process in which a metal layer is formed on the pattern obtained by the development process (preferably one that has been subjected to at least one of the heating process and the post-development exposure process).

[0407] The metal layer is not particularly limited, and existing metal species can be used, with examples including copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals, with copper and aluminum being more preferred, and copper being even more preferred.

[0408] The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, methods described in Japanese Patent Publication No. 2007-157879, Japanese Patent Publication No. 2001-521288, Japanese Patent Publication No. 2004-214501, Japanese Patent Publication No. 2004-101850, U.S. Patent No. 7888181B2, and U.S. Patent No. 9177926B2 can be used. For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and methods combining these can be considered. More specifically, patterning methods combining sputtering, photolithography and etching, and patterning methods combining photolithography and electroplating can be mentioned. Preferred embodiments of the plating include electroplating using copper sulfate or copper cyanide plating solutions.

[0409] The thickness of the metal layer is preferably 0.01 to 50 μm at the thickest part, and more preferably 1 to 10 μm.

[0410] <Applications> The manufacturing method of the cured product of the present invention, or the fields in which the cured product can be applied, include insulating films for electronic devices, interlayer insulating films for redistribution layers, and stress buffer films. Other applications include sealing films, substrate materials (base films and coverlays for flexible printed circuit boards, interlayer insulating films), or etching to form patterns on insulating films for the above-mentioned mounting applications. For more information on these applications, please refer to, for example, Science & Technology Co., Ltd., "High-Functionality and Application Technologies of Polyimides," April 2008, supervised by Masaaki Kakimoto; CMC Technical Library, "Fundamentals and Development of Polyimide Materials," November 2011; and the Japan Polyimide and Aromatic Polymer Research Association, ed., "Latest Polyimide Fundamentals and Applications," NTS, August 2010.

[0411] The method for manufacturing the cured product of the present invention, or the cured product of the present invention, can also be used for manufacturing printing plates such as offset plates or screen printing plates, for etching molded parts, and for manufacturing protective lacquers and dielectric layers in electronics, particularly microelectronics.

[0412] (Laminate and Method for Manufacturing a Laminate) The laminate of the present invention refers to a structure having multiple layers made of the cured product of the present invention. The laminate is a laminate containing two or more layers made of the cured product, and may be a laminate with three or more layers. Of the two or more layers made of the cured product included in the above laminate, at least one is 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 due to the above shrinkage, it is also preferable that all the layers made of the cured product included in the above laminate are made of the cured product of the present invention.

[0413] In other words, the method for manufacturing the laminate of the present invention preferably includes a method for manufacturing the cured product of the present invention, and more preferably includes repeating the method for manufacturing the cured product of the present invention multiple times.

[0414] The laminate of the present invention preferably comprises two or more layers made of cured material, with a metal layer preferably included between any of the layers made of cured material. The metal layer is preferably formed by the metal layer formation step described above. That is, the method for manufacturing the laminate of the present invention preferably further includes a metal layer formation step in which a metal layer is formed on the layers made of cured material, between multiple cured material manufacturing steps. The preferred embodiment of the metal layer formation step is as described above. As the laminate, for example, a laminate is preferred that includes at least three layers in which a first layer made of cured material, a metal layer, and a second layer made of cured material are laminated in this order. It is preferable that both the first layer made of cured material and the second layer made of cured material are layers made of cured material of the present invention. The resin composition of the present invention used to form the first layer made of cured material and the resin composition of the present invention used to form the second layer made of cured material may have the same composition or may have different compositions. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.

[0415] <Lamination Process> The method for manufacturing a laminate of the present invention preferably includes a lamination process. The lamination process is a series of steps that include performing, in this order, at least one of the following on the surface of a pattern (resin layer) or metal layer: (a) film formation process (layer formation process), (b) exposure process, (c) development process, (d) heating process, and post-development exposure process. However, the method may also involve repeating at least one of the following: (a) film formation process and (d) heating process and post-development exposure process. Furthermore, at least one of the following: (d) heating process and post-development exposure process may be followed by (e) metal layer formation process. Needless to say, the lamination process may further include the above-mentioned drying process and the like as appropriate.

[0416] If further lamination is performed after the lamination process, a surface activation treatment step may be performed after the exposure step, the heating step, or the metal layer formation step. Plasma treatment is an example of a surface activation treatment. Details of the surface activation treatment will be described later.

[0417] The above lamination process is preferably performed 2 to 20 times, and more preferably 2 to 9 times. For example, a configuration with 2 to 20 resin layers, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferred, and a configuration with 2 to 9 resin layers is even more preferred. Each of the above layers may have the same composition, shape, film thickness, etc., or they may be different.

[0418] In the present invention, it is particularly preferable to form a cured product (resin layer) of the resin composition of the present invention so as to cover the metal layer after providing the metal layer. Specifically, examples include repeating the steps in the order of (a) film formation, (b) exposure, (c) development, (d) heating and post-development exposure, and (e) metal layer formation, or repeating the steps in the order of (a) film formation, (d) heating and post-development exposure, and (e) metal layer formation. By alternately performing the lamination step of stacking the resin composition layer (resin layer) of the present invention and the metal layer formation step, the resin composition layer (resin layer) and the metal layer of the present invention can be alternately stacked.

[0419] (Surface Activation Treatment Step) The manufacturing method of the 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 is 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 surface activation treatment step may be performed on the resin composition layer 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 on at least a portion of both the metal layer and the post-exposure resin composition layer. It is preferable to perform the surface activation treatment on at least a portion of the metal layer, and it is preferable to perform the surface activation treatment on a portion or all of the area on the surface of the metal layer where the resin composition layer is formed. By performing the surface activation treatment on the surface of the metal layer in this way, the adhesion to the resin composition layer (film) provided on its surface can be improved. It is also preferable to perform the surface activation treatment on a portion or all of the post-exposure resin composition layer (resin layer). By performing the surface activation treatment on the surface of the resin composition layer in this way, the adhesion to the metal layer and resin layer provided on the surface-activated surface can be improved. In particular, when developing negative film, if the resin composition layer is cured, it is less susceptible to damage from surface treatment and adhesion is easily improved. Surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of International Publication No. 2021 / 112189. This is incorporated herein by reference.

[0420] (Semiconductor Devices and Methods for Manufacturing the Same) The present invention also discloses semiconductor devices including a cured product or a laminate of the present invention. Furthermore, the present invention also discloses a method for manufacturing a semiconductor device including a method for manufacturing a cured product or a laminate of the present invention. Specific examples of semiconductor devices in which the resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer can be found in paragraphs 0213 to 0218 and Figure 1 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0421] The present invention will be described in more detail below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not depart 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.

[0422] <Synthesis of Polymers> [Synthesis Example P-1-1: Synthesis of Resin (P-1, Mw 30,000) (Precursor to Cyclic Resin)] 12.7 g of 4,4'-oxydiphthalic acid dianhydride (ODPA), 8.0 g of bisphthalic acid dianhydride (BPDA), 18.0 g of 2-hydroxyethyl methacrylate (HEMA), 23.9 g of pyridine, and 250 mL of diglyme (diethylene glycol dimethyl ether) are mixed and stirred at 60°C for 4 hours to synthesize diesters of ODPA and BPDA with HEMA. The reaction mixture is then cooled to -10°C, and 17.0 g of thionyl chloride is added over 60 minutes while maintaining the temperature at -10±5°C. After diluting with 50 mL of N-methylpyrrolidone, a solution prepared by dissolving 12.2 g of 4,4'-diaminodiphenyl ether (DADPE) in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture over 60 minutes at -10±5°C, and the mixture is stirred at room temperature (25°C) for 2 hours. Then, 10.0 g of ethanol is added and the mixture is stirred at room temperature for 1 hour. Next, 6000 g of water is added to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) is stirred for 15 minutes. The precipitate (solid polyimide precursor) after stirring is filtered and dissolved in 500 g of tetrahydrofuran (THF). 6000 g of water (poor solvent) is added to the resulting solution to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) is stirred for 15 minutes. The precipitate after stirring is filtered again and dried under reduced pressure at 45°C for 1 day to obtain 45.3 g of powdered resin P-1. The weight-average molecular weight (Mw) is 30,000. １¹H-NMR confirms that the structure of resin P-1 is represented by the following formula P-1. The weight-average molecular weight and number-average molecular weight are measured by the following method. A high-speed GPC instrument HLC-8420GPC (manufactured by Tosoh Corporation) is used, with a TSK guard column Super AW-H (4.6 mm × 35 mm) as the guard column and two TSKgel Super AWM-H (4.6 mm × 150 mm) columns connected in series for GPC measurement. A 0.01 mol / L lithium bromide NMP (N-methyl-2-pyrrolidone) solution is used as the eluent. In the following synthesis examples, unless otherwise specified, the method for measuring the weight-average molecular weight and number-average molecular weight is the same as above.

[0423]

[0424] Resin P-1 is a random copolymer containing the two types of repeating units described above in a molar ratio of 60:40.

[0425] Furthermore, by changing the equivalent amount of DADPE used, resin P-1 with Mw values ​​of 15,000, 20,000, 40,000, and 50,000 can also be synthesized.

[0426] [Synthesis Example P-1-2: Synthesis of Resin (P-1, Mw 28,000) (Precursor to Cyclic Resin)] 28.18 g of ODPA and 8.91 g of BPDA are placed in a separable flask, 39.69 g of HEMA and 136.83 g of THF are added, and the mixture is stirred at room temperature (25°C). While stirring, 24.66 g of pyridine is added to obtain the reaction mixture. After the exothermic reaction is complete, the mixture is allowed to cool to room temperature and left for 16 hours. Next, under ice cooling, a solution of 62.46 g of dicyclohexylcarbodiimide (DCC) dissolved in 61.57 g of THF is added to the reaction mixture over 40 minutes while stirring, followed by 26.98 g of DADPE suspended in 119.73 g of THF, which is added over 60 minutes while stirring. After further stirring at room temperature for 2 hours, 7.17 g of ethyl alcohol is added and the mixture is stirred for 1 hour, then 136.83 g of THF is added. The precipitate formed in the reaction mixture is removed by filtration to obtain the reaction solution. The obtained reaction solution is added to 716.21 g of ethanol to produce a precipitate consisting of crude polymer. The produced crude polymer is filtered off and dissolved in 403.49 g of THF to obtain a crude polymer solution. The obtained crude polymer solution is added dropwise to 8470.26 g of water to precipitate the polymer, and the precipitate (water-polyimide precursor mixture) is stirred for 15 minutes. The precipitate after stirring is filtered again and dried under reduced pressure at 45°C for 1 day to obtain 75.3 g of powdered resin P-1. The weight-average molecular weight (Mw) is 28,000. １ H-NMR confirms that the structure of resin P-1 is represented by formula P-1.

[0427] [Synthesis Examples P-2 to P-16: Synthesis of resins P-2 to P-16 (precursors of cyclized resins)] Resins P-2 to P-16, having a weight-average molecular weight (Mw) of 30,000, can be synthesized by the same method as in Synthesis Example P-1-1, except that the raw materials, reagents, and their amounts are appropriately changed.

[0428]

[0429] Resin P-2 is a random copolymer containing the two types of repeating units described above in a molar ratio of 75:25.

[0430]

[0431]

[0432] In the structural formula of resin P-4, R represents either the group represented by R-1 or the group represented by R-2. * represents a bonding site. The molar ratio of the group represented by R-1 to the group represented by R-2 is 50:50.

[0433]

[0434]

[0435]

[0436]

[0437] Resin P-8 is a random copolymer containing the two types of repeating units described above in a molar ratio of 50:50. In the structural formula of resin P-8, R represents the group represented by R-1 or the group represented by R-3. * represents a bonding site. The molar ratio of the group represented by R-1 to the group represented by R-3 is 50:50.

[0438]

[0439]

[0440]

[0441]

[0442]

[0443]

[0444]

[0445] Resin P-15 is a random copolymer containing the two types of repeating units described above in a molar ratio of 50:50.

[0446]

[0447] Resin P-16 is a random copolymer containing the two types of repeating units described above in a molar ratio of 50:50.

[0448] [Synthesis Example P-17: Synthesis of Resin P-17 (Cyclic Resin)] -Synthesis Example AA-1- Mix 48.65 g (225 mmol) of 3,3'-dihydroxybenzidine and 375 mL of dimethylformamide in a flask. Add 98.21 g (450 mmol) of di-t-butyl dicarbonate dropwise under ice cooling. Stir at 60°C for 5 hours after the addition is complete. After the reaction is complete, cool to room temperature, then add 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, and stir at 60°C for 3 hours. After the reaction is complete, filter by suction filtration and add the filtrate dropwise to 500 mL of water. White crystals precipitated, and the precipitated solid was collected by suction filtration. The obtained white solid was recrystallized and purified using 1000 mL of acetone at 60°C. 125 g (85.6% yield) of the following intermediate (AA-1a) was obtained. The structure of (AA-1a) is shown below. The following structure is １ This is confirmed by the 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)

[0449]

[0450] Mix 75.0 g (115.6 mmol) of (AA-1a) with 500 mL of methylene chloride in a flask. Add 131.8 g (1156 mmol) of trifluoroacetic acid at room temperature, then stir at 40°C for 5 hours. After the reaction is complete, add 250 mL of methanol and then 117.0 g (1156 mmol) of triethylamine dropwise under ice cooling. Pale yellow crystals will precipitate, and collect the precipitated solid by suction filtration. Wash with 750 mL of methanol to obtain 40.5 g of (AA-1) (yield 73%). The structure of (AA-1) is shown below. The structure shown below is １ This is confirmed by the 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)

[0451]

[0452] -Synthesis Example AT-1- (AT-1) was obtained by the same method as in Synthesis Example AA-1, except that 3,3'-dihydroxybenzidine was replaced with p-methoxyphenol. The structure of (AT-1) is shown below. The following structure is １ This is confirmed by the H-NMR spectrum. １ H-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)

[0453]

[0454] Dissolve 30.0 g (57.64 mmol) of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride and 0.08 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical in 120 g of N-methylpyrrolidone (NMP) to obtain a solution. Then, dissolve 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) in 100 g of NMP, and add dropwise to the above solution over 1 hour at a temperature of 0°C to 10°C. Stir at 25°C for 60 minutes, then add 18.2 g of pyridine and 14.7 g of acetic anhydride, and react at 80°C for 4 hours. After the reaction is complete, cool to 25°C and dilute with 200 g of tetrahydrofuran. Next, the reaction solution is added dropwise to a mixture of 2.0 L of methanol and 0.5 L of water, stirred for 15 minutes, and then the polyimide is filtered. Next, the resin is re-slurred with 1 L of water, filtered, re-slurred again with 1 L of methanol, filtered, and dried under reduced pressure at 40°C for 10 hours. Then, the dried resin is dissolved in 250 g of tetrahydrofuran, 40 g of ion exchange resin (MB-1: Organo Co., Ltd.) is added, stirred for 4 hours, the ion exchange resin is filtered and removed, and then the polyimide is precipitated in 2 L of methanol and stirred for 15 minutes. The polyimide is filtered and dried under reduced pressure at 45°C for 1 day to obtain cyclized resin P-17. The weight-average molecular weight of the obtained cyclized resin P-17 is 30,000. Cyclized resin P-17 is a resin having repeating units represented by the following formula P-17. The structure of the repeating unit is: １ It is determined from the H-NMR spectrum.

[0455]

[0456] Resin P-17 is a random copolymer containing the two types of repeating units described above in a molar ratio of 50:50. The terminal structure of resin P-17 (resin terminal structure) is represented by the group R-4. * indicates a bonding site.

[0457] [Synthesis Example P-18: Synthesis of Resin P-18 (Cyclic Resin)] 33.6 g (64.5 mmol) of 4,4'-(4,4'-isopropylidene diphenoxy)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 the mixture was stirred at 200°C for 3 hours under a nitrogen atmosphere to obtain polyimide. Next, 0.1 g of TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl free radical) and 50.4 g (324 mmol) of MOI (2-isocyanatoethyl methacrylate) are added at room temperature, and after raising the temperature to 60°C, 0.1 g of Neostan U-600 (manufactured by Nitto Kasei Co., Ltd., inorganic bismuth) is added and the mixture is stirred for 3 hours. 630 ml of THF is added to the resulting polyimide solution, and the mixture is added dropwise to 2500 ml of methanol to precipitate the polymer. The polymer is filtered and collected, and dried under reduced pressure at 40°C for 1 day to obtain 40 g of polyimide cyclized resin P-18 as a powder. The weight-average molecular weight of the obtained cyclized resin P-18 is 30,000. Cyclized resin P-18 is a resin having repeating units represented by the following formula P-18. The structure of the repeating unit is: １ It is determined from the H-NMR spectrum.

[0458]

[0459] Resin P-18 is a random copolymer containing the two types of repeating units described above in a molar ratio of 50:50. The terminal structure of resin P-18 (resin terminal structure) is represented by the group R-5. * indicates a bonding site.

[0460] [Synthesis Examples P-19 to P-21: Synthesis of Resins P-19 to P-21 (Cyclic Resins)] Resins P-19 to P-22, having a weight-average molecular weight (Mw) of 30,000, can be synthesized by the same method as in Synthesis Example P-18, except by appropriately changing the raw materials, reagents, and their amounts.

[0461]

[0462] Resin P-19 is a random copolymer containing the two types of repeating units described above in a molar ratio of 50:50. The terminal structure of resin P-19 (resin terminal structure) is represented by the group R-6. * indicates a bonding site.

[0463]

[0464] Resin P-20 is a random copolymer containing the four types of repeating units described above in a molar ratio of 25:25:25:25. The terminal structure of resin P-20 (resin terminal structure) is represented by the group R-4. * indicates a bonding site.

[0465]

[0466] Resin P-21 is a random copolymer containing the four types of repeating units described above in a molar ratio of 25:25:25:25. The terminal structure of resin P-21 (resin terminal structure) is represented by the group R-4. * indicates a bonding site.

[0467] [Synthesis Example P-22: Synthesis of Resin P-22 (Cyclic Resin)] 33.6 g (64.5 mmol) of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride and 21.7 g (52.9 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane are dissolved in 200 ml of NMP and stirred at 200°C for 3 hours under a nitrogen atmosphere. 630 ml of THF is added to the resulting polyimide solution, and the mixture is added dropwise to 2500 ml of methanol to precipitate the polymer. The polymer is filtered and collected, then dried under reduced pressure at 40°C for 1 day to obtain polyimide P-22 as a powder with a weight-average molecular weight of 30,000.

[0468]

[0469] <Examples 1-161 and Comparative Examples 1-3> In each example, the components listed in the table below were mixed to obtain each resin composition. In the comparative examples, the components listed in the table below were mixed to obtain comparative compositions. Specifically, the content of each component listed in the table was the amount (parts by mass) indicated in the "parts by mass" column of each column in the table. The amount of solvent used was the amount that resulted in the solid content concentration of the composition being the "solid content concentration (mass%)" in the table, and the solvent was mixed at the mixing ratio (mass ratio) indicated in the "ratio" column of each solvent. The obtained resin compositions and comparative compositions were pressure filtered using a polytetrafluoroethylene filter with a pore size of 0.8 μm. In the table, "-" indicates that the composition does not contain the corresponding component.

[0470] When two or more compounds are used as components other than additives and solvents, the "Type" and "Parts by Mass" columns are separated by a " / ". Furthermore, when two or more compounds are used as resin P, the "Mw" column is also separated by a " / ". In these columns, the order of entries separated by " / " corresponds to each other. When two or more additive and solvent components are included, the amount of the component listed in the "Type" column is the "Parts by Mass" listed in the column immediately below it (i.e., the column directly below the "Type" column).

[0471]

[0472]

[0473]

[0474]

[0475]

[0476]

[0477]

[0478]

[0479]

[0480]

[0481]

[0482]

[0483]

[0484]

[0485]

[0486]

[0487]

[0488]

[0489]

[0490]

[0491]

[0492] [Resin P] ・P-1 to P-22: Resins P-1 to P-22 described in the above synthesis example. The weight-average molecular weight (Mw) of each resin is shown in the table.

[0493] [Polymerizable Compounds] ・M-1: NK Ester 4G (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) ・M-2: Compound with the following structure (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0494]

[0495] • M-3: NK Ester A-DCP (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) • M-4: Viscoat #802 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) • M-5: NK Ester TMPT (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) • M-6: NK Ester A-9300 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0496] [Polymerization Initiators] ・I-1: IRGACURE OXE 01 (BASF) ・I-2: Compound with the following structure

[0497]

[0498] • I-3: Compound with the following structure (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0499]

[0500] • I-4: Compound with the following structure (manufactured by Sartomer)

[0501]

[0502] • I-5: TR-PBG-304 (manufactured by TRONLY) • I-6: TR-PBG-305 (manufactured by TRONLY) • I-7: TR-PBG-3057 (manufactured by TRONLY) • I-8: Compound with the following structure

[0503]

[0504] I-9: Benzoyl peroxide (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0505] [Base Generators] ・AR-1 to AR-5: Compounds with the following structure

[0506]

[0507] [Compound A] ・A-1 to A-9: Compounds with the following structure (manufactured by Tokyo Chemical Industry Co., Ltd.) ・A-10 to A-15: Compounds with the following structure

[0508]

[0509] [Synthesis of Compound A] -Synthesis of Compounds A-10 to A-14- Compounds A-10 to A-14 can be synthesized in accordance with the method described in International Publication No. 2022 / 034201, except that the raw materials used and their amounts are appropriately changed.

[0510] -Synthesis of Compound A-15- Compound A-15 can be synthesized according to the method described in Japanese Patent Publication No. 48-037422, except that the raw materials used and their amounts are appropriately changed.

[0511] [Polymerization inhibitors] ・B-1 to B-5: Compounds with the following structure (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0512]

[0513] [Silane coupling agent] ・C-1: Compound with the structure shown below ・C-2: Compound with the structure shown below ・C-3: Compound with the structure shown below ・C-4: Compound with the structure shown below ・C-5: X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.) ・C-6: KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0514]

[0515] [Antioxidants] ・D-1: Compound with the following structure

[0516]

[0517] • D-2: Irganox 3114 (BASF) • D-3: Irganox 1330 (BASF) • D-4: Irganox 1010 (BASF) • D-5: Irganox MD 1024 (BASF)

[0518] [Migration Inhibitors] ・E-1: Benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.) ・E-2: 8-Azaadenine (manufactured by Tokyo Chemical Industry Co., Ltd.) ・E-3: 5-Aminotetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.) ・E-4: Tetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0519] [Additives] ・F-1: N-phenyldiethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.) ・F-2: Compound with 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: Methyl acetoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) ・F-6: Ethyl acetoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) ・F-7: Tetraisopropyl titanate (manufactured by Tokyo Chemical Industry Co., Ltd.) • F-8: Compound with the following structure • F-9: Compound with the following structure • F-10: Compound with the following structure • F-11: Ester of 2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-1,1'-spirobi(1H-indene)-5,5',6,6',7,7'-hexaol and 1,2-naphthoquinone-2-diazo-5-sulfonic acid (NQD (naphthoquinone diazide)) • F-12: Compound with the following structure • F-13: Compound with the following structure • F-14: Compound with the following structure • F-15: Compound with the following structure

[0520]

[0521] [Solvents] ・S-1: γ-Butyrolactone (manufactured by Tokyo Chemical Industry Co., Ltd.) ・S-2: Dimethyl sulfoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) ・S-3: N-methyl-2-pyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) ・S-4: Ethyl lactate (manufactured by Tokyo Chemical Industry Co., Ltd.) ・S-5: γ-Valerolactone (manufactured by Tokyo Chemical Industry Co., Ltd.) ・S-6: 3-Methoxy-N,N-dimethylpropanamide (manufactured by Tokyo Chemical Industry Co., Ltd.) ・S-7: 3-Butoxy-N,N-dimethylpropanamide (manufactured by KJ Chemicals Co., Ltd.) ・S-8: Cyclopentanone (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0522] <Evaluation> [Evaluation of void suppression after high-temperature storage test] The following evaluation was performed using the resin composition of the example and the comparative composition of the comparative example. The results obtained are shown in the table above. The resin composition or comparative composition prepared in each example and comparative example was applied in layers by spin coating onto an 8-inch Si wafer with a Cu (copper) wiring pattern (Si wafer with a 1:1 line-and-space pattern (comb-type) Cu wiring pattern with a width of 10 μm and a thickness of 5 μm) (hereinafter also referred to as "substrate") that had not undergone pretreatment, to form a resin composition layer or comparative composition layer. The substrate on which the obtained resin composition layer or comparative composition layer was formed was dried on a hot plate at 100°C for 5 minutes to form a resin composition layer or comparative composition layer on the substrate with a uniform thickness and the film thickness indicated in the "Film Thickness (μm)" column of the table. The resin composition layer or comparative composition layer on the substrate was subjected to 500 mJ / cm². ２Exposure is performed with the specified exposure energy. In the example where "M" is written in the "Exposure Conditions" column of the table, a stepper is used as the light source, and exposure is performed with light of the exposure wavelength (nm) listed in the "Exposure Wavelength (nm)" column of the table. In the example where "D" is written in the "Exposure Conditions" column of the table, a direct exposure device (Adtec DE-6UH III) is used as the light source, and a photomask is not used. Laser direct imaging exposure is performed over a 100 μm square area with light of the exposure wavelength (nm) listed in the "Exposure Wavelength (nm)" column of the table. After that, development is performed for 60 seconds with the developer listed in the table to obtain a 100 μm square resin layer. "CP" in the table represents cyclopentanone. "GBL" in the table represents γ-butyrolactone. "CP / GBL" in the table represents a developer containing CP and GBL in a CP / GBL (mass ratio) of 1 / 1. In the table, if "-" is indicated in the columns for exposure wavelength, exposure conditions, or developer, exposure and development are not performed. In the case where a numerical value is indicated in the "Cure Temperature" column of the table, the resin layer after exposure is heated using a hot plate in a nitrogen atmosphere at a heating rate of 10°C / min until it reaches the temperature indicated in the "Cure Temperature (°C)" column of the table, and then maintained at the above temperature for the time (minutes) indicated in the "Cure Time (min)" column of the table to obtain a cured product. In the case where "IR" is indicated in the "Cure Temperature (°C)" column of the table, the resin layer is heated using an infrared lamp heating device (Advance Riko Co., Ltd., RTP-6) in a nitrogen atmosphere at a heating rate of 10°C / min until it reaches 230°C, and then maintained at the above temperature for 180 minutes to obtain a cured product. The substrate with the obtained cured product is left in a chamber at a temperature of 175°C under atmospheric pressure for 192 hours. Cross-sectional SEM (scanning microscope) measurements were performed to evaluate the void area ratio between the hardened material and the Cu wiring pattern (metal layer). The void area ratio was calculated using the following formula: Void area ratio (%) = (Area of ​​voids observed by SEM measurement) / (Area of ​​Cu wiring observed by SEM measurement) × 100. The obtained void area ratio value was evaluated according to the evaluation criteria below. The evaluation results are recorded in the "Void Suppression" column of the table.The smaller the void area ratio, the better the adhesion of the cured material after high-temperature storage testing. This means that corrosion of the metal wiring can be suppressed even when exposed to high-temperature conditions, and the formation of voids between the cured material and the metal layer can be suppressed over a long period of time. -Evaluation Criteria- A: Void area ratio is 0.5% or less. B: Void area ratio is greater than 0.5% and 1.0% or less. C: Void area ratio is greater than 1.0% and 1.5% or less. D: Void area ratio is greater than 1.5%.

[0523] [Evaluation of copper oxide film thickness after high-temperature storage test] The following evaluations were performed using the resin composition of the example and the comparative composition of the comparative example, and the results obtained are shown in the table above. A substrate with a cured product prepared in the same manner as above was subjected to a high-temperature storage test, which involved leaving it in a chamber at 175°C under atmospheric pressure for 192 hours. Cross-sectional SEM (scanning microscope) measurements were performed to measure the thickness of the copper oxide film between the Cu wiring pattern and the cured product. The thickness of the obtained copper oxide film was evaluated according to the evaluation criteria below. The evaluation results are shown in the "Suppression of copper oxide film thickness" column of the table. The smaller the thickness of the copper oxide film, the more the deformation of the Cu wiring pattern is suppressed. -Evaluation criteria- A: The thickness of the copper oxide film is 130 nm or less. B: The thickness of the copper oxide film is greater than 130 nm and 150 nm or less. C: The thickness of the copper oxide film is greater than 150 nm and 170 nm or less. D: The thickness of the copper oxide film is greater than 170 nm.

[0524] From the above results, it can be seen that the cured product formed from the resin composition of the present invention can suppress the formation of voids between the cured product and the metal layer, even when exposed to high-temperature conditions. Furthermore, it can be seen that the cured product formed from the resin composition of the present invention is less prone to copper oxide formation, even when exposed to high-temperature conditions. Therefore, even when the cured product formed from the resin composition of the present invention is in contact with the metal layer for a long period of time or is exposed to high-temperature conditions, the adhesion between the cured product and the metal layer does not deteriorate easily, and corrosion of metal wiring can be suppressed. The comparative composition does not contain compound A. It can be seen that the cured product formed from the comparative composition develops voids and copper oxide between the metal layer and the cured product after a long period of time.

[0525] <Examples 1001-1161> The resin compositions used in Examples 1-161 are applied in layers to the surface of a copper thin layer formed on a resin substrate by spin coating, and dried at 100°C for 5 minutes to form a photosensitive film with a thickness of 20 μm. Then, the film is exposed using a stepper (Nikon Corporation, NSR1505 i6). Exposure is 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 above exposure, the film is developed with cyclopentanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain the layer pattern. Next, the film is heated in a nitrogen atmosphere at a heating rate of 10°C / min until it reaches 230°C, and then maintained at 230°C for 180 minutes to form an interlayer insulating film for redistribution layers. This interlayer insulating film for redistribution layers has excellent insulating properties. Semiconductor devices are also manufactured using this interlayer insulating film for redistribution layers. The semiconductor devices in all of the embodiments operate without any problems.

[0526] The present invention provides a resin composition that yields a cured product in which the generation of voids and metal oxides between the cured product and the metal layer is suppressed over a long period of time, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for manufacturing the cured product, a method for manufacturing the laminate, a method for manufacturing a semiconductor device including the method for manufacturing the cured product, and a semiconductor device containing the cured product.

[0527] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application No. 2024-166570, filed on 25 September 2024, the contents of which are incorporated herein by reference.

Claims

1. A resin composition comprising at least one resin P selected from the group consisting of cyclized resins and precursors of cyclized resins, and a compound A represented by the following formula (1). In formula (1), R １１ ~R １５ Each of these independently represents a hydrogen atom or a substituent. １１ ~R １５ At least two of them may be joined together to form a ring. １１ This represents a group represented by the following formula (G-1) or (G-2). In formulas (G-1) and (G-2), * represents a bonding site. In formula (G-2), R Ａ１１ represents a hydrogen atom or substituent.

2. R in formula (1) above １５ The resin composition according to claim 1, wherein represents a hydrogen atom.

3. R in the formula (1) １１ and R １４ represent a hydrogen atom, and the resin composition according to claim 1.

4. R in formula (1) above １２ and R １３ The resin composition according to claim 3, wherein at least one of the atoms represents a hydrogen atom.

5. The resin composition according to claim 1, wherein the molecular weight of compound A is 750 or less.

6. The resin composition according to claim 1, wherein the resin P is polyimide or a polyimide precursor.

7. The resin composition according to claim 1, satisfying at least one of the following (i) and (ii): (i) The resin P has radical polymerizable groups. (ii) The resin composition comprises a compound having radical polymerizable groups in addition to the resin P and the compound A.

8. The resin composition according to claim 1, wherein the content of compound A is 0.005 to 30% by mass with respect to the total solid content of the resin composition.

9. A resin composition according to any one of claims 1 to 8, used for forming an interlayer insulating film for a redistribution layer.

10. A cured product obtained by curing the resin composition according to any one of claims 1 to 8.

11. A laminate comprising two or more layers made of the cured material described in claim 10, wherein a metal layer is included between any of the layers made of the cured material.

12. 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 8 onto a substrate to form a film.

13. A method for producing a cured product according to claim 12, comprising an exposure step of selectively exposing the film, and a developing step of developing the film using a developer to form a pattern.

14. A method for producing a cured product according to claim 13, comprising a heating step of heating the film to 50 to 450°C.

15. A method for manufacturing a laminate, comprising the method for manufacturing a cured product described in claim 14.

16. A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured product as described in claim 14.

17. A semiconductor device comprising the cured product described in claim 10.

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