Photocurable resin composition, cured product, laminate, method for producing cured product, method for producing laminate, method for producing semiconductor device, semiconductor device, and photobase generator

Abstract

Provided are: a photocurable resin composition containing a compound represented by formula (A-1) and a resin that is a polyimide precursor having a polymerizable group; a cured product obtained by curing the photocurable 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; a semiconductor device including the cured product; and a novel base generator.

Description

Photocurable resin composition, cured product, laminate, method for manufacturing the cured product, method for manufacturing the laminate, method for manufacturing a semiconductor device, semiconductor device, and photobase generator

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

[0002] In modern times, resin materials manufactured from resin compositions containing resins are utilized in various fields. For example, resins such as polyimide are used in 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, resins such as polyimide are used in the form of a photocurable resin composition containing a resin such as a polyimide precursor. Such a photocurable resin composition can be applied to a substrate, for example by coating, to form a resin film, and then, if necessary, exposure, development, heating, etc., can be performed to form a cured product on the substrate. Since photocurable resin compositions can be applied by known methods, they offer excellent manufacturing adaptability, such as a high degree of freedom in designing the shape, size, and application position of the photocurable resin composition to be applied. In addition to the high performance of resins such as polyimide, the industrial application development of the above-mentioned photocurable resin compositions is increasingly expected from the viewpoint of such excellent manufacturing adaptability.

[0004] For example, Patent Document 1 describes a photosensitive resin composition characterized by containing a carboxylic acid represented by and an ionic base generator of a base.

[0005] International Publication No. 2017 / 141734

[0006] In photocurable resin compositions containing polyimide precursors, curing at low temperatures is sometimes performed from the viewpoint of suppressing thermal deformation of the substrate and other components, and saving energy. For example, in recent years, due to reasons such as the multilayering of semiconductor laminates, heating at high temperatures (e.g., 200°C or higher) can cause warping of the semiconductor substrate, so curing at low temperatures (e.g., 180°C or lower) is desired.

[0007] The present invention aims to provide a photocurable resin composition that yields a cured product with excellent film strength even when cured at low temperatures, a cured product obtained by curing the photocurable 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. The present invention also aims to provide a novel base generator.

[0008] Examples of typical embodiments of the present invention are shown below. <1> A photocurable resin composition containing a compound represented by formula (A-1) and a resin which is a polyimide precursor having polymerizable groups. In formula (A-1), Ar represents an aromatic ring structure, or a structure in which two or more single bonds or aromatic ring structures are linked by a linking group, R １ <2> The photocurable resin composition according to <1>, wherein the compound represented by formula (A-1) comprises the compound shown in formula (A-2a) or formula (A-2b) below. In equations (A-2a) and (A-2b), R １２ represents an acyl group or a nitro group, m2 represents 0 or 1, L ａ１is a single bond, -O-, -S-, -NR Ｎ２ -, -C(R ｘ１ R ｘ２ ), -C(=O)-, and L ａ２ is a single bond, -O-, -S-, -NR Ｎ２ -, -C(R ｘ１ R ｘ２ ), -C(=O)-, R Ｎ２ , R ｘ１ and R ｘ２ each independently represents a monovalent organic group, y represents 0 or 1. When y is 0, L ａ２ does not exist, and R ｙ１ and R ｙ２ each independently represents a monovalent organic group. y1 and y2 each independently represent an integer from 0 to 3. When y1 and y2 are 2 or more, adjacent R ｙ１ to each other or adjacent R ｙ２ to each other may combine to form a ring. X is a counter cation, which is a cation containing a positively charged nitrogen atom. <3> The photocurable resin composition according to <1> or <2>, wherein X is a cation represented by the following formulas (X-1) to (X-4). In the formulas (X-1) to (X-4), R １０１ to R １１９ each independently represents a hydrogen atom, an alkyl group or an aryl group, and R １０１ to R １１９Adjacent groups among them may form a ring via any linking group. <4> The photocurable resin composition according to <3>, wherein X is a cation represented by formula (X-2), formula (X-3), or formula (X-4). <5> The photocurable resin composition according to any one of <1> to <4>, wherein the acid dissociation constant pKa at 25°C in a dimethyl sulfoxide solution of the conjugate acid of the amine in X is 10 to 45. <6> The photocurable resin composition according to any one of <1> to <5>, further comprising a radical polymerization initiator different from the compound represented by formula (A-1). <7> The photocurable resin composition according to <6>, wherein the radical polymerization initiator different from the compound represented by formula (A-1) is a (keto)oxime ester compound. <8> The photocurable resin composition according to any one of <1> to <7>, wherein the resin has at least one of the substructure represented by the following formula (B-1) and the substructure represented by formula (B-2). In formula (B-1), X １ represents an organic group with 4+m valence, Y １ represents a 2+n valent organic group, R １ R represents a group containing a polymerizable group. ２ represents a group containing a polymerizable group, n is an integer from 0 to 6, m is an integer from 0 to 6, and n+m is an integer of 1 or more. In formula (B-2), X １ represents an organic group with 4+m valence, Y １ represents a 2+n valent organic group, A ｘ１ and A ｘ２ represents a monovalent organic group, R １ R represents a group containing a polymerizable group. ２ represents a group containing a polymerizable group, n is an integer from 0 to 6, m is an integer from 0 to 6, and n+m is an integer of 1 or more, where A ｘ１ and A ｘ２ If at least one of them has a polymerizable group, then n+m may be 0. <9> R in formula (B-1) above １ and R ２ , and also R in formula (B-2) １ , R ２ A ｘ１ and A ｘ２The photocurable resin composition according to <8>, wherein the group contains a group having an ethylenically unsaturated bond. <10> The X in the above formulas (B-1) and (B-2) １ A photocurable resin composition according to <8> or <9>, wherein the group is a group having an alicyclic hydrocarbon. <11> A photocurable resin composition according to any one of <1> to <10>, further comprising a polymerizable compound with a molecular weight of less than 3,000. <12> A photocurable resin composition according to any one of <1> to <11>, further comprising an amine compound. <13> A photocurable resin composition according to any one of <1> to <12>, further comprising a sensitizer. <14> A photocurable resin composition according to any one of <1> to <13>, further comprising a chain transfer agent. <15> A cured product obtained by curing a photocurable resin composition according to any one of <1> to <14>. <16> A laminate comprising two or more layers made of the cured product according to <15>, with a metal layer between any of the layers made of the cured product. <17> A method for producing a cured product, comprising a film-forming step of applying a photocurable resin composition according to any one of <1> to <16> onto a substrate to form a film. <18> A method for producing a cured product according to <17>, comprising an exposure step of selectively exposing the film and a developing step of developing the film using a developer to form a pattern. <19> A method for producing a cured product according to <17> or <18>, comprising a heating step of heating the film at 50 to 450°C. <20> A method for producing a laminate, comprising a method for producing a cured product according to any one of <17> to <19>. <21> A method for producing a semiconductor device, comprising a method for producing a cured product according to any one of <17> to <19>. <22> A semiconductor device comprising the cured product according to <15>. <23> A base generator represented by the following formula (A-1). In formula (A-1), Ar represents an aromatic ring structure, or a structure in which two or more aromatic ring structures are linked by a linking group, and R １is a monovalent organic group or halogen atom, n1 is an integer from 1 to 4, and all n1 structures are bonded to the aromatic ring structure of Ar by a single bond without a linking group, m1 is an integer from 0 to 4, X is a countercation and is a cation containing a positively charged nitrogen atom, nx1 is an integer of 1 or more, and when X is an a-valent cation, (a × nx1) is the same number as n1, and when X is a quaternary alkylammonium cation, m1 is 1 to 4, or n1 is 2 or more, or Ar is a substituted phenyl group or an aromatic ring structure other than a phenyl group. <24> The base generating agent described in <23>, represented by the following formula (A-2a) or formula (A-2b). In equations (A-2a) and (A-2b), R １２ represents an acyl group or a nitro group, m2 represents 0 or 1, L ａ１ These are single bonds, -O-, -S-, -NR Ｎ２ -, -C(R ｘ１ R ｘ２ ) -, -C (=O) -, L ａ２ These are single bonds, -O-, -S-, -NR Ｎ２ -, -C(R ｘ１ R ｘ２ ) represents either - or -C (=O)-, R Ｎ２ , R ｘ１ and R ｘ２ Each of these independently represents a monovalent organic group, and y indicates either 0 or 1, where 0 is L ａ２ It does not exist, R ｙ１ and R ｙ２ Each independently represents a monovalent organic group, y1 and y2 independently represent integers from 0 to 3, and if y1 and y2 are 2 or greater, adjacent R ｙ１ R's mutual or adjacent R's ｙ２ They may bond with each other to form a ring, and X is a countercation, a cation containing a positively charged nitrogen atom. <25> The base generator according to <23> or <24>, wherein the above X is a cation represented by the following formulas (X-1) to (X-4). In formulas (X-1) to (X-4), R １０１ ~R １１９ Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and R１０１ ~R １１９ Adjacent groups may form a ring via any linking group. <26> The base generating agent according to any one of <23> to <25>, wherein the acid dissociation constant pKa at 25°C in the dimethyl sulfoxide solution of the conjugate acid of the amine in X is 10 to 45.

[0009] The present invention provides a photocurable resin composition that yields a cured product with excellent film strength even when cured at low temperatures, a cured product obtained by curing the photocurable resin composition, a laminate containing 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 containing the cured product. Furthermore, the present invention provides a novel base generator.

[0010] 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.

[0011] (Photocurable resin composition) The photocurable resin composition of the present invention (hereinafter also simply referred to as "photocurable resin composition") contains a compound represented by formula (A-1) (hereinafter also referred to as "compound A") and a resin which is a polyimide precursor having polymerizable groups. In formula (A-1), Ar represents an aromatic ring structure, or a structure in which two or more aromatic ring structures are linked by a linking group, and R １ is a monovalent organic group or halogen atom, n1 is an integer from 1 to 4, and all n1 structures are bonded by a single bond to the aromatic ring structure of Ar, m1 is an integer from 0 to 4, X is a countercation containing a positively charged nitrogen atom, nx1 is an integer of 1 or more, and if X is an a-valent cation, (a × nx1) is the same number as n1, and if X is a quaternary alkylammonium cation, then m1 is 1 to 4, or n1 is 2 or more, or Ar is a substituted phenyl group or an aromatic ring structure other than a phenyl group.

[0012] The photocurable 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 photosensitive film subjected to exposure and development using a developer containing an organic solvent. The photocurable 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 photocurable resin composition of the present invention is preferably used to form a photosensitive film subjected to negative-type development. In the present invention, negative-type development refers to development in which unexposed areas are removed by development during exposure and development, and positive-type development refers to development in which exposed areas are removed by development. As the above exposure method, the above developer, and the above development method, for example, the exposure method, the developer, and the development method described in the exposure step, and the development step, respectively, in the description of the method for manufacturing a cured product described later, can be used.

[0013] The photocurable resin composition of the present invention yields a cured product with excellent film strength even when cured at low temperatures. The mechanism by which the above effect is obtained is unknown, but it is presumed to be as follows.

[0014] The compound represented by formula (A-1) has n units of structure that are bonded to the aromatic ring structure of Ar by single bonds without linking groups, thus extending the conjugated structure and resulting in longer absorption wavelengths. This is thought to allow for sufficient decomposition by exposure light, generating bases. Furthermore, the compound represented by formula (A-1) undergoes photobleaching after absorbing exposure light, making base generation more likely even in the deeper parts of the film. These generated bases promote imidation in polyimide and polyimide precursors during subsequent heating, resulting in cured products with excellent mechanical properties even at low temperatures. Additionally, the anion in the compound represented by formula (A-1) is a relatively strong acid anion and is thought to form a strong salt with the countercation. As a result, the compound represented by formula (A-1) is less likely to decompose in the composition, and the compound itself is thought to have a long pot life. Moreover, because the compound represented by formula (A-1) is less likely to decompose as described above, base generation during storage of the composition is suppressed, the promotion of resin imidation in the composition is suppressed, and the storage stability of the composition is increased. Furthermore, because it possesses a photodegradation mechanism accompanied by decarboxylation, it functions not only as a base generator but also as a radical polymerization initiator, and is thought to contribute to radical polymerization in pattern formation. Moreover, it is thought that the generation of a sufficient amount of base promotes the decomposition and elimination of polymerizable groups in the resin present in the polyimide precursor.

[0015] Furthermore, Patent Document 1 neither describes nor suggests any photocurable resin composition containing a resin that falls under the category of a specific resin.

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

[0017] <Compound A> The photocurable resin composition of the present invention contains a compound represented by formula (A-1) (Compound A). In formula (A-1), Ar represents an aromatic ring structure, or a structure in which two or more aromatic ring structures are linked by a single bond or a linking group, R １is a monovalent organic group or halogen atom, n1 is an integer from 1 to 4, and all n1 structures are bonded by a single bond to the aromatic ring structure of Ar, m1 is an integer from 0 to 4, X is a countercation containing a positively charged nitrogen atom, nx1 is an integer of 1 or more, and if X is an a-valent cation, (a × nx1) is the same number as n1, and if X is a quaternary alkylammonium cation, then m1 is 1 to 4, or n1 is 2 or more, or Ar is a substituted phenyl group or an aromatic ring structure other than a phenyl group.

[0018] In this invention, "glyoxylate" means R-(C=O)-(C=O)-O － This indicates that R represents a hydrogen atom or an organic group. A "glyoxylate group" is *-(C=O)-(C=O)-O － The group is represented by , and * indicates a bonding site with another element.

[0019] [Ar] In formula (A-1), Ar represents an aromatic ring structure, or a structure in which two or more aromatic ring structures are linked by a single bond or a linking group. The aromatic ring in Ar may be an aromatic hydrocarbon ring or an aromatic heteroring. As the aromatic hydrocarbon ring, a hydrocarbon ring having 6 to 20 carbon atoms is preferred, and a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, or pyrene ring is preferred, with a benzene ring being even more preferred. As the aromatic heteroring, a hydrocarbon ring having 6 to 20 ring members is preferred, and an aromatic heteroring having 5 or 6 ring members, or a ring structure formed by the condensation of a heteroaromatic ring having 5 or 6 ring members and a benzene ring is even more preferred. Examples of aromatic heterocycles include pyridine rings, pyrimidine rings, pyrazine rings, triazine rings, pyrrole rings, imidazole rings, pyrazole rings, oxazole rings, thiazole rings, triazole rings, furan rings, thiophene rings, benzofuran rings, benzothiophene rings, indole rings, indazole rings, dibenzofuran rings, dibenzothiophene rings, carbazole rings, benzocarbazole rings, fluorene rings, and benzofluorene rings. In aromatic heterocycles, the heteroatoms are preferably oxygen atoms, sulfur atoms, or nitrogen atoms.

[0020] In a structure in which two or more aromatic ring structures are linked by a single bond or a linking group, examples of the linking group include -O-, -S-, -NR Ｎ２ -, -C(R ｘ１ R ｘ２ ), -C(=O)-, -S(=O)-, -S(=O) ２ - or a group represented by a combination thereof, and -O-, -S-, -NR Ｎ２ - or -C(R ｘ１ R ｘ２ )- are more preferable. R Ｎ２ , R ｘ１ and R ｘ２ each independently represent a monovalent organic group, and an alkyl group or an aryl group is preferable. As the above alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, an alkyl group having 1 to 4 carbon atoms is further preferable, and a methyl group is particularly preferable. The above alkyl group may be linear, branched, cyclic, or any structure formed by these bonds. The above aryl group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, but an aromatic hydrocarbon group is preferable. As the aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable, a phenyl group or a naphthyl group is more preferable, and a phenyl group is further preferable. The above alkyl group may further have a substituent, and examples of the substituent include an aryl group, an alkoxy group, an alkylcarbonyl group, a halogen atom, etc. The above aryl group may further have a substituent, and examples of the substituent include an aryl group, an alkyl group, an alkoxy group, an alkylcarbonyl group, a halogen atom, etc.

[0021] Examples of the structure in which two or more aromatic ring structures are linked by a single bond or a linking group include biphenyl, diphenyl ether, diphenyl sulfide, diphenyl methane, diphenyl ethylamine, triphenylamine, benzophenone, diphenyl sulfoxide, diphenyl sulfone, etc.

[0022] When Ar is a structure in which two or more aromatic ring structures are linked by a single bond or a linking group,

[0023] When Ar has a condensed ring structure of 3 or more rings, it is preferable that there is only one condensed ring structure of 3 or more rings in one molecule. Ar is more preferably the following structural formula group from the viewpoint of enhancing light absorption at 365 nm and enhancing base generation efficiency.

[0024] As Ar, the structure described in the following formula (X1-1) is also preferably used.

[0025] In formula (X1-1), X １１ and X １２ each independently represent an aromatic hydrocarbon group, and L ａ１ and L ａ２ each independently represent a single bond, -O-, -S-, -NR Ｎ２ -, -CR Ｘ１ R Ｘ２ - or -C(=O)-, and R Ｎ２ , R Ｘ１ and R Ｘ２ each independently represent a hydrogen atom, an alkyl group or an aryl group, and L ａ１ and L ａ２ do not simultaneously become a single bond, y represents 0 or 1, and when y is 0, L ａ２ does not exist;

[0026] In formula (X1-1), X １１ and X １２ each independently represent an aromatic hydrocarbon group. The number of carbon atoms of the aromatic hydrocarbon group represented by X １１ and X １２ is preferably 6-20, more preferably 6-18. The aromatic hydrocarbon group may be a monocyclic ring or a condensed ring. Specific examples of the aromatic hydrocarbon group include a benzene ring group, a naphthalene ring group and an anthracene ring group, preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring.

[0027] The L ａ１ and L ａ２ of formula (X1-1) each independently represent a single bond, -O-, -S-, -NR Ｎ２ -, -CR Ｘ１ R Ｘ２ - or -C(=O)-, representing a single bond, -O-, -S- or -CRＸ１ R Ｘ２ - is preferable.

[0028] In equation (X1-1), y represents either 0 or 1, and if y is 0, L ａ１ There is no such thing. That is, when y in equation (X1-1) is 0, the group represented by equation (X1-1) is the group represented by equation (X1-1a), and when y in equation (X1-1) is 1, the group represented by equation (X1-1) is the group represented by equation (X1-1b).

[0029] When y in equation (X1-1) is 0, L ａ２ is a single bond, -O-, -S- or -CR Ｘ１ R Ｘ２ It is preferable that it be -, and more preferably that it be a single bond, -O-, or -S-.

[0030] R Ｎ２ , R Ｘ１ and R Ｘ２ Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and is preferably an alkyl group or an aryl group, more preferably an alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 5. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. When the aryl group is an aromatic hydrocarbon group, the number of carbon atoms is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6 or 7. When the aryl group is an aromatic heterocyclic group, the number of carbon atoms constituting the ring is preferably 1 to 15, more preferably 1 to 10. Examples of heteroatoms include nitrogen, oxygen, and sulfur atoms. The number of heteroatoms constituting the ring is preferably 1 to 3, more preferably 1 to 2. The aryl group may be a monocyclic or a fused ring.

[0031] When y in equation (X1-1) is 1, L ａ１ It is preferable that it is a single bond. Also, L ａ２ is -O-, -S-, or -CR Ｘ１ R Ｘ２- is preferable. L ａ１ and L ａ２ The following embodiments are examples of preferred combinations: L ａ１ L is a single bond. ａ２ The state in which -O-. L ａ１ L is a single bond. ａ２ A mode in which -S-. L ａ１ L is a single bond. ａ２ ga-CR Ｘ１ R Ｘ２ - (particularly preferred, R Ｘ１ and R Ｘ２ A configuration in which each of the elements is an alkyl group having 1 to 8 carbon atoms.

[0032] The aromatic ring represented by Ar in compound A may include, but is not limited to, the following structures. These can be used in any combination. １ ~R ９ Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, with alkyl groups or aryl groups being preferred, and alkyl groups being more preferred. Preferred embodiments of alkyl groups and aryl groups are as described above. Ｎ２ , R Ｘ１ R Ｘ２ The preferred embodiments of alkyl and aryl groups are similar to those in the following formula. In particular, R ２ Ethyl groups, n-butyl groups, and 2-ethylhexyl groups are particularly preferred. ５ , R ６ It is particularly preferable that the group simultaneously be a methyl group, an ethyl group, a n-propyl group, or a n-butyl group.

[0033] Specifically, the following structural groups can be suitably used. ａ１ ~R ａ３２ Each of these independently represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyloxy group, an arylaminocarbonyloxy group, a nitro group, or a glyoxylate group, with alkyl groups or aryl groups being preferred, and alkyl groups being more preferred. Preferred embodiments of alkyl groups and aryl groups are as described above for RＮ２ , R Ｘ１ R Ｘ２ The preferred embodiments of alkyl and aryl groups are similar to those described below. The preferred embodiments of acyl groups are described in R １ This is similar to the preferred embodiment of the acyl group in [the relevant context].

[0034]

[0035] [R １ ] In formula (A-1), R １ represents a monovalent organic group or halogen atom, and alkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkylamino groups, arylamino groups, halogen atoms, acyl groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups, alkylaminocarbonyloxy groups, arylaminocarbonyloxy groups, hydroxyl groups, carboxyl groups, mercapto groups, and nitro groups are preferred. Each of these substituents may be present in multiple independent groups, and adjacent substituents may form a ring with any linking group, and the formed ring may be an aromatic ring.

[0036] The above R １ If the alkyl group is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms is more preferred, an alkyl group having 1 to 4 carbon atoms is even more preferred, and a methyl group is particularly preferred. The alkyl group may be linear, branched, cyclic, or have a structure formed by bonding these.

[0037] The above R １When the aryl group is an aryl group, it may be an aromatic hydrocarbon group or an aromatic heterocyclic group, but an aromatic hydrocarbon group is preferred. When the aryl group is an aromatic hydrocarbon group, the number of carbon atoms is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferred to be 6 or 7. When the aryl group is an aromatic heterocyclic group, the number of carbon atoms constituting the ring is preferably 1 to 15, more preferably 1 to 10. Examples of heteroatoms include nitrogen atoms, oxygen atoms, and sulfur atoms. The number of heteroatoms constituting the ring is preferably 1 to 3, more preferably 1 to 2. The aryl group may be a monocyclic or fused ring.

[0038] The above R １ When R is an acyl group, it is preferable that the acyl group be an alkylcarbonyl group or an arylcarbonyl group. １ When is an alkoxy group, alkylthio group, alkylcarbonyl group, alkylamino group, alkylcarbonyloxy group, or alkylaminocarbonyloxy group, preferred embodiments of the alkyl group in these groups are as described above. １ The preferred embodiment is the same as when R is an alkyl group. １ When is an aryloxy group, an arylthio group, an arylcarbonyl group, an arylamino group, an arylcarbonyloxy group, or an arylaminocarbonyloxy group, a preferred embodiment of the aryl group in these groups is the R described above. １ This is similar to the preferred embodiment when is an alkyl group.

[0039] [n1] n1 is an integer between 1 and 4, preferably between 2 and 4, more preferably 2 or 3, and even more preferably 2. It is also preferable that n1 be 1.

[0040] [m1] m1 represents an integer from 0 to 4, preferably an integer from 0 to 3, and more preferably an integer from 0 to 2.

[0041] [X] X is a countercation, a cation containing a positively charged nitrogen atom. X is not particularly limited as long as it has a cation on the nitrogen atom, but "N ＋ It is preferable that the structure represented by "-H" is included. The positively charged nitrogen atom is preferably substituted with an organic group, and the bonding site between the nitrogen atom and the organic group is preferably a carbon atom. The nitrogen atom and the carbon atom may be linked by a single bond (N-C) or a double bond (N=C).

[0042] X is a cation containing a nitrogen atom, and the nitrogen atom may be bonded to other atoms or structures by saturated or unsaturated bonds. The unsaturated bonds may be included in a conjugated structure and may be aromatic. It is preferable that X is a cation represented by the following formula (Xx) or formula (Xy). In equations (Xx) and (Xy), R ２０１ ~R ２０５ Each of these independently represents a hydrogen atom or an organic group, R ２０１ ~R ２０３ Two or more of these may be linked together to form a ring structure, R ２０４ and R ２０５ These may be linked together to form a ring structure.

[0043] In equations (Xx) and (Xy), R ２０１ ~R ２０５ It is preferable that R represents an organic group. ２０１ ~R ２０４ The organic group in is N as described in formulas (Xx) and (Xy). ＋ The bonding site is preferably a carbon atom, nitrogen atom, oxygen atom, sulfur atom, or phosphorus atom, and more preferably a carbon atom or nitrogen atom. In the above embodiment, R ２０１ ~R ２０４ The organic group in is also preferably a group composed of a carbon atom, nitrogen atom, oxygen atom, sulfur atom, or phosphorus atom at the aforementioned bonding site, and a carbon atom, nitrogen atom, and hydrogen atom. ２０１ ~R ２０４Examples of organic groups in this context include alkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, monoalkylamino groups, dialkylamino groups, monoarylamino groups, diarylamino groups, and alkylarylamino groups. Preferred embodiments of alkyl and aryl groups, which are or are contained within these groups, are shown below. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 2 to 10. When the aryl group is an aromatic hydrocarbon group, the number of carbon atoms is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6 or 7. When the aryl group is an aromatic heterocyclic group, the number of carbon atoms constituting the ring is preferably 1 to 15, more preferably 1 to 10. Examples of heteroatoms include nitrogen, oxygen, and sulfur atoms. The number of heteroatoms constituting the ring is preferably 1 to 3, more preferably 1 to 2. The aryl group may be a monocyclic or fused ring. ２０１ ~R ２０４ If the group is an organic group, it may have substituents. Examples of substituents include aryl groups, vinyl groups, alkyloxycarbonyl groups, epoxy groups, etc. A preferred embodiment of the aryl group as a substituent is R ２０１ ~R ２０４ The preferred embodiment of the aryl group is the same as in the above. The preferred embodiment of the alkyl group in the alkyloxycarbonyl group as a substituent is R ２０１ ~R ２０４ This is similar to the preferred embodiment of the alkyl group described above.

[0044] The above R ２０５ The organic group in formula (Xy) is N ＋ The bonding site is preferably a carbon atom, a nitrogen atom, or a phosphorus atom, and more preferably a carbon atom or a phosphorus atom. In the above embodiment, R ２０５ The organic group in the above-mentioned bond site is also preferably a group composed of a carbon atom, a nitrogen atom, or a phosphorus atom, and a carbon atom, a nitrogen atom, and a hydrogen atom. ２０５ The organic group in this case is * = C(R Ｃ１) ２ Or * = P(R) Ｐ１ ) ３ It is preferable that the group is represented by *. * represents the N listed in formula (Xy). ＋ This represents the bonding site with R. Ｃ１ Each of these independently represents a hydrogen atom or a monovalent organic group, and includes hydrogen atoms, alkyl groups, optionally substituted amino groups, and -N=R. Ｃ２ It is preferable that the group is represented by R. Ｃ２ * represents a monovalent organic group, and * = C(R Ｃ３ ) ２ Or * = P(R) Ｃ４ ) ３ It is preferable that the group is represented by *. Ｃ１ R represents the bonding site with N inside. Ｃ３ R represents a monovalent organic group, preferably an amino group that may be substituted, and more preferably a dialkylamino group substituted with an alkyl group having 1 to 4 carbon atoms. Ｃ４ R represents a monovalent organic group, and a substituted amino group is preferred. Ｐ１ Each of these independently represents a hydrogen atom, an alkyl group, an optionally substituted amino group, and -N=R Ｃ２ It is preferable that the group is represented by R. Ｃ２ The preferred embodiment is as described above. Ｃ１ , R Ｃ３ , R Ｃ４ and R Ｐ１ Examples of amino groups that may be substituted in include monoalkylamino groups, dialkylamino groups, monoarylamino groups, diarylamino groups, alkylarylamino groups, and the like. Ｃ１ and R Ｐ１ A preferred embodiment of the alkyl group in the above substituent, the alkyl group included in the above substituent, and the aryl group is R ２０１ ~R ２０４ This is similar to the preferred embodiment of the alkyl and aryl groups in the above.

[0045] R ２０１ ~R ２０３The ring structure formed by the bonding of these elements is preferably a five-membered ring or a six-membered ring, with a six-membered ring being more preferable. Furthermore, the above ring structure may form a fused ring with another ring structure. ２０４ and R ２０５ The ring structure formed by the bonding of these elements is preferably a five-membered ring or a six-membered ring, with a six-membered ring being more preferred. The formed ring may be a nitrogen-containing heteroaromatic ring containing nitrogen atoms, and may contain two or more nitrogen atoms within the same ring. Furthermore, the above ring structure may form a fused ring with another ring structure.

[0046] X may contain heteroatoms such as O, S, and P in addition to nitrogen atoms, as described in Non-Patent Literature: Angew. Chem. Int. Ed., 51, 9525-9529 (2012) and the Journal of Synthetic Organic Chemistry, Japan (Vol. 81, No. 8, (2023), p. 829) as an organic superstrong base (phosphazene (-N=PR ３ ) or (phosphatran (P-(NRR) ３ It is also preferable to have ). Specific examples of compounds are listed below: BTPP, iBu-PAP, P1-tBu, P2-tBu, ｔ Bu-P4 is one example.

[0047] Furthermore, multiple nitrogen atoms may be present in one molecule of X. The number of nitrogen atoms in one molecule of X is preferably, for example, 1 to 10, and more preferably 1 to 6. An embodiment in which the number is 2 to 6 is also one of the preferred embodiments of the present invention. Furthermore, multiple nitrogen atoms may be present in one molecule of X.

[0048] X is preferably a monovalent cation. That is, the number of positively charged nitrogen atoms in X in one molecule is preferably 1.

[0049] From the countercation X to H ＋ Excluding the above, preferred structures include primary amines (saturated and unsaturated), secondary amines (saturated and unsaturated), tertiary amines (saturated and unsaturated), quaternary amines (saturated and unsaturated), heteroaromatic rings, amidines, guanidines, and biguanides, among which amidines, guanidines, and biguanides are preferred.

[0050] Examples of primary amines include alkylamines such as hexylamine, 2-ethylhexylamine, dodecylamine, stearylamine, benzylamine, and 1-adamantylamine, and arylamines such as aniline.

[0051] Examples of secondary amines include linear aliphatic amines such as dibutylamine and N,N-(bis)hydroxyethylamine, branched aliphatic amines such as diisopropylamine, and cyclic aliphatic amines such as morpholine, thiomorpholine, piperidine, pyrrolidine, piperazine, imidazolidine, and pyrazolidine decahydroquinoline. Examples of tertiary amines include linear aliphatic amines such as triethylamine, tributylamine, trioctylamine, and diisopropylethylamine, and amines containing aromatic groups such as triphenylamine, benzyldimethylamine, DMAP (dimethylaminopyridine), N,N-dimethylaniline, and N-phenyldiethanolamine. Amines having a bridgehead position are also preferred, such as DABCO (1,4-diazabicyclo[2.2.2]octane). Examples of quaternary amines include tetrabutylammonium bromide, tetrabutylammonium acetate, benzyltributylammonium bromide, and N-(benzoylmethyl)-N.N-dimethyl-N-butylammonium bromide. Examples of divalent amines include ethylenediamine, 1,3-propanediamine, N,N'-dimethylethylenediamine (abbreviated as DMEDA), N,N,N',N'-tetramethylethylenediamine (abbreviated as TMEDA), piperazine (anhydrous), and 1,4-phenylenediamine. Examples of trivalent amines include diethylenetriamine, 2,2'-diamino-N-methyldiethylamine, N,N',N''-trimethyldiethylenetriamine, N,N,N',N'',N''-pentamethyldiethylenetriamine (abbreviated as PMDETA), 1,4,7-trimethyl-1,4,7-triazacyclononane, and N,N,N',N'',N''-pentakis(2-hydroxypropyl)diethylenetriamine. Examples of tetravalent amines include tris(2-aminoethyl)amine (abbreviated as TAEA), triethylenetetramine, 1,4,7,10-tetraazacyclododecane, tris[2-(dimethylamino)ethyl]amine (abbreviated as Me6TREN), and N,N,N',N'',N''',N'''-hexamethyltriethylenetetramine (abbreviated as HMTETA).Examples of heteroaromatic compounds include pyrrole, imidazole, pyridine, pyrimidine, pyrazole, oxazole, thiazole, triazole, tetrazole, and indole. Amidines include "R-C (=NR). １ ) - NR ２ R ３ It is not limited to those that have the "structure". １ , R ２ , R ３ Each of these groups independently represents a hydrogen atom or a substituent, and adjacent groups may form a ring. For example, DBU (1,8-diazabicyclo[5.4.0]-7-undecene), DBN (1,5-diazabicyclo[4.3.0]-5-nonene), etc., can be suitably used. As for guanidines, "R ２ R ３ N-C (=NR １ ) - NR ２ R ３ It is not limited to those that have the "structure". １ , R ２ , R ３ Each of these groups independently represents a hydrogen atom or a substituent, and adjacent groups may form a ring. For example, guanidine, cyanoguanidine, acetylguanidine, TBD (1,5,7-triazabicyclo[4.4.0]deca-5-ene), MTBD (7-methyl-1,5,7-triazabicyclo[4.4.0]deca-5-ene), TMG (1,1,3,3-tetramethylguanidine), BTMG (2-tert-butyl-1,1,3,3-tetramethylguanidine), etc. can be suitably used. Biguanides include "R ２ R ３ N-C (= N-R １ ) - NR １ ―C(=N-R) １ ) - NR ２ R ３ It is not limited to those that have an "R" structure. １ , R ２ , R ３Each of these groups independently represents a hydrogen atom or a substituent, and adjacent groups may form a ring. Examples include metformin, 1,2-dicyclohexyl-4,4,5,5-tetramethyl biguanide, and 1,2-diisopropyl-3-[bis(dimethylamino)methylene]guanide. Other examples of amino cations represented by X include biguanide compounds described in International Publication No. 2014 / 208632, compounds having an N atom and a P atom in the same molecule described in Japanese Patent Publication No. 2011-80032, and quaternary alkylamines described in International Publication No. 2015 / 199219.

[0052] Among these, X is preferably a cation represented by the following formulas (X-1) to (X-4), and more preferably a cation represented by formula (X-2), formula (X-3), or formula (X-4). In formulas (X-1) to (X-4), R １０１ ~R １１９ Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and R １０１ ~R １１９ Adjacent groups may form a ring via any linking group.

[0053] In formula (X-1), R １０１ ~R １０３ Of these, at least one preferably represents an alkyl group or an aryl group, and preferably an alkyl group. Also, in formula (X-1), R １０１ ~R １０３ Of these, at least two preferably represent an alkyl group or an aryl group, and preferably represent an alkyl group. １０１ ~R １０３ The number of carbon atoms in the alkyl group is preferably 1 to 20, and more preferably 2 to 10. １０１ ~R １０３When the aryl group in is an aromatic hydrocarbon group, the number of carbon atoms is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6 or 7. When the aryl group is an aromatic heterocyclic group, the number of carbon atoms constituting the ring is preferably 1 to 15, more preferably 1 to 10. Examples of heteroatoms include nitrogen, oxygen, and sulfur atoms. The number of heteroatoms constituting the ring is preferably 1 to 3, more preferably 1 to 2. The aryl group may be a monocyclic or fused ring. １０１ ~R １０３ If is an alkyl group or an aryl group, they may have substituents. Examples of substituents include aryl groups, vinyl groups, alkyloxycarbonyl groups, epoxy groups, etc. A preferred embodiment of the aryl group as a substituent is R １０１ ~R １０３ This is similar to the preferred embodiment of the aryl group in the above alkyloxycarbonyl group. The preferred embodiment of the alkyl group in the alkyloxycarbonyl group as a substituent is R １０１ ~R １０３ This is similar to the preferred embodiment of the alkyl group in the above.

[0054] R １０１ ~R １０３ Of these, at least two of the ring structures formed are preferably five-membered or six-membered rings, with six-membered rings being more preferred. Furthermore, if multiple ring structures are formed in the molecule, they may form fused rings.

[0055] Specific examples of the structure represented by formula (X-1) are shown below, but the present invention is not limited to these.

[0056] In formula (X-2), R １０４ ~R １０７ Of these, at least one preferably represents an alkyl group or an aryl group, and preferably an alkyl group. Also, in formula (X-2), R １０４ ~R １０７ Of these, at least two preferably represent alkyl groups or aryl groups, and preferably represent alkyl groups. １０４ ~R １０７Preferred embodiments of alkyl and aryl groups in R １０１ ~R １０３ This is similar to the preferred embodiment of these groups in (X-2). Also, in formula (X-2), R １０４ and R １０７ It is preferable that a ring structure is formed via a linking group. A six-membered ring structure is preferred as the formed ring structure, and an aliphatic six-membered ring structure is more preferred. In formula (X-2), R １０５ and R １０６ Either all of them are hydrogen atoms, or R １０５ and R １０６ It is preferable that a ring structure is formed via a linking group. A 5- to 7-membered ring structure is preferred as the formed ring structure, and an aliphatic 5- to 7-membered ring structure is more preferred.

[0057] Specific examples of the structure represented by formula (X-2) are shown below, but the present invention is not limited to these.

[0058] In formula (X-3), R １０８ ~R １１２ Of these, at least one preferably represents an alkyl group or an aryl group, and preferably an alkyl group. Also, in formula (X-3), R １０８ ~R １１２ Of these, at least two preferably represent alkyl groups or aryl groups, and preferably represent alkyl groups. １０８ ~R １１１ Preferred embodiments of alkyl and aryl groups in R １０１ ~R １０３ This is similar to the preferred embodiment of these groups in (X-3). Also, in formula (X-3), R １０８ and R １１２ It is preferable that a ring structure is formed via a linking group. A six-membered ring structure is preferred as the formed ring structure, and an aliphatic six-membered ring structure is more preferred. In formula (X-3), R １１０ and R １１１ It is also preferable that a ring structure is formed via a linking group. A 5- to 7-membered ring structure is preferred as the formed ring structure, and an aliphatic 5- to 7-membered ring structure is more preferred. Among these, in formula (X-3), R １０９R represents a hydrogen atom or an alkyl group. １０８ and R １１２ The linking group forms the above ring structure, R １１０ and R １１１ Either R forms the above ring structure via a linking group, １０８ R represents a hydrogen atom or an alkyl group. １０９ ~R １１２ It is preferable that this represents an alkyl group.

[0059] Specific examples of the structure represented by formula (X-3) are shown below, but the present invention is not limited to these.

[0060] In formula (X-4), R １１３ ~R １１９ Of these, at least one preferably represents an alkyl group or an aryl group, and preferably an alkyl group. Also, in formula (X-4), R １１３ ~R １１９ Of these, at least two preferably represent an alkyl group or an aryl group, and preferably represent an alkyl group. Here, R １１４ R is an alkyl group having a substituent, １１３ , R １１５ ~R １１９ Preferably, represents an alkyl group. As a substituent, in the above embodiment, R １１３ and R １１５ It is preferable that R is an isopropyl group or a cyclohexyl group, and more preferably an isopropyl group. In the above embodiment, R １１７ ~R １１９ It is preferable that it be a methyl group.

[0061] Specific examples of the structure represented by formula (X-3) are shown below, but the present invention is not limited to these.

[0062] In formula (X-4), R １１０ and R １１１ It is also preferable that the ring structure is formed via a linking group. A 5- to 7-membered ring structure is preferred as the formed ring structure, and an aliphatic 5- to 7-membered ring structure is more preferred.

[0063] Furthermore, it is also preferable that X is a cation represented by the following formulas (X-5) to (X-9). In formulas (X-5) to (X-8), R １２１ ~R １２７ represents a hydrogen atom or an organic group. Preferably, the organic group is an alkyl group. Preferably, the alkyl group is a methyl group, ethyl group, isopropyl group, isobutyl group, t-butyl group, or t-octyl group. A ring may be formed between adjacent substituents. The formed ring is preferably a five-membered or six-membered ring containing an N atom and / or a P atom. These phosphazene bases include, for example, iminotris(dimethylamino)phosphorane, tert-butylimino-tris(dimethylamino)phosphorane, N'-tert-butyl-N,N,N',N',N'',N''-hexamethylphospholiimoid acid triamide (abbreviated as P1-t-Bu), tert-octylimino-tris(dimethylamino)phosphorane (abbreviated as P1-t-Oct), tert-butylimino-tri(pyrrolidino)phosphorane (abbreviated as P1-t-Bu-tris(tetramethylene) or BTPP), 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (abbreviated as BEMP), and 1-ethyl -2,2,4,4,4-pentakis(dimethylamino)-2λ5,4λ5-catenadi(phosphazene), tetramethyl(tris(dimethylamino)phosphoranylidene)phosphate triamide-Et-imine (abbreviation: P2-Et), 1-tert-butyl-2,2,4,4,4-pentakis(dimethylamino)-2λ5,4λ5-catenadi(phosphazene) (abbreviation: P2-t-Bu), 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)phosphoranylideneamino]-2λ5,4λ5-catenadi(phosphazene) (abbreviation: P4-t-Bu) (all manufactured by Sigma-Aldrich Co., Ltd.) can be suitably used.

[0064] In formula (X-9), R １７３ ~R １７８represents an organic group, preferably an alkyl group. Preferably the alkyl group is a methyl group, ethyl group, isopropyl group, or isobutyl group. A ring may be formed between adjacent substituents. The formed ring is preferably a 5-membered to 8-membered ring containing an N atom and / or a P atom. It is more preferable that the N atom is in the bridgehead position to form a tertiary amine. These triaminophosphine bases can preferably include, for example, tris(dimethylamino)phosphine (abbreviated as HMPT), tris(diethylamino)phosphine (abbreviated as HEPT), tris(1-pyrrolidinyl)phosphine, 2,8,9-trimethyl-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane (abbreviated as Verkade superstrong base), [2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane-2,8,9-tris(1-methylethyl)] (abbreviated as iPr-PAP), and 2,8,9-triisobutyl-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane (abbreviated as iBu-PAP) (all manufactured by Sigma-Aldrich Co., Ltd.).

[0065] The conjugate acid of the amine in X (i.e., the cation formed by the addition of a proton to the amine (RNH) ＋ The acid dissociation constant pKa of the dimethyl sulfoxide solution of )) at 25°C is preferably 10 to 45, more preferably 11 to 40, even more preferably 12 to 35, and most preferably 13 to 32. The above pKa is calculated by setting X to RNH ＋ When expressed as (where R represents an organic group, and R and N are connected by a single or double bond), Log １０ ([RN][H ＋ ] / [RNH ＋ This is the value expressed as ]). Here, the above pKa can be the value listed in the literature, and if it is not listed in the literature, it can be calculated using the following software package. Software package: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs)

[0066] -nx1- nx1 is an integer greater than or equal to 1, and if X is an a-valent cation, then (a × nx1) is the same number as n1. Here, it is preferable that X is a monovalent cation and that n1 and nx1 are the same number.

[0067] [Formula (A-2a) or Formula (A-2b)] Compound A is also preferably a compound represented by the following formula (A-2a) or formula (A-2b). In equations (A-2a) and (A-2b), R １２ represents an acyl group or a nitro group, m2 represents 0 or 1, L ａ１ These are single bonds, -O-, -S-, -NR Ｎ２ -, -C(R ｘ１ R ｘ２ ) -, -C (=O) -, L ａ２ These are single bonds, -O-, -S-, -NR Ｎ２ -, -C(R ｘ１ R ｘ２ ) represents either - or -C (=O)-, R Ｎ２ , R ｘ１ and R ｘ２ Each of these independently represents a monovalent organic group, and y indicates either 0 or 1, where 0 is L ａ２ It does not exist, R ｙ１ and R ｙ２ Each independently represents a monovalent organic group, y1 and y2 independently represent integers from 0 to 3, and if y1 and y2 are 2 or greater, adjacent R ｙ１ R's mutual or adjacent R's ｙ２ They may bond with each other to form a ring, and X is a countercation, a cation containing a positively charged nitrogen atom.

[0068] In equations (A-2a) and (A-2b), R １２ A preferred embodiment when is an acyl group is R in formula (A-1). １ Preferred embodiments in which is an acyl group, particularly R １ The embodiment is the same as when is an alkylcarbonyl group or an arylcarbonyl group. In formula (A-2a), from the viewpoint of sensitivity, it is preferable that m2 is 1. In formulas (A-2a) and (A-2b), L ａ１ , L ａ２A preferred embodiment of and y is L in the above formula (X1-1). ａ１ , L ａ２ This is similar to the preferred embodiment of and y. In formulas (A-2a) and (A-2b), R ｙ１ and R ｙ２ A preferred embodiment is R in formula (A-1). １ This is similar to the preferred embodiment. In formulas (A-2a) and (A-2b), it is preferable that both y1 and y2 are 0. If y1 and y2 are 2 or more, adjacent R ｙ１ R's mutual or adjacent R's ｙ２ They may bond with each other to form a ring, and the formed ring may be an aromatic ring, an aliphatic ring, a hydrocarbon ring, or a heterocycle. In formulas (A-2a) and (A-2b), the preferred embodiment of X is the same as the preferred embodiment of X in formula (X-1).

[0069] [Physical Properties of Compound A] The molecular weight of Compound A is preferably less than 3000, more preferably less than 2000, even more preferably less than 1000, and most preferably less than 800. The lower limit is not particularly limited, but for example, it is 200 or more.

[0070] The glyoxylate value (g / mol, initiator molecular weight per glyoxylate group) of compound A is preferably 80 to 1000. The upper limit is preferably 800 or less, and more preferably 700 or less. The lower limit is preferably 100 or more, and more preferably 120 or more.

[0071] The molar absorption coefficient of compound A is 1 to 30,000 (L・mol) at 365 nm. －１ ・cm －１ Preferably, 10 to 20,000 (L・mol) －１ ・cm －１ ) is more preferable, and 20 to 10000 (L・mol) －１ ・cm －１ ) is more preferably 30 to 5000 (L・mol) －１ ・cm －１ ) is most preferred. The Gram absorption coefficient of the initiator is 50 to 10000 (L·g) at 365 nm. －１ ・cm －１Preferably, 100 to 7000 (L・g) －１ ・cm －１ ) is more preferable, and 200 to 6000 (L・g －１ ・cm －１ ) is even more preferable, with 300 to 5000 (L・g －１ ・cm －１ ) is most preferable. By setting it within this range, the base can be generated uniformly even in thick films (1 μm to 10 μm), and the internal stress of the film can be relaxed, and the warping of the coating film can be reduced. The molar extinction coefficient of compound A shall be measured by the following method. 12.5 mg of compound A is weighed accurately and placed in a 100 mL volumetric flask. Acetonitrile is added to this and dissolved completely. 2 mL of this solution is taken out with a volumetric pipette and made up in a 25 mL volumetric flask. This will be the measurement sample. The measurement sample is added to a 1 cm square 5 mL quartz glass cell, and the absorbance is measured under air to calculate the molar extinction coefficient. An example of a measuring device is an ultraviolet-visible-near-infrared spectrophotometer (UH4150, manufactured by Hitachi High-Tech Corporation).

[0072] When compound A has both E and Z geometric isomers, compound A may be the E geometric isomer, the Z geometric isomer, or a mixture of the E and Z geometric isomers. For convenience, the chemical structural formulas show only one isomer, but unless otherwise specified, neither the E nor the Z isomer is selected or distinguished. Furthermore, the above chemical structural formulas also include forms in which the E and Z isomers are mixed.

[0073] The maximum absorption wavelength of compound A is preferably in the wavelength range of 230 to 380 nm. There may be one maximum absorption wavelength or two or more. If there are two or more maximum absorption wavelengths, they are preferably separated by 20 nm or more, and more preferably by 50 nm or more.

[0074] Compound A may be a liquid or a solid at room temperature and pressure (25°C, 760 mmHg). If it is a liquid, its boiling point is preferably 200°C or higher, more preferably 250°C or higher, and even more preferably 300°C or higher at room pressure. Purification is usually carried out by vacuum distillation. In this case, to suppress the thermal decomposition of compound A, the distillation temperature at 1 mmHg is preferably less than 120°C, more preferably less than 100°C, and even more preferably less than 80°C. The viscosity of compound A when it is a liquid is not particularly limited, but is between 1 mPa.s and 1 × 10⁻⁶ at 25°C. ６ mPa·s is the most common unit, and 1 × 10⁻⁶ mPa·s to 1 × 10⁻⁶ mPa·s. ５ mPa·s is preferred, and 1 × 10 ２ mPa. s ~ 1 × 10⁻⁶ ４ mPa·s is more preferable. It can also be dissolved in the solvent described later, diluted, and then stored or used.

[0075] When compound A is a solid, its melting point is preferably 50 to 150°C, more preferably 60 to 130°C, and even more preferably 70 to 120°C, from the viewpoint of solubility in the solvent.

[0076] When compound A is in the form of particles, the 50% integrated value of compound A measured by dynamic light scattering (DLS) is preferably 0.001 to 1000 μm, more preferably 0.01 to 100 μm, and even more preferably 0.1 to 10 μm, from the viewpoint of handling and solubility in solvents.

[0077] The following describes impurities that may be included in compound A. The water content in compound A is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less, per 100 parts by mass of compound A. The lower limit can be 0 parts by mass, 0.0001 parts by mass, 0.001 parts by mass, or 0.01 parts by mass. The organic solvent content in compound A is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less, per 100 parts by mass of compound A. The lower limit can be 0 parts by mass, 0.0001 parts by mass, 0.001 parts by mass, or 0.01 parts by mass. The organic acid and organic acid anhydride content in compound A is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less, per 100 parts by mass of compound A. The lower limit can be 0 parts by mass, 0.0001 parts by mass, 0.001 parts by mass, or 0.01 parts by mass. Examples of organic acids include formic acid, acetic acid, propionic acid, pivalic acid, succinic acid, phthalic acid, and benzoic acid. Examples of organic acid anhydrides include these anhydrides. The content of organic base in compound A is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less, per 100 parts by mass of compound A. The lower limit can be 0 parts by mass, 0.0001 parts by mass, 0.001 parts by mass, or 0.01 parts by mass. Examples of organic bases include triethylamine, dimethylamine, diethylamine, pyridine, piperidine, pyrrolidine, morpholine, or amines used in the production of compound A. The halogen content in compound A is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 1 part by mass or less, per 100 parts by mass of compound A.The lower limit can be 0 parts by mass, 0.0001 parts by mass, 0.001 parts by mass, or 0.01 parts by mass. Examples of halogens include Cl, Br, F, I, etc., and may also be organic compounds having these halogen atoms. They may also be ions of these halogens. The residual metal content in compound A is preferably 0.1 parts by mass or less, more preferably 0.01 parts by mass or less, and even more preferably 0.001 parts by mass or less, per 100 parts by mass of compound A. It is even more preferably less than 0.0001 parts by mass, and particularly preferably below the detection limit. The type of residual metal is not particularly limited, but examples include Li, Na, Mg, Al, K, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb, Ti, V, As, Ag, Sn, Ba, W, Au, Zr, etc.

[0078] [Synthesis Method] Compound A is synthesized by combining a halogen compound such as methyl chloroglyoxylate or ethyl chloroglyoxylate with AlCl ３ , SnCl ４ Arylglyoxylic acid esters can be synthesized by the Friedel-Craft reaction in the presence of Lewis acids, etc., followed by hydrolysis in the presence of an acid or base to obtain arylglyoxylic acid, and then neutralization with the corresponding amine, amidine, guanidine, biguanide, phosphazene, etc., to form a counter salt. Alternatively, arylglyoxylic acid can be directly formed by the Friedel-Craft reaction and subsequent hydrolysis of oxalyl chloride and an aromatic compound, and then neutralization with the corresponding amine, amidine, guanidine, biguanide, phosphazene, etc., to form a counter salt.

[0079] Specific examples of compound A include the compound used as compound A in the examples described later.

[0080] The content of compound A in the total solid content of the photocurable composition is preferably 0.1 to 50% by mass. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 45% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. In the photocurable composition of the present invention, compound A may be used alone or two or more types. When two or more types are used, it is preferable that their total amount is within the above range.

[0081] When the photocurable composition contains other radical polymerization initiators as described later, the content of compound A relative to the total content of compound A and other radical photopolymerization initiators is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more.

[0082] Compound A can be combined with a sensitizer, as described later, to increase its photodegradation efficiency and base generation efficiency. Coumarin-based, anthracene-based, and anthraquinone-based sensitizers are more preferably used in combination. The mass ratio of compound A to sensitizer is not particularly limited, but the amount of sensitizer used in combination with 100 parts by mass of compound A is preferably 1 to 1000 parts by mass, and more preferably 10 to 100 parts by mass.

[0083] <Specific Resin> The photocurable resin composition of the present invention contains a polyimide precursor having polymerizable groups.

[0084] [Polyimide Precursor] In this specification, a polyimide precursor is a resin having at least one structure represented by the following formula (AM-1) or formula (AM-2). A resin that undergoes a chemical structure change upon heating to become polyimide is preferred, and a resin that undergoes a ring-closing reaction upon heating to form a ring structure to become polyimide is more preferred. In formula (AM-1) or formula (AM-2), R １ represents a tetravalent organic group, R ２ represents a monovalent organic group, and A is -O- or -NR ３ - represents R ３ represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with other structures.

[0085] The polyimide precursor may or may not undergo imidization treatment. Imidization treatment here refers to heating reactions at 50°C or higher, ring-closing reactions using imidization catalysts (acid catalysts, base catalysts, condensing agents, etc.), and chemical imidization (dehydration reactions using acetic anhydride / pyridine, triphenyl phosphite, etc.). Specifically, it is preferable that the resin exhibits an increased imidization rate (preferably heat) upon external stimulation.

[0086] 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, "main chain" refers to the relatively longest bonding chain in the resin molecule, and "side chains" refer to the other bonding chains. 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. In addition to the imide structure, polyimide may also be a so-called polyamide imide, which has amide bonds within its molecular chain. In this specification, an amide bond 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.

[0087] The imidization rate (also called the "ring closure rate") of a specific resin is acceptable if it is less than 100% from the viewpoint of the film strength and insulating properties of the resulting organic film, but is preferably 99% or less, more preferably 90% or less, even more preferably 70% or more, particularly preferably 50% or less, even more preferably 30% or less, and most preferably 20% or less. The lower limit of the above imidization rate is not particularly limited and may be 0% or more. The above imidization rate is measured, for example, by the method described below.

[0088] In this invention, the imidization rate can be calculated by the following method. A specific resin is dissolved in γ-butyrolactone, diluted to a viscosity of 2,000 mPa·s, and applied to a silicon wafer by spin coating to form a resin layer. If a resin layer cannot be formed due to reasons such as low solubility of the resin in γ-butyrolactone, the solvent may be changed to another solvent. Other solvents that can be used include solvents contained in photocurable resin compositions, such as NMP. The viscosity may also be changed as appropriate within an adjustable range. The silicon wafer to which the obtained resin layer has been applied is dried on a hot plate at 110°C for 5 minutes to obtain a resin layer with a uniform thickness of approximately 15 μm on the silicon wafer after film formation. Here, if only a resin solution with low viscosity can be obtained, and it is difficult to obtain a resin layer with a thickness of 15 μm, the film thickness may be changed as appropriate. For example, if the film thickness is 5 μm or more, a similar value for the imidization rate can be obtained. The above resin layer was measured using the ATR method with Nicoleti S20 (manufactured by Thermofisher), with a measurement range of 4000–700 cm. －１ The measurement was taken 50 times. 1380 cm －１ Nearby (1350-1450 cm) －１ (If there are multiple peaks, the peak height of the one with the highest peak intensity) and 1500 cm －１ Nearby (1460-1550 cm) －１The imidization index A of the resin is calculated by dividing the value by the peak height of the peak with the maximum peak intensity (if there are multiple peaks). The film is heated at a rate of 10°C / min under a nitrogen atmosphere and heated to 350°C for 1 hour. The imidization index B is calculated in the same manner, and the value obtained by dividing the imidization index A by the imidization index B is calculated as the imidization rate of the resin. In measuring the imidization rate, the resin to be measured for imidization rate can be obtained from the composition by, for example, the following method: A solution of 1 g of the composition and 2 g of tetrahydrofuran is added to 50 g of methanol or water and crystallized to precipitate the resin, which is then filtered. The filtrate is collected, dissolved in 3.0 g of THF (tetrahydrofuran), added to 50 g of methanol or water and crystallized, filtered, and dried at 40°C for 20 hours to obtain the resin.

[0089] [Polymerizable Groups] Radical polymerizable groups are preferred as polymerizable groups. Examples of polymerizable groups include groups having ethylenically unsaturated bonds, epoxy groups, oxetanyl groups, benzoxazolyl groups, etc., with groups having ethylenically unsaturated bonds being preferred. Examples of groups having ethylenically unsaturated bonds include vinyl groups, allyl groups, vinylphenyl groups, (meth)acryloyl groups, maleimide groups, and groups having a norbornene skeleton. Among these, (meth)acryloyl groups, vinylphenyl groups, or maleimide groups are preferred, and from the viewpoint of reactivity, (meth)acryloyl groups are more preferred. Furthermore, from the viewpoint of reducing dielectric loss tangent, vinylphenyl groups or maleimide groups are preferred. The (meth)acryloyl group is preferably composed of a (meth)acryloxy group or a (meth)acrylamide group, and from the viewpoint of reactivity, it is more preferred to be composed of a (meth)acryloxy group. Furthermore, from the viewpoint of adhesion, the hydrophobic vinylphenyl group is preferred.

[0090] Furthermore, it is preferable that the resin has the following formula (M-1) or the following formula (M-2) as a partial structure containing polymerizable groups. １ However, it is more preferable that it be represented by any of the following formulas (Lb-1), (Lb-2), or (Lb-3), or a combination thereof. In formula (M-1), L１ L represents an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a group consisting of any or a combination of the following formulas (Lb-1) to (Lb-3). ２ R indicates a single bond or an organic group with (k+1) valency. ２１ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, A represents a group containing any of an epoxy group, an oxetanyl group, or a group having an ethylenically unsaturated bond, r represents 0 or 1, k represents an integer from 1 to 6, and * represents a bonding site with other structures. In formula (M-2), L １ L represents an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a group consisting of any or a combination of the following formulas (Lb-1) to (Lb-3). ２ R indicates a single bond or an organic group with (k+1) valency. ２１ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, A represents a group containing either an epoxy group, an oxenyl group, or a group having an ethylenically unsaturated bond, k represents an integer from 1 to 6, and * represents a bonding site with other structures. In formulas (Lb-1) to (Lb-3), Lc １ x represents an alkylene group having 2 to 12 carbon atoms, an arylene group having 6 to 18 carbon atoms, or a combination thereof, and x, y, and z represent integers from 0 to 30.

[0091] In formula (M-1), L １ The group is preferably an alkylene group, a phenylene group, or a group consisting of any or a combination of formulas (Lb-1) to (Lb-3) having 1 to 12 carbon atoms, and more preferably an alkylene group, a phenylene group, or a group consisting of any or a combination of formulas (Lb-1) to (Lb-3) having 2 to 6 carbon atoms. １It is preferable that Lc1 is a group represented by formulas (Lb-1) to (Lb-3), or by a combination thereof, and it is also preferable that it is a group represented by formula (Lb-1), formula (Lb-2), or by a combination thereof. In formulas (Lb-1) to (Lb-3), Lc1 is preferably an alkylene group having 2 to 8 carbon atoms, an arylene group having 6 to 10 carbon atoms, or a combination thereof, and is more preferably an alkylene group having 2 to 8 carbon atoms. In formulas (Lb-1) to (Lb-3), x, y, and z each independently represent an integer from 1 to 30, preferably an integer from 1 to 20, and more preferably an integer from 1 to 10.

[0092] In formula (M-1), L ２ The group represents a single bond or a (k+1) valent organic group, preferably a single bond or a saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and more preferably a single bond or a saturated aliphatic hydrocarbon group having 2 to 6 carbon atoms. The hydrogen atoms in the saturated aliphatic hydrocarbon group or aromatic hydrocarbon group may be substituted with known substituents.

[0093] In formula (M-1), R ２１ The hydrogen atom or an alkyl group having 1 to 10 carbon atoms is preferred, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is more preferred, and a hydrogen atom or a methyl group is even more preferred.

[0094] In formula (M-1), A is preferably a group having an ethylenically unsaturated bond, and is preferably a (meth)acryloyl group, a vinylphenyl group, or a maleimide group. Other known groups having an ethylenically unsaturated bond, such as a vinyl group or an allyl group, may also be used.

[0095] In formula (M-1), k is more preferably an integer between 1 and 3, and even more preferably 1 or 2. Furthermore, k being 1 is also one of the preferred embodiments of the present invention.

[0096] In formula (M-1), * is preferably a bonding site with a carbon atom, and more preferably a bonding site with a carbon atom included in the main chain of a specific resin.

[0097] In formula (M-2), L １ , L ２ , R ２１A preferred embodiment of A, k and * is L in formula (M-1). １ , L ２ , R ２１ This is similar to the preferred embodiments of A, k, and *.

[0098] The content of polymerizable groups relative to the total mass of the specific resin (polymerizability value) is preferably 0.2 to 4.0 mmol / g, more preferably 0.5 to 3.5 mmol / g, and even more preferably 1.0 to 3.4 mmol / g. In particular, the content of radical polymerizable groups relative to the total mass of the specific resin (radical polymerizability value) is preferably 0.2 to 4.0 mmol / g, more preferably 0.5 to 3.5 mmol / g, and even more preferably 0.5 to 1.0 mmol / g. For example, the content of vinylphenyl groups in the resin in the composition can be calculated by the following method. The calculation method is the same for other polymerizable groups and radical polymerizable groups. 1 g of the composition is added to 50 g of methanol or water and crystallized to precipitate the specific resin, which is then filtered. The filtrate is collected, dissolved in 3.0 g of THF (tetrahydrofuran), added to 50 g of methanol or water and crystallized, filtered, and dried at 40°C for 20 hours. After dissolving 0.1 g of the dried specific resin described above in 0.9 g of didimethyl sulfoxide, １ The amount of vinylphenyl groups is calculated by measuring with 1H-NMR. １ The number of 1H-NMR scans will be 640. For example, tetramethylsilane will be used as the reference substance. １ The molar amount of vinylphenyl groups in a specific resin can be calculated from the ratio of the integrated intensity of the peak around 5.0–7.0 ppm derived from vinylphenyl groups in the 1H-NMR chart to the integrated intensity of the peak derived from the reference substance, the amount of the reference substance, and the amount of the specific resin. The molar amounts of other structures can also be measured by calculating the integrated intensity of the peaks corresponding to each structure.

[0099] [Partial Structure] The specific resin preferably has at least one of the partial structures represented by the following formula (B-1) and the partial structure represented by the following formula (B-2), and preferably includes the partial structure represented by the following formula (B-2). In formula (B-1), X １represents an organic group with 4+m valence, Y １ represents a 2+n valent organic group, R １ R represents a group containing a polymerizable group. ２ represents a group containing a polymerizable group, n is an integer from 0 to 6, m is an integer from 0 to 6, and n+m is an integer of 1 or more. In formula (B-2), X １ represents an organic group with 4+m valence, Y １ represents a 2+n valent organic group, A ｘ１ and A ｘ２ represents a monovalent organic group, R １ R represents a group containing a polymerizable group. ２ represents a group containing a polymerizable group, n is an integer from 0 to 6, m is an integer from 0 to 6, and n+m is an integer of 1 or more, where A ｘ１ and A ｘ２ If at least one of the components has a polymerizable group, then n+m may be 0.

[0100] -X １ - In formula (B-1) or formula (B-2), X １ It is preferable, but not limited to, a structure derived from an acid anhydride monomer. The acid anhydride monomer is not particularly limited as long as it has two cyclic acid anhydride groups in one molecule. It may be an aromatic acid anhydride, an aliphatic acid anhydride, or a mixture thereof. Furthermore, from the viewpoint of the ultraviolet light transmittance of the specific resin, X １ Preferably, the group is one having an alicyclic hydrocarbon.

[0101] X １ The following formulas (Xp-1) to (Xp-23) are preferably used. In the following formulas (Xp-1) to (Xp-23), *1 represents the bonding site with the carbonyl group indicated as *1 in the following formula (BX-1) or formula (BX-2), and *2 represents the bonding site with the carbonyl group indicated as *2 in the following formula (BX-1) or formula (BX-2). The following formulas (BX-1) and (BX-2) are formulas (B-1) and (B-2) respectively to which the symbols *1 and *2 have been added for convenience.

[0102] In equations (Xp-1) to (Xp-23), L either does not exist independently, or is a single bond, -CH=CH-, -CH ２ CH ２ -ien-CH ２ -, -C (CH ３ ) ２ -, or -C (CF ３ ) ２ - represents R １ and R ２ Each of these independently represents a hydrogen atom or a substituent, R １ and R ２ They may bond to form a ring structure, and the formed ring may be an aromatic ring, R １ and R ２ R can also form a ring to create a benzene ring. If multiple L molecules are present in one molecule, they may be the same or different. ３ , R ４ , R ５ , R ６ Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and adjacent R ３ ~R ６ The divalent organic groups may be linked to form a ring. ７ , R ８ n1 represents one of the following: alkyl group, aryl group, fluoroalkyl group, fluoroaryl group, alkoxy group, aryloxy group, hydroxyl group, carboxyl group, or halogen atom. n1 and n2 each independently represent integers from 0 to 4. If stereogeometric isomers exist, the distinction between cis / trans and endo / exo is not particularly limited.

[0103] In formulas (Xp-1) to (Xp-23), X １ ~X ４ represents a single bond or a divalent linking group, and is either a single bond or -C(Rx) ２ - (Rx represents a hydrogen atom or substituent. If Rx is a substituent, they may be linked together to form a ring), -O-, -S (=O) ２ -, -C(=O), -S-, -NR Ｎ-, alkylene group, cycloalkylene group, alkenylene group, alkylylene group, arylene group, heteroarylene group, -C(=O)O-, -C(=O)NH-, or combinations thereof are preferred, single bond or -C(Rx) ２ - is more preferable. When Rx represents a substituent, specific examples include an alkyl group, an alkyl group which may be substituted with a fluorine atom, or a fluorenyl group. Ｎ represents a hydrogen atom or an organic group, preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom or an alkyl group.

[0104] Linking group X １ ~X ４ Furthermore, it is even more preferable that the linking group is a divalent group represented by the following general formula (X1-1) in that it exhibits excellent mechanical strength. In equation (X1-1), n ​​and m each independently represent either 0 or 1. １ , T ２ Each of these independently represents a single bond, -O-, -S-, or -NR-. Here, R represents a hydrogen atom, an alkyl group, or an aryl group. P １ , P ２ , and, P ３ Each of these independently represents one of the following: an aromatic group having 6 to 12 carbon atoms, a heterocyclic group having 5 to 12 carbon atoms, an aliphatic group having 1 to 12 carbon atoms, or an alicyclic group having 4 to 12 carbon atoms. １ , P ２ and P ３ Each of these groups may have further substituents, such as alkyl groups, fluoroalkyl groups, aryl groups, alkoxy groups, aryloxy groups, hydroxyl groups, carboxyl groups, and halogen atoms. The positions of these substitutions are not particularly limited. Q １ and Q ２ Each is independently a single bond, -C(R) ２ -, -O-, -S-, -NR-, -C(=O)O-, -C(=O)NR-, -C(=O)-, -OC(=O)O-, -OC(=O)NR-, -NRC(=O)NR-, -S(=O)-, -S(=O) ２This represents a divalent organic group consisting of one or a combination thereof. Here, R independently represents a hydrogen atom, an alkyl group, a fluoroalkyl group, or an aryl group, and R groups may be bonded to each other to form a ring. p and q independently represent 0 or 1.

[0105] Linking group X １ ~X ４ More specifically, the following structure is preferred because it can achieve both high strength and high elongation.

[0106] Commercially available acid anhydride monomers include, for example, pyromellitic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 4-chloroformylphthalic anhydride, trimellitic anhydride, tetrachlorophthalic anhydride, phthalic anhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-oxydiphthalic anhydride, 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride, 4,4'-biphthalic anhydride, tetrabromophthalic anhydride, 3,4'-oxydiphthalic anhydride, 4-(1-propynyl)phthalic anhydride, 4,4'-(ethyn-1,2-diyl)diphthalic anhydride, bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid)1,4-phenylene, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride Examples include (sublimation purified products), pyromellitic anhydride (sublimation purified products), 4-phenylethynylphthalic anhydride, tetrafluorophthalic anhydride, 4,4'-sulfonyl diphthalic anhydride, 4-ethynylphthalic anhydride, and diphenyl-2,3,3',4'-tetracarboxylic dianhydride.Examples of aliphatic dianhydrides include bicyclo[2.2.2]octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, ethylenediaminetetraacetic acid dianhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic acid dianhydride, meso-butane-1,2,3,4-tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, and 4-(2,5-dioxotetrahydrofuran-3 The following can be suitably used: -yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, octahydrobiphenylene-4a,8b:4b,8a-tetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, and 3-(carboxymethyl)-1,2,4-cyclopentanetricarboxylic acid 1,4:2,3-dianhydride.

[0107] Other acid anhydrides that can be used include CpODA (manufactured by ENEOS), BzDA (manufactured by ENEOS), BzDAxx (manufactured by ENEOS), BNBDA (manufactured by ENEOS), TMPBP-TME (manufactured by Honshu Chemical Co., Ltd.), BPZ-TME (manufactured by Honshu Chemical Co., Ltd.), BPF-PA (manufactured by JFE Chemical Co., Ltd.), and 5,5′-[p-phenylenebis(oxycarbonyl)]diphthalic anhydride (trade name: TAHQ, manufactured by Manac Co., Ltd.), which can be suitably used to enhance the transparency of polyimide or amical resin.

[0108] In addition, acid anhydrides described in International Publication No. 2022 / 019253, Japanese Patent Publication No. 2023-166413, and International Publication No. 2022 / 019255 can be suitably used.

[0109] -Y １ - In formula (B-1) or formula (B-2), Y １The structure is preferably derived from a diamine monomer, but is not limited thereto. The diamine monomer is not particularly limited as long as it has two primary amino groups in one molecule. It may be an aromatic diamine, an aliphatic diamine, or a mixture thereof.

[0110] Y １ The structure is preferably one of the following formulas (Yp-1) to (Yp-16). * indicates a bonding site with a nitrogen atom.

[0111] In equations (Yp-1) to (Yp-16), L has the same meaning as described above. １０ ~R １５ Each of these independently represents one of the following: an alkyl group, an aryl group, a fluoroalkyl group, a fluoroaryl group, an alkoxy group, an aryloxy group, a hydroxyl group, a carboxyl group, or a halogen atom. １６ and R １７ Each of the following independently represents a hydrogen atom, an alkyl group, or an aryl group. a to f each independently represent an integer from 0 to 3. n represents an integer from 1 to 12. R １０ ~R １５ The replacement position is not specifically designated.

[0112] In formulas (Yp-1) to (Yp-16), Y １ or Y ２ represents a single bond or a divalent linking group, and is either a single bond or -C(Rx) ２ - (Rx represents a hydrogen atom or substituent. If Rx is a substituent, they may be linked together to form a ring), -O-, -S (=O) ２ -, -C(=O), -S-, -NR Ｎ -, alkylene group, cycloalkylene group, alkenylene group, alkylylene group, arylene group, heteroarylene group, -C(=O)O-, -C(=O)NH-, or combinations thereof are preferred, single bond or -C(Rx) ２ - is more preferable. When Rx represents a substituent, specific examples include an alkyl group, an alkyl group which may be substituted with a fluorine atom, or a fluorenyl group. Ｎrepresents a hydrogen atom or an organic group, preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom or an alkyl group.

[0113] Linking group Y １ or Y ２ Furthermore, it is even more preferable that the linking group is a divalent group represented by the following general formula (Y1-1) in that it exhibits excellent mechanical strength. In formula (Y1-1), each group T １ , T ２ , P １ , P ２ , P ３ Q １ Q ２ n, m, p, and q are equivalent to equation (X1-1).

[0114] Linking group Y １ or Y ２ More specifically, the following structure is preferred because it can achieve both high strength and high elongation.

[0115] Examples of commercially available diamine monomers mentioned above include aromatic diamines such as 4,4'-diaminodiphenylsulfone, 1,5-naphthalenediamine, 4,4'-diaminostilbene-2,2'-disulfonic acid, m-xylylenediamine, p-xylylenediamine, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylsulfone, 4,4'-methylenebis(2,6-diethylaniline), 1,3-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-Methylenebis(2-chloroaniline), 1,4-Bis[2-(4-aminophenyl)-2-propyl]benzene, 4,4'-Diamino-2,2'-Biphenyldisulfonic acid, 1,4-Phenylenediamine, o-Tolidine, m-Tolidine, 1,3-Phenylenediamine, 4-Aminobenzylamine, 2,2-Bis[4-(4-aminophenoxy)phenyl]propane, 2,5-Dimethyl-1,4-Phenylene Diamine, 9,9-bis(4-aminophenyl)fluorene, o-dianisidine, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(trifluoromethyl)benzidine, 2,7-diaminofluorene, 3,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethylbenzidine, 9,9-bis(4-amino-3-methylphenyl)fluorene, bis(3-amino-4-hydrox bis(4-aminophenoxy)sulfone, 3-aminobenzylamine, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 4,4'-bis(4-aminophenoxy)biphenyl, 1,1-bis(4-aminophenyl)cyclohexane, 4,6-diaminoresorcinol, 3,4'-diaminodiphenyl ether, 4,4'-ethylenedianiline, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene, 2,6-diaminoanthraquinone, bis(2-aminophenyl)sulfide, 1,3-Bis[2-(4-aminophenyl)-2-propyl]benzene, 1,3-Bis(4-aminophenoxy)benzene, Bis[4-(3-aminophenoxy)phenyl]sulfone, Bis[4-(4-aminophenoxy)phenyl]sulfone, 4,4'-Methylenebis(2-ethyl-6-methylaniline), Bis(4-aminophenyl)sulfide, 3,7-Diamino-2,8-Dimethyldibenzothiophenesulfone, 4,4'-Diamino-3,3'-Dimethyldiphenylmethane, 2,4,5,6-Tetrafluoro-1,3-Phenylenediamine, 4,4''-Diamino-p Examples include terphenyl, 3,3'-dimethylnaphthidine, 4,4'-diaminobenzophenone, 4,4'-diaminooctafluorobiphenyl, 3,3'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,6-diaminocarbazole, 9,9-bis(4-amino-3-fluorophenyl)fluorene, 9,9-bis(4-amino-3-chlorophenyl)fluorene, 4,4'-diamino-2,2'-dimethylbibenzyl, 9,9-bis(4-aminophenyl)fluorene, and 2,3,5,6-tetrafluoro-1,4-phenylenediamine. Suitable aliphatic diamines include, for example, bicyclo[2.2.1]heptanedimethanamine (isomer mixture), 4,4'-methylenebis(cyclohexylamine) (isomer mixture), 4,4'-methylenebis(2-methylcyclohexylamine) (isomer mixture), isophoronediamine (cis-, trans- mixture), 1,3-bis(aminomethyl)cyclohexane (cis-, trans- mixture), 1,4-bis(aminomethyl)cyclohexane (cis-, trans- mixture), 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-cyclohexanediamine (cis-, trans- mixture), and 1,4-cyclohexanediamine (cis-, trans- mixture).

[0116] Other diamines that can be used include BPF-AN (manufactured by JFE Chemical Co., Ltd.) and pyridazine-based sulfur-containing diamine APP (manufactured by Nippon Materials Technology Co., Ltd.), which can be suitably used to enhance the transparency of polyimide or amical resins.

[0117] In addition, diamines described in Japanese Patent Publication No. 2023-166413 and International Publication No. 2022 / 019255 can be suitably used.

[0118] -R １ , R ２ - In equation (B-1) or equation (B-2), R １ and R ２ The symbol represents a group containing a polymerizable group. The preferred embodiment of the polymerizable group is as described above.

[0119] In formula (B-1) or (B-2), R １ or R ２ The polymerizable group shown is preferably a structure represented by the following formula (AA-1). In formula (AA-1), Lx １ The bond is a single bond, -O-, -NR １ -, -C(=O)O-, -OC(=O)-, -OC(=O)O-, -C(=O)NR ２ -, -NR ２ C(=O)-, -NR ２ C(=O)O-, -OC(=O)NR ２ -, -NR ２ C(=O)NR ３ -, -NR ３ C(=O)NR ２ -, -CH ２ CH(OH)-CH ２ -, or -CH ２ CH(OR ４ ) - CH ２ - indicates Lx ２ -O-, -NR １ -, -C(=O)O-, -OC(=O)-, -OC(=O)O-, -C(=O)NR ２ -, -NR ２ C(=O)-, -NR ２ C(=O)O-, -OC(=O)NR ２ -, -NR ２ C(=O)NR ３ -, -NR ３ C(=O)NR ２ -, -CH ２ CH(OH)-CH ２ -, or -CH ２CH(OR ４ ) - CH ２ - indicates R １ R represents a hydrogen atom or a monovalent organic group. ２ R represents a hydrogen atom or a monovalent organic group. ３ R represents a hydrogen atom or a monovalent organic group. ４ represents a monovalent organic group, La represents the group shown in the following formula (La-1), Lb represents a C1 to C12 r4+1 valent hydrocarbon group, a group consisting of any or a combination of the following formulas (Lb-1) to (Lb-3), A represents an epoxy group, an oxetanyl group, or a group having an ethylenically unsaturated bond, r1 represents 0 or 1, r2 represents 0 or 1, r3 represents an integer from 0 to 5, r4 represents an integer from 1 to 10, and * represents X in formula (C-1) or formula (C-2). １ (R ２ (If Y) １ (R １ (In the case of) This indicates the binding site with In formula (La-1), Ra １ Ra ２ Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and * represents Lx １ The wavy lines indicate the bonding sites with Lb or A, respectively. In formulas (Lb-1) to (Lb-3), Lc1 represents an alkylene group having 2 to 12 carbon atoms, an arylene group having 6 to 18 carbon atoms, or a combination thereof, and x, y, and z each independently represent an integer from 1 to 30.

[0120] In formula (AA-1), Lx １ Regarding the structure illustrated, the left side is X in equation (C-1) or equation (C-2). １ Or Y １ Alternatively, it indicates the bonding site with an oxygen atom, with the right side representing the bonding site with La (when r1=1), Lb (when r1=0 and r2=an integer from 1 to 5), or A (when r1=0 and r2=0). For example, L Ｘ１ If is -C(=O)O-, then the carbon atom is X in formula (P-1) or formula (P-2). １ Or Y ２or a bonding site with an oxygen atom, where the oxygen atom is a bonding site with La, Lb, or A. In formula (AA-1), Lx １ -O-, -C(=O)O-, -NR ２ C(=O)O-, -OC(=O)NR ２ -, -CH ２ CH(OH)-CH ２ -, or -CH ２ CH(OR ４ ) - CH ２ It is preferable that it be -, and more preferably -O- or -C(=O)O-.

[0121] R １ R is preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom. ２ R is preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom. ３ R is preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom. ４ The group is preferably an alkyl group or an aryl group, and more preferably an alkyl group.

[0122] In formula (AA-1), La represents the group shown in formula (La-1), and in formula (La-1), Ra １ , Ra ２ Each of these is preferably a hydrogen atom, a C1-C10 alkyl group, or a phenyl group, more preferably a hydrogen atom or a C1-C10 alkyl group, and even more preferably a methyl group. １ and Ra ２ Another preferred embodiment of the present invention is one in which one of the atoms is a hydrogen atom and the other is an alkyl group having 1 to 10 carbon atoms (preferably a methyl group).

[0123] In formula (AA-1), r1 is 1 or 0, and is preferably 0.

[0124] In formula (AA-1), Lx ２ -O-, -C(=O)O-, -NR ２ C(=O)O-, -OC(=O)NR ２ -, -CH ２ CH(OH)-CH ２ -, or -CH ２ CH(OR４ ) - CH ２ It is preferable that it be -, and more preferably that it be -O-.

[0125] In formula (AA-1), r2 is 1 or 0, and if Lb is one of formulas (Lb-1) to (Lb-3), or a combination thereof, it is preferably 1.

[0126] In formula (AA-1), when Lb is a C1-C12 r4+1 valent hydrocarbon group, Lb is preferably a C1-C12 r4+1 valent saturated aliphatic hydrocarbon group, and more preferably a C2-C6 r4+1 valent saturated aliphatic hydrocarbon group. For example, when r4=1, Lb is preferably a C1-C12 alkylene group, and more preferably an alkylene group. The hydrocarbon group in Lb, or the hydrogen atom in the saturated aliphatic hydrocarbon group, may be substituted with known substituents.

[0127] Furthermore, Lb is preferably a group represented by formulas (Lb-1) to (Lb-3), or a combination thereof, and is also preferably a group represented by formula (Lb-1), formula (Lb-2), or a combination thereof. In formulas (Lb-1) to (Lb-3), Lc1 is preferably an alkylene group having 2 to 8 carbon atoms, an arylene group having 6 to 10 carbon atoms, or a combination thereof, and is more preferably an alkylene group having 2 to 8 carbon atoms. In formulas (Lb-1) to (Lb-3), x, y, and z each independently represent an integer from 1 to 30, preferably an integer from 1 to 20, and more preferably an integer from 1 to 10.

[0128] In formula (AA-1), r3 represents an integer from 0 to 5, preferably an integer from 0 to 3, and preferably 0, 1, or 2. An embodiment in which r3 is from 1 to 5 and Lb includes any of formulas (Lb-1) to (Lb-3) is also one of the preferred embodiments of the present invention. The structures represented by formulas (Lb-1) to (Lb-3) are thought to be easily decomposed by heating. Therefore, for example, when heating (for example, heating to 180°C or higher) is performed during the formation of the cured product, the structures represented by formulas (Lb-1) to (Lb-3) are decomposed, making it easier for the resin to orient in the cured product, and it is presumed that the CTE (coefficient of thermal expansion) is likely to decrease.

[0129] In formula (AA-1), A represents an epoxy group, an oxetanyl group, or a group having an ethylenically unsaturated bond, and is preferably a group having an ethylenically unsaturated bond. Preferred groups having an ethylenically unsaturated bond include (meth)acryloyl groups, vinylphenyl groups, or maleimide groups. Other known groups having an ethylenically unsaturated bond, such as vinyl groups and allyl groups, may also be used.

[0130] In formula (AA-1), r4 is preferably an integer from 1 to 6, more preferably an integer from 1 to 3, and even more preferably 1 or 2.

[0131] -A ｘ１ , A ｘ２ - In formula (B-2), AX １ AX ２ It is preferably an alkyl group, an aryl group, or a group represented by the above formula (AA-1), and more preferably a group represented by the above formula (AA-1).

[0132] In formula (B-1), m is preferably an integer between 0 and 2. Furthermore, the embodiment in which m is 0 is also one of the preferred embodiments of the present invention. In formula (B-1), n ​​is preferably an integer between 0 and 2, and more preferably 1 or 2. In formula (B-1), n+m is preferably an integer between 1 and 4, and more preferably 1 or 2. In formula (B-2), m is preferably an integer between 0 and 2. Furthermore, the embodiment in which m is 0 is also one of the preferred embodiments of the present invention. In formula (B-2), n is preferably an integer between 0 and 2. Furthermore, the embodiment in which n is 0 is also one of the preferred embodiments of the present invention. In formula (B-2), n+m is preferably an integer between 0 and 4, and more preferably 0, 1 or 2. Furthermore, in formula (C-2), A Ｘ２ and A Ｘ２ Another preferred embodiment of the present invention is one in which at least one of the elements is a group represented by the above formula (A-1), and n+m is 0.

[0133] Among these, R in formula (B-1) above １ and R ２ , and also R in formula (B-2) １ , R ２ A ｘ１ and A ｘ２ However, it is preferable that the group includes a group having an ethylenically unsaturated bond. However, in the above embodiment, one of n and m in formula (B-1) may be 0, and at least one of n and m in formula (B-2) may be 0. Examples of groups having an ethylenically unsaturated bond include vinyl groups, allyl groups, vinylphenyl groups, (meth)acryloyl groups, maleimide groups, and groups having a norbornene skeleton. Among these, (meth)acryloyl groups, vinylphenyl groups, or maleimide groups are preferred, and from the viewpoint of reactivity, (meth)acryloyl groups are more preferred. Furthermore, from the viewpoint of reducing the dielectric loss tangent, vinylphenyl groups or maleimide groups are preferred. The (meth)acryloyl group is preferably composed of a (meth)acryloxy group or a (meth)acrylamide group, and from the viewpoint of reactivity, it is more preferable that it constitutes a (meth)acryloxy group.

[0134] [Content of substructures] The total content of the substructure represented by formula (B-1) or formula (B-2) relative to the total repeating units of the specified resin is preferably 50 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, and particularly preferably 90 mol% or more. The upper limit of the above content is not particularly limited and may be 100 mol%. Furthermore, if the specified resin contains the substructure represented by formula (A-1a), it may contain two or more substructures represented by formula (A-1a) with different structures. In that case, it is preferable that the total amount is within the above range. If the specified resin contains the substructure represented by formula (A-1b), it may contain two or more substructures represented by formula (A-1b) with different structures. In that case, it is preferable that the total amount is within the above range. In particular, the total content of the substructure represented by formula (B-2) relative to the total repeating units of the specific resin is preferably 1 mol% or more, more preferably 10 mol% or more, even more preferably 50 mol% or more, and particularly preferably 80 mol% or more.

[0135] [Physical Properties of Specific Resins] The weight-average molecular weight (Mw) of the specific resin 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 degree of molecular weight dispersion of the above-mentioned specific resin 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 degree of 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, the degree of molecular weight dispersion is a value calculated by weight-average molecular weight / number-average molecular weight. When a photocurable 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.

[0136] [Acid Value] From the viewpoint of storage stability and adhesion, the acid value of the specific resin is preferably 0.066 to 0.400 mmol / g, more preferably 0.069 to 0.356 mmol / g, and even more preferably 0.071 to 0.321 mmol / g. Furthermore, the acid value of the specific resin is preferably 3.70 to 22.5 mg KOH / g, more preferably 3.85 to 20.0 mg KOH / g, and even more preferably 4.00 to 18.0 mg KOH / g. The above acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.

[0137] Furthermore, from the viewpoint of adhesion, it is also preferable that the specific resin is a polyamic acid ester in which the acidic functional groups at a pH below 8.0 are less than 0.1 mg KOH / g, and the acidic functional groups at a pH of 8.0 or higher are 3.70 to 22.5 mg KOH / g when titrated under the following conditions. Conditions: 0.300 g of resin is completely dissolved in 80 mL of NMP, then 5 mL of water is mixed in, and the mixture is titrated with a 0.01 mol / L NaOH aqueous solution. Whether or not it is completely dissolved can be confirmed by visual inspection by checking for the absence of residual material. If the above amount of resin does not completely dissolve in NMP, the amount of resin may be appropriately reduced and measured at the concentration in which it is completely dissolved. The acidic functional groups at a pH below 8.0 are preferably less than 0.01 mg KOH / g, and more preferably less than 0.001 mg KOH / g. The acidic functional groups at a pH of 8.0 or higher are preferably 3.70 to 22.5 mg KOH / g, and more preferably 4.00 to 18.0 mg KOH / g.

[0138] [Amine Value] From the viewpoint of storage stability of the composition, the amine value of the specific resin is preferably 0.100 mmol / g or less, more preferably 0.0001 to 0.090 mmol / g, and even more preferably 0.001 to 0.080 mmol / g. The lower limit of the above amine value is not particularly limited and may be 0.00 mmol / g. The above amine value was measured by dissolving 0.62 g of resin in 50 mL of diglym, and then adding 10 mL of acetic acid to prepare a measurement solution. This solution was then titrated with an acetic acid solution of 0.01 N (0.01 mol / L) perchloric acid and the neutralization point was detected.

[0139] [Transmittance] When the specific resin is used to form a film with a thickness of 5 μm, the transmittance at a wavelength of 365 nm is preferably 10% or more, more preferably 20% or more, even more preferably 30% or more, and most preferably 50% or more. The upper limit of the above transmittance is not particularly limited and may be 100% or less. The above film can be obtained, for example, by dissolving the specific resin in γ-butyrolactone, coating it on a transparent substrate, and then heating it at 100°C for 5 minutes. Considering solvent solubility, N-methylpyrrolidone or the like may be used instead of γ-butyrolactone. Furthermore, the transparent substrate is not particularly limited as long as it is measurable, and glass substrates, or quartz substrates if greater transparency is required, can be used.

[0140] [Synthesis Method for Specific Resins] As a synthesis method for specific resins, general methods for synthesizing polyamic acid or polyamic acid esters, or polyimides can be used. Specific resins as polyimide precursors can be obtained using methods such as: reacting tetracarboxylic dianhydride with a diamine at low temperature; reacting tetracarboxylic dianhydride with a diamine at low temperature to obtain polyamic acid and then esterifying it with a condensing agent or alkylating agent; obtaining a diester from tetracarboxylic dianhydride with an alcohol and then reacting it with a diamine in the presence of a condensing agent; obtaining a diester from tetracarboxylic dianhydride with an alcohol and then acid-halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with a diamine. Of the above production methods, the method of obtaining a diester from tetracarboxylic dianhydride with an alcohol and then acid-halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with a diamine is more preferred. Examples of the condensing agents include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride. Examples of the alkylating agents include N,N-dimethylformamide dimethylacetal, N,N-dimethylformamide diethylacetal, N,N-dialkylformamide dialkylacetal, trimethyl orthoformate, and triethyl orthoformate. Examples of the halogenating agents include thionyl chloride, oxalyl chloride, and phosphorus oxychloride. In the method for producing the specific resin, it is preferable to use an organic solvent in the reaction. One or more organic solvents may be used. The organic solvent can be appropriately determined depending on the raw materials, but examples include pyridine, diethylene glycol dimethyl ether (diglym), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone. In the method for producing specific resins, it is preferable to add a basic compound during the reaction.The basic compound may be one type or two or more types. The basic compound can be appropriately determined depending on the raw materials, but examples include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undeca-7-ene, and N,N-dimethyl-4-aminopyridine.

[0141] -End-Sealing Agents- In the manufacturing method of a specific resin, it is preferable to seal off carboxylic acid anhydrides, acid anhydride derivatives, or amino groups remaining at the ends of the resin, such as polyimide precursors, in order to further improve storage stability. When sealing off carboxylic acid anhydrides and acid anhydride derivatives remaining at the ends of the resin, examples of end-sealing agents include monoalcohols, phenols, thiols, thiophenols, and monoamines. From the perspective of reactivity and film stability, it is more preferable to use monoalcohols, phenols, or monoamines. Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol; secondary alcohols such as isopropanol, 2-butanol, cyclohexyl alcohol, cyclopentanol, and 1-methoxy-2-propanol; and tertiary alcohols such as t-butyl alcohol and adamantane alcohol. Preferred phenolic compounds include phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, hydroxystyrene, and other phenolic compounds.Furthermore, preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, Examples include 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. Furthermore, when encapsulating the amino groups at the ends of the resin, it is possible to encapsulate them with compounds having functional groups that can react with amino groups. Preferred encapsulants for amino groups include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, and sulfonic acid carboxylic acid anhydrides, with carboxylic acid anhydrides and carboxylic acid chlorides being more preferred. Preferred carboxylic acid anhydrides include acetic anhydride, propionic anhydride, oxalic acid anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and 5-norbornene-2,3-dicarboxylic acid anhydride.Furthermore, preferred carboxylic acid chloride compounds include acetyl chloride, acrylate chloride, propionyl chloride, methacrylate chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantane carbonyl chloride, heptafluorobutyryl chloride, stearate chloride, and benzoyl chloride.

[0142] Furthermore, as a terminal encapsulant, it is also preferable to use a compound having a polymerizable group in addition to a functional group that can react with an amino group. The polymerizable group is not limited as long as it can form a new organic bond. Examples of organic bonds that can be formed include carbon-carbon bonds, ester bonds, amide bonds, imide bonds, urea bonds, and urethane bonds. The above organic bonds are formed by radical crosslinking, cationic crosslinking, photodimerization, and by being induced by light or heat from combinations of carboxylic acid-alcohol, carboxylic acid-amine, isocyanate-alcohol, isocyanate-amine, etc. Preferred polymerizable groups include (meth)acrylic groups, styryl groups, carbon-carbon unsaturated groups, maleimide groups, epoxy groups, oxetane groups, and isocyanate groups.

[0143] -Solid Precipitation- The method for producing a specific resin may include a step of precipitating a solid. Specifically, after filtering off the water-absorbing by-products of the dehydrating condensing agent present in the reaction solution as needed, the obtained polymer component is added to a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof, and the polymer component is precipitated as a solid. By drying this precipitate, a polyimide precursor or the like can be obtained. To improve the degree of purity, the polyimide precursor or the like may be repeatedly redissolved, reprecipitation, and dried. Furthermore, the method may include a step of removing ionic impurities using an ion exchange resin.

[0144] [Examples of specific resins] Specific examples of specific resins include the resins used in the examples.

[0145] [Content] The content of the specific resin in the photocurable resin composition of the present invention is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and even more preferably 30% by mass or more, based on the total solid content of the photocurable resin composition. Furthermore, the content of the resin in the photocurable resin composition of the present invention is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on the total solid content of the photocurable resin composition. The photocurable resin composition of the present invention may contain only one type of specific resin, or it may contain two or more types. When it contains two or more types, it is preferable that the total amount is within the above range.

[0146] <Other Resins> The photocurable resin composition of the present invention may also contain other resins different from the specified resin described above (hereinafter also simply referred to as "other resins"). Examples of other resins are resins different from the specified resin, and include polyimide precursors, polyimides, polybenzoxazole precursors, polybenzoxazoles, polyamideimide precursors, polyamideimides, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, polyester resins, and the like. Examples of other polyimide precursors, other polyimides, polybenzoxazole precursors, polybenzoxazoles, polyamideimide precursors, and polyamideimides include compounds described in paragraphs 0017 to 0138 of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0147] When the photocurable resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total solid content of the photocurable resin composition. In the photocurable resin composition of the present invention, the content of other resins is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on the total solid content of the photocurable resin composition. In one preferred embodiment of the photocurable resin composition of the present invention, the content of other resins is also low. In the above embodiment, the content of other resins is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the photocurable resin composition. The lower limit of the above content is not particularly limited, and it is sufficient if it is 0% by mass or more. The photocurable resin composition of the present invention may contain only one other resin, or it may contain two or more other resins. When it contains two or more resins, it is preferable that the total amount is within the above range.

[0148] <Polymerizable Compounds> The photocurable resin composition of the present invention preferably contains polymerizable compounds with a molecular weight of less than 3,000.

[0149] Examples of polymerizable compounds include polymerizable compounds having radical polymerizable groups (radical crosslinking agents) or other crosslinking agents. Among these, polymerizable compounds having radical polymerizable groups are preferred. The polyfunctional polymerizable compounds described above are preferably polymerizable compounds having two or more radical polymerizable groups.

[0150] [Radical Crosslinking Agent] The photocurable 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.

[0151] 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. Here, the polyfunctional polymerizable compound described above is preferably a compound having two or more ethylenically unsaturated bonds, and may also have three or more. As for the compound having two or more ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferred, a compound having 2 to 10 ethylenically unsaturated bonds is more preferred, and a compound having 2 to 6 is even more preferred. From the viewpoint of the film strength of the resulting pattern (cured product), the photocurable resin composition of the present invention may also preferably contain a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds.

[0152] 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.

[0153] Specific examples of radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and 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.

[0154] 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.

[0155] 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.

[0156] 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.

[0157] 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).

[0158] Suitable radical crosslinking agents include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Unexamined Patent Publication No. 51-037193, Japanese Unexamined Patent Publication No. 02-032293, and Japanese Unexamined Patent Publication No. 02-016765, as well as urethane compounds having an ethylene oxide-based skeleton as described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418. Compounds having an amino or sulfide structure within the molecule, as described in Japanese Unexamined Patent Publication No. 63-277653, Japanese Unexamined Patent Publication No. 63-260909, and Japanese Unexamined Patent Publication No. 01-105238, can also be used as radical crosslinking agents.

[0159] The radical crosslinking agent may be a radical crosslinking agent having an acidic group such as a carboxyl group or a phosphate group. The radical crosslinking agent having an acidic group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent obtained by reacting the unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group. Particularly preferred is a radical crosslinking agent obtained by reacting the unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group, wherein the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include M-510 and M-520, which are polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

[0160] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mg KOH / g, and more preferably 1 to 100 mg KOH / g. When the acid value of the radical crosslinking agent is within the above range, it exhibits excellent handling properties during manufacturing and excellent developability. It also exhibits good polymerization properties. The above acid value is measured in accordance with the description in JIS K 0070:1992.

[0161] As radical crosslinking agents, radical crosslinking agents having at least one selected from the group consisting of urea bonds and urethane bonds (hereinafter also referred to as "crosslinking agent U") are also preferred. Examples of crosslinking agent U include compounds described in paragraphs 0133 to 0143 of International Publication No. 2023 / 190064. This content is incorporated herein by reference. In addition, polyfunctional urethane (meth)acrylates having a secondary or tertiary amine structure as described in Japanese Patent Application Publication No. 2024-119727, polyfunctional urethane (meth)acrylates having an isocyanuric ring as described in International Publication No. 2024 / 237134, etc., are also suitably used. This content is incorporated herein by reference.

[0162] From the viewpoint of pattern resolution and film stretchability, it is preferable to use a bifunctional methacrylate or acrylate in the photocurable 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 difunctional acrylates and difunctional 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. In the photocurable resin composition of the present invention, a monofunctional radical crosslinking agent can preferably be used as the radical crosslinking agent, from the viewpoint of suppressing warping of the pattern (cured product).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.

[0163] 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 photocurable 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.

[0164] 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.

[0165] [Other Crosslinking Agents] The photocurable 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 the 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 photobase generator, and more preferably compounds having multiple groups in the 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 base. The acid or base is preferably an acid or base generated from a photoacid generator or photobase generator in the exposure step. 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.

[0166] [Other Radical Polymerization Initiators] The photopolymerization initiator contained in the photocurable resin composition of the present invention may include a compound different from compound A (hereinafter also referred to as "other photopolymerization initiator"). By using compound A and other photopolymerization initiators in combination, it is possible to adjust the balance between suppressing the generation of residue, suppressing discoloration, and maintaining stability over time. When compound A and other photopolymerization initiators are used in combination, the content of the other photopolymerization initiator is preferably 10 to 90 parts by mass per 100 parts by mass of compound A. The upper limit is preferably 80 parts by mass or less, and more preferably 70 parts by mass or less. The lower limit is preferably 20 parts by mass or more, and more preferably 30 parts by mass or more. Furthermore, it is also preferable that the photopolymerization initiator used in the present invention is substantially compound A only. According to this embodiment, the generation of discoloration caused by the photopolymerization initiator can be suppressed. When the photopolymerization initiator is substantially compound A only, it means that the content of compound A in the photopolymerization initiator is 99% by mass or more, preferably 99.9% by mass or more, and more preferably compound A only.

[0167] Other photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, and α-aminoketone compounds. Other photopolymerization initiators are preferably trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, hexaarylbiimidazole compounds, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds, or 3-aryl-substituted coumarin compounds, more preferably oxime compounds, α-hydroxyketone compounds, α-aminoketone compounds, or acylphosphine compounds, even more preferably α-aminoketone compounds or oxime compounds, and particularly preferably oxime compounds.

[0168] Other photopolymerization initiators include the compounds described in paragraphs 0065 to 0111 of Japanese Patent Publication No. 2014-130173, the compounds described in Japanese Patent Publication No. 6301489, and MATERIAL STAGE 37-60p, vol. 19, No. 3. Peroxide-based photopolymerization initiators described in 2019, photopolymerization initiators described in International Publication No. 2018 / 221177, photopolymerization initiators described in International Publication No. 2018 / 110179, photopolymerization initiators described in JP 2019-043864, photopolymerization initiators described in JP 2019-044030, peroxide-based initiators described in JP 2019-167313, aminoacetophenone-based initiators having an oxazolidine group described in JP 2020-055992, JP 2013- Oxime-based photopolymerization initiator described in Japanese Patent Publication No. 190459, polymer described in Japanese Patent Application Publication No. 2020-172619, compound represented by formula 1 described in International Publication No. 2020 / 152120, compound described in Japanese Patent Application Publication No. 2021-181406, photopolymerization initiator described in Japanese Patent Application Publication No. 2022-013379, compound represented by formula (1) described in Japanese Patent Application Publication No. 2022-015747, fluorine-containing fluorene oxime ester-based photoinitiator described in Japanese Patent Application Publication No. 2021-507058, Chinese Patent Application Publication No. 11 Initiators described in Specification No. 0764367, initiators described in Japanese Patent Publication No. 2022-518535, initiators described in International Publication No. 2021 / 175855, compounds described in Taiwan Patent Application Publication No. 202200534, compounds described in Japanese Patent Application Publication No. 2022-078550, compounds described in Korean Published Patent No. 10-2017-0087330, compounds described in International Publication No. 2022 / 075452, oxime ester compounds described in Chinese Patent Application Publication No. 110066225, Korean Compounds described in Japanese Patent Publication No. 10-2022-0076157, compounds described in paragraphs 0042-0062 of International Publication No. 2019 / 013112 having a triarylamine or N-arylcarbazole skeleton, oxime ester-based photopolymerization initiators described in Japanese Patent Publication No. 7219378, photopolymerization initiators described in Korean Published Patent No. 10-2021-0146174, photopolymerization initiators described in International Publication No. 2019 / 013112, photopolymerization initiators described in Japanese Patent Publication No. 2023-033731,Initiators described in Japanese Patent Publication No. 2022-515524, initiators described in Japanese Patent Publication No. 2023-517304, initiators described in Chinese Patent Application Publication No. 114149517, aminoketone compounds described in Chinese Patent Application Publication No. 115925596, compounds described in Japanese Patent Application Publication No. 2023-159489, compounds described in Japanese Patent Application Publication No. 2023-159487, compounds described in Taiwan Patent Application Publication No. 202336003, compounds described in Chinese Patent Application Publication No. 113527138, organosilicon compounds described in Japanese Patent Publication No. 2022-502526, Korean Published Patent Examples include the oxime compound described in Japanese Patent Publication No. 10-2017-0009794, the photopolymerization initiator described in Korean Published Patent Publication No. 10-2023-0033862, the oxime ester compound described in Japanese Patent Publication No. 2019-519518, the polyfunctional polymer photopolymerization initiator described in Japanese Patent Publication No. 2024-517534, the photopolymerization initiator described in International Publication No. 2024 / 085227, the compound described in Japanese Patent Publication No. 2024-521379, the photopolymerization initiator described in Japanese Patent Publication No. 2024-523053, and the oxime ester initiator described in Chinese Patent Application Publication No. 117510396.

[0169] Specific examples of hexaarylbiimidazole compounds include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole.

[0170] Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all manufactured by IGM Resins B.V.), and Irgacure 184, Irgacure 1173, Irgacure 2959, and Irgacure 127 (all manufactured by BASF). Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins B.V.), and Irgacure 907, Irgacure 369, Irgacure 369E, and Irgacure 379EG (all manufactured by BASF). Commercially available acylphosphine compounds include Omnirad 819 and Omnirad TPO (both manufactured by IGM Resins B.V.), and Irgacure 819 and Irgacure TPO (both manufactured by BASF).

[0171] Examples of oxime compounds include the compounds described in paragraph 0142 of International Publication No. 2022 / 085485, the compounds described in Japanese Patent No. 5430746, the compounds described in Japanese Patent No. 5647738, the compounds represented by general formula (1) and the compounds described in paragraphs 0022 to 0024 of Japanese Patent Publication No. 2021-173858, and the compounds represented by general formula (1) and the compounds described in paragraphs 0117 to 0120 of Japanese Patent Publication No. 2021-170089. Specific examples of oxime compounds include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one, and 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime). Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE03-NP, Irgacure OXE04, Irgacure OXE05 (all manufactured by BASF), TR-PBG-301, TR-PBG-304, TR-PBG-305, TR-PBG-309, TR-PBG-3054, TR-PBG-3057, TR-PBG-314, TR-PBG-327, TR-PBG-345, TR-PBG-346, TR-PBG-358, TR-PBG-365, TR-P Examples include BG-380, TR-PBG-610, TR-PBG-A, TR-PBG-B, TR-NPI-807, TR-PSS-206, TR-NPI-800, TR-NPI-20400 (all manufactured by TRONLY), and ADEKA optomer N-1919 (manufactured by ADEKA Corporation, photopolymerization initiator 2 described in Japanese Patent Publication No. 2012-014052). Furthermore, it is also preferable to use compounds that do not produce color or compounds that are highly transparent and resistant to discoloration as oxime compounds.Commercially available products include ADEKA Arclus NCI-730, NCI-831, NCI-831E, NCI-930 (all manufactured by ADEKA Corporation), SpeedCure PDO (manufactured by ARKEMA Sartmar), SPI-02, SPI-03, SPI-05, SPI-06, SPI-07 (manufactured by SAMYANG), and Nikkacure YJ-04(T), IW-15, TG-10, TG-05, TKG-01 (manufactured by Nippon Chemical Industrial Co., Ltd.).

[0172] Other photopolymerization initiators may include oxime compounds having a fluorene ring, oxime compounds having a skeleton in which at least one benzene ring of the carbazole ring is replaced by a naphthalene ring, oxime compounds having a fluorine atom, oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, oxime compounds in which a substituent having a hydroxyl group is attached to the carbazole skeleton, and compounds described in paragraphs 0143 to 0149 of International Publication No. 2022 / 085485.

[0173] Among these, the photocurable resin composition preferably contains a (keto)oxime ester compound as another photopolymerization initiator. Examples of (keto)oxime ester compounds include those described in paragraph 0121 of Japanese Patent Application Publication No. 2023-111491, etc. The compounds used in the present examples can also be suitably used.

[0174] As an alternative photopolymerization initiator, the compound represented by formula (OX-1) can also be used.

[0175] In formula (OX-1), X １ａ R represents a divalent linking group containing at least one selected from the group consisting of aromatic rings and heterocycles. １ａ R represents a hydrogen atom or an acyl group. ２ａ R represents an alkyl or aryl group. ３ａ and R ４ａ Each of these independently represents a hydrogen atom or an alkyl group, and Alk １ and Alk ２ Each of these independently represents an alkyl group, R ３ａ and R ４ａThey may be bonded together to form a ring, Alk １ and Alk ２ The elements may be joined together to form a ring, and n represents either 0 or 1.

[0176] X in equation (OX-1) １ａ Examples of divalent linking groups represented by include divalent aromatic ring groups, divalent heterocyclic groups, divalent groups formed by linking two or more aromatic ring groups via single bonds or linking groups, divalent groups formed by linking two or more heterocyclic groups via single bonds or linking groups, and divalent groups formed by linking an aromatic ring group and a heterocyclic group via single bonds or linking groups. Examples of linking groups that link aromatic ring groups to each other, heterocyclic groups to each other, or an aromatic ring group and a heterocyclic group include -CH ２ -, -O-, -CO-, -S-, -NR ｘ - And combinations thereof, etc. are examples. ｘ This represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.

[0177] X in equation (OX-1) １ａ It is preferably a group represented by any of formulas (X-1) to (X-13), more preferably a group represented by formula (X-1), formula (X-2), formula (X-4), formula (X-6), or formula (X-8), and even more preferably a group represented by formula (X-2) or formula (X-6).

[0178] In the formula R Ｘ１ ~R Ｘ９ Each of these independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and * represents a bond.

[0179] R Ｘ１ ~R Ｘ９ The alkyl group represented by is preferably 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms. The alkyl group may be linear, branched, or cyclic. The alkyl group may have substituents. Examples of substituents include halogen atoms and aryl groups.

[0180] R Ｘ１ ~R Ｘ９The number of carbon atoms in the alkenyl group represented by is preferably 2 to 15, and more preferably 2 to 10. The alkenyl group may be linear, branched, or cyclic. The alkenyl group may have substituents. Examples of substituents include halogen atoms and aryl groups.

[0181] R Ｘ１ ~R Ｘ９ The number of carbon atoms in the alkynyl group represented by is preferably 2 to 15, and more preferably 2 to 10. The alkynyl group may be linear, branched, or cyclic. The alkynyl group may have substituents. Examples of substituents include halogen atoms and aryl groups.

[0182] R Ｘ１ ~R Ｘ９ When the aryl group represented is an aromatic hydrocarbon group, the number of carbon atoms is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6. The aryl group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and aryl groups.

[0183] R Ｘ１ ~R Ｘ９ When the aryl group represented is an aromatic heterocyclic group, a five-membered or six-membered ring is preferred. The heteroatoms of the aromatic heterocyclic group are preferably oxygen, nitrogen, and sulfur atoms. The number of heteroatoms of the aromatic heterocyclic group is preferably 1 to 3. The aromatic heterocyclic group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and aryl groups.

[0184] R in equation (OX-1) １ａ represents a hydrogen atom or an acyl group, and an acyl group is preferred.

[0185] R in equation (OX-1) ２ａ R represents an alkyl group or an aryl group, and is preferably an alkyl group because the generated radical is highly reactive. ２ａThe number of carbon atoms in the alkyl group represented by is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkyl group may have substituents, but is preferably an unsubstituted alkyl group. ２ａ The alkyl group represented by is preferably an unsubstituted linear or branched alkyl group, and more preferably an unsubstituted linear alkyl group. ２ａ The number of carbon atoms in the aryl group represented by is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6. The aryl group may have substituents, but it is preferably an unsubstituted aryl group.

[0186] R in equation (OX-1) ３ａ and R ４ａ Each of these independently represents a hydrogen atom or an alkyl group, and a hydrogen atom is preferred. ３ａ and R ４ａ The number of carbon atoms in the alkyl group represented by is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkyl group may have substituents, but is preferably an unsubstituted alkyl group. ３ａ and R ４ａ These may be bonded together to form a ring. The formed ring is preferably a five-membered or six-membered ring, and more preferably a five-membered or six-membered aliphatic hydrocarbon ring.

[0187] Alk in equation (OX-1) １ and Alk ２Each of these independently represents an alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkyl group may have substituents, but is preferably an unsubstituted alkyl group. Alk １ and Alk ２ The elements may be bonded together to form a ring, and it is preferable that a ring is formed. The formed ring is preferably a five-membered or six-membered ring, more preferably a five-membered or six-membered aliphatic hydrocarbon ring, and even more preferably a cyclopentane ring or a cyclohexane ring.

[0188] In formula (OX-1), n ​​represents either 0 or 1, and is preferably 0.

[0189] Specific examples of compounds represented by formula (OX-1) include the compounds described in paragraphs 0092 to 0096 of Japanese Patent Publication No. 2012-113104 and the compounds described in paragraph 0041 of Japanese Patent Publication No. 2012-189997.

[0190] As an alternative photopolymerization initiator, the compound represented by formula (OX-2) can also be used.

[0191]

[0192] In formula (OX-2), R １ｂ and R ２ｂ Each of these independently represents a substituent, R ３ｂ ~R ７ｂ Each of these independently represents a hydrogen atom or a substituent, and Ar １ｂ represents an aryl group which may have substituents, and n represents 0 or 1.

[0193] R １ｂ and R ２ｂExamples of substituents represented by include alkyl groups and aryl groups, with alkyl groups being preferred. The number of carbon atoms in the alkyl group is preferably 1 to 15, and more preferably 1 to 10. The alkyl group may be linear, branched, or cyclic. The alkyl group may have substituents. Examples of substituents include halogen atoms, aryl groups, alkenyl groups, alkynyl groups, and aryl groups. The number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6. The aryl group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and aryl groups.

[0194] R ３ｂ ~R ７ｂ The substituents represented by include halogen atoms, alkyl groups, and aryl groups. Examples of alkyl groups and aryl groups are those mentioned above. ３ｂ ~R ７ｂ It is preferable that it is a hydrogen atom.

[0195] Ar １ｂ Ar represents an aryl group which may have substituents. １ｂ It is preferable that the group is an aromatic hydrocarbon group which may have substituents. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6. Examples of substituents include halogen atoms, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, alkylthio groups, arylthio groups, nitro groups, and acyl groups, with acyl groups being preferred.

[0196] As an alternative photopolymerization initiator, the compound represented by formula (OX-3) can also be used.

[0197]

[0198] In formula (OX-3), Ar １ｃ Ar represents an aromatic ring group with (k+m+1) valency or a heterocyclic ring group with (k+m+1) valency. ２ｃ R represents a (k+2) valent aromatic ring group or a (k+2) valent heterocyclic group, １ｃ ~R３ｃ Each of these independently represents a substituent, L １ｃ is a single bond or CR １１ｃ R １２ｃ Represents R １１ｃ and R １２ｃ Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, X １ｃ ha-CH ２ It represents -, -N-, -O-, or -S-, where k represents 0 or 1, m represents an integer from 0 to 4, and n represents 0 or 1.

[0199] R １ｃ and R ２ｃ The substituents represented by include alkyl groups and aryl groups, with alkyl groups being preferred. The number of carbon atoms in the alkyl group is preferably 1 to 15, and more preferably 1 to 10. The alkyl group may be linear, branched, or cyclic. The alkyl group may have substituents. Examples of substituents include halogen atoms, aryl groups, alkenyl groups, alkynyl groups, and aryl groups. The number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6. The aryl group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and aryl groups. ２ｃ It is preferable that the alkyl group has a branched or cyclic structure.

[0200] R ３ｃ Examples of substituents represented by include halogen atoms, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, and acyl groups, with acyl groups being preferred.

[0201] L １ｃ is a single bond or CR １１ｃ R １２ｃ Represents R １１ｃ and R １２ｃ Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group. １１ｃ and R １２ｃ The alkyl and aryl groups in R １ｃ and R ２ｃThis is synonymous with alkyl and aryl groups in [the given context]. When k is 1, L １ｃ It is preferable that the bond is a single bond.

[0202] X １ｃ is, -CH ２ It represents -, -N-, -O-, or -S-, with -O- or -S- being preferred.

[0203] Ar １ｃ represents a (k+m+1) valent aromatic ring group or a (k+m+1) valent heterocyclic group, and is preferably a (k+m+1) valent aromatic ring group. The aromatic ring group is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group.

[0204] Ar ２ｃ represents a (k+2) valent aromatic ring group or a (k+2) valent heterocyclic group, and is preferably a (k+2) valent aromatic ring group. The aromatic ring group is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group.

[0205] k represents 0 or 1, preferably 0. m represents an integer from 0 to 4, preferably 0 or 1, more preferably 1. n represents 0 or 1, preferably 0.

[0206] Other photopolymerization initiators that can be suitably used include ketoxime ester compounds having an allyl oil oxy group at the ortho position, represented by formula (OX-4). Examples of such compounds include those described in Chinese Patent Application Publication No. 117342977.

[0207] In formula (OX-4), R １ｄ and R ２ｄ Each of these independently represents an alkyl group, an aryl group, or a heterocyclic group; R ３ｄ , R ４ｄ , R ５ｄ , R ６ｄ These are, independently, hydrogen atoms, halogen atoms, CN, and NO. ２ CF ３ ,R,OR,SR,SOR,SO ２R represents R or NRR', where R and R' each independently represent an alkyl group or an aryl group, and when R and R' are present together, R and R' may be bonded to form a ring, and one or more -CH groups in the alkyl group or aryl group represented by R and R' ２ Each of the hyphens may be independently substituted with -O-, -N-, -S-, -CO-, -COO-, -OCO-, or a benzene ring; R ７ｄ , R ８ｄ and R ９ｄ Each of these independently represents either a hydrogen atom or a methyl group.

[0208] Other photopolymerization initiators that can be suitably used include compounds represented by formula (OX-5). Examples of such compounds include those described in International Publication No. 2024 / 101219.

[0209] In formula (OX-5), R １ｅ ~R ５ｅ Each of these independently represents a hydrocarbon group which may have substituents, and n represents an integer from 0 to 4.

[0210] Specific examples of oxime compounds include the following compounds.

[0211]

[0212] Other photopolymerization initiators may be used, including bifunctional or trifunctional or more functional photopolymerization initiators. Specific examples of bifunctional or trifunctional or more functional photopolymerization initiators include the compounds described in paragraph 0148 of International Publication No. 2022 / 065215.

[0213] The content of the photopolymerization initiator in the total solids of the photocurable resin composition is preferably 1 to 20% by mass. The lower limit is preferably 2% by mass or more, and more preferably 3% by mass or more. The upper limit is preferably 15% by mass or less, and more preferably 10% by mass or less.

[0214] The content of compound A in the photopolymerization initiator is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. The upper limit can be 100% by mass or less.

[0215] In a photocurable resin composition, the ratio of photopolymerization initiator to polymerizable compound is preferably 2 to 100 parts by mass of photopolymerization initiator per 100 parts by mass of polymerizable compound. The upper limit is preferably 80 parts by mass or less, and more preferably 50 parts by mass or less. The lower limit is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more.

[0216] The ratio of compound A to polymerizable compound in the photocurable resin composition is preferably 2 to 100 parts by mass of compound A per 100 parts by mass of polymerizable compound. The upper limit is preferably 80 parts by mass or less, and more preferably 50 parts by mass or less. The lower limit is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more.

[0217] In the photocurable resin composition of the present invention, one type of photopolymerization initiator 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.

[0218] [Sensitizer] The photocurable 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 Michla's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyrideneindanone, and p-dimethylaminobenzylideneindanone. Non, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin Phosphorus, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylate ethyl), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, diethylaminobenzoate Examples include soamyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazol, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, etc. Other sensitizing dyes may also be used. For details on sensitizing dyes, refer to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which are incorporated herein by reference.When the photosensitive 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 photosensitive resin composition. The sensitizer may be used alone or in combination of two or more types.

[0219] [Amine Compounds] From the viewpoint of resolution, it is preferable for the photocurable resin composition to contain amine compounds. The amine compound is preferably a compound that acts as a sensitizer, and more preferably a compound that has a sensitizing effect on photoradical polymerization initiators. The sensitizer absorbs specific active radiation and enters an electronically excited state. The sensitizer in the electronically excited state comes into contact with thermal radical polymerization initiators, photoradical polymerization initiators, etc., causing effects such as 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. In addition, if some of the amine compound remains in the cured product, acids generated in the cured product and acids introduced from outside the cured product are quenched, and as a result the oxidation of metals is suppressed, the adhesion may be improved.

[0220] Preferred amine compounds include compounds containing a benzene ring structure with a dialkylamino group or a dihydroxyalkylamino group as a substituent.

[0221] Examples of amine compounds include Michlaz ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyrideneindanone, p-dimethylaminobenzylideneindanone, 2- (p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbon Nyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylate ethyl), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, dimethylaniline, bis(4-dimeth Examples include (p-(p-dimethylaminophenyl)methane, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazol, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, etc.

[0222] Among these, the amine compound is preferably the compound represented by the following formula (AN-1) or the following formula (AN-2) (hereinafter also referred to as "compound A"). In formula (AN-1), R １１ and R １２ Each of these independently represents a hydrogen atom or a monovalent organic group, R １１ and R １２ At least one of them contains a group represented by formula (R-1), and Ar １ R represents an aromatic ring structure which may have substituents or fused rings, n1 represents an integer of 2 or more, when n1 is 2, X represents a single bond or a divalent linking group, when n1 is 3 or more, X represents an n1valent linking group. In formula (AN-2), R ２１ and R ２２ Each of these independently represents a hydrogen atom or a monovalent organic group, R ２１ and R ２２ At least one of them contains a group represented by formula (R-1), and Ar ２ represents an aromatic ring structure which may have substituents or fused rings, and n2 represents an integer of 1 or more. In formula (R-1), R Ｒ１ and R Ｒ２ Each of these independently represents a hydrogen atom or a monovalent organic group, and there are m R Ｒ１ Each of them may be the same or different, and there are m R Ｒ２ These elements may be the same or different, m represents an integer greater than or equal to 2, and * represents a connection point with another structure.

[0223] In formula (AN-1), R １１ and R １２ Preferably, all of these are groups represented by formula (R-1). １１ and R １２ If one of them is a hydrogen atom or a monovalent organic group different from the group represented by formula (R-1), then R １１ and R １２ Preferably, one of the groups is a monovalent organic group different from the group represented by formula (R-1). Examples of monovalent organic groups different from the group represented by formula (R-1) include alkyl groups and aryl groups, with alkyl groups being preferred and methyl groups being more preferred.

[0224] In the group represented by formula (R-1), R Ｒ１ and R Ｒ２ Each of these independently represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom or a methyl group. Ｒ１ and R Ｒ２ It is also a preferred embodiment that all of them are hydrogen atoms. In formula (R-1), m represents an integer of 2 or more, preferably an integer between 2 and 4, more preferably 2 or 3, and even more preferably 2. Specific examples of the group represented by formula (R-1) are given below, but the present invention is not limited thereto. In the following specific examples, * is synonymous with * in formula (R-1).

[0225] In equation (AN-1), Ar １ represents an aromatic ring structure which may have substituents or fused rings. In formula (AN-1), Ar １ The aromatic ring structure may be either an aromatic hydrocarbon ring structure or an aromatic heterocyclic ring structure, but the aromatic hydrocarbon ring structure is preferred, and the benzene ring structure is more preferred. Examples of substituents include alkyl groups, aryl groups, halogen atoms, etc., with alkyl groups being preferred, and methyl groups being more preferred. Examples of fused rings include cycloalkanes, aromatic rings, etc., with cyclopropane rings being preferred.

[0226] In formula (AN-1), n1 represents an integer between 2 and 4, preferably 2 or 3, and more preferably 2.

[0227] In formula (AN-1), when n1 is 2, X represents a single bond or a divalent linking group. The divalent linking group is preferably an alkylene group, a haloalkylene group, an arylene group, or a combination thereof. The hydrogen atoms in these groups may be substituted with known substituents such as hydroxyl groups or halogen atoms. The alkylene group is preferably an alkylene group having 1 to 4 carbon atoms, and more preferably a methylene group, an ethylene group, or an isopropylene group. The arylene group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, but is preferably an aromatic hydrocarbon group, and more preferably a phenylene group.

[0228] In formula (AN-1), when n1 is 3 or greater, X represents an n1-valent linking group. The n1-valent linking group is preferably an aliphatic hydrocarbon group, an aromatic group, or a combination thereof. The hydrogen atoms in these groups may be substituted with known substituents such as hydroxyl groups. The aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, and more preferably a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms. The aromatic group is preferably an aromatic hydrocarbon group, and more preferably an aromatic hydrocarbon group having 6 carbon atoms.

[0229] In formula (AN-2), R ２１ and R ２２ A preferred embodiment is R in formula (AN-1). １１ and R １２ This is similar to the preferred embodiment.

[0230] In equation (AN-2), Ar ２ represents an aromatic ring structure which may have substituents or fused rings. Examples of the above aromatic ring structures include a benzene ring structure, a carbazole ring structure, a fluorene ring structure, etc. Examples of the above substituents include alkyl groups, aryl groups, halogen atoms, etc., with alkyl groups being preferred and methyl groups being more preferred. Examples of the above fused rings include cycloalkanes, aromatic rings, etc., with cyclopropane rings being preferred. Below, Ar ２The present invention is not limited to the following specific examples. In the examples below, * represents the bonding site with the nitrogen atom in formula (AN-2).

[0231] In formula (AN-2), n2 is preferably an integer between 1 and 3, and more preferably 1 or 2.

[0232] Among these, compound A is the compound represented by the above formula (AN-1), and R in the above formula (AN-1) １１ and R １２ These are all groups represented by formula (R-1), and the embodiment in which m in formula (R-1) is 2 is preferred. Preferred embodiments of other symbols in the above embodiment are as described in the explanation of formula (AN-1) above.

[0233] The molecular weight of compound A is preferably 1,000 or less, more preferably 800 or less, and even more preferably 500 or less. The lower limit of the molecular weight is not particularly limited, but for example, it is preferably 150 or more, and more preferably 200 or more.

[0234] When the photocurable resin composition contains an amine compound, the content of the amine compound 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 photocurable resin composition. The amine compound may be used alone or in combination of two or more types.

[0235] Furthermore, other sensitizing dyes may be used as sensitizers. Details of sensitizing dyes can be found in paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which are incorporated herein by reference.

[0236] [Chain Transfer Agent] The photocurable resin composition of the present invention may contain a chain transfer agent. A chain transfer agent is 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. ２Compounds 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 generating radicals after oxidation and deprotonation. Thiol compounds are particularly preferred.

[0237] 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.

[0238] If the photocurable 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 photocurable 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.

[0239] Furthermore, a preferred embodiment of the present invention is that the photocurable resin composition of the present invention contains two or more polymerization initiators as polymerization initiators. Specifically, it is preferable that the photocurable resin composition of the present invention contains a photopolymerization initiator and a thermal polymerization initiator described later, or contains the above-mentioned photoradical polymerization initiator and photoacid generator.

[0240] 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.

[0241] 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.

[0242] [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.

[0243] 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.

[0244] 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 photocurable 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.

[0245] <Base Generator> The photocurable resin composition of the present invention may further contain a base generator different from compound A. 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. By containing a thermal base generator in the photocurable 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 included in semiconductor packages. 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, phthalimide derivative compounds, and acyloxyimino compounds. Specific examples of nonionic base-generating agents include compounds represented by formula (B1), formula (B2), or formula (B3).

[0246] In formulas (B1) and (B2), Rb １ , Rb ２ and Rb ３ Each of these independently represents an organic group that does not have a tertiary amine structure, a halogen atom, or a hydrogen atom. However, Rb １ and Rb ２ They cannot simultaneously become hydrogen atoms. Also, Rb １ , Rb ２ and Rb ３None of these structures have a carboxyl group. In this specification, a tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to carbon atoms of a hydrocarbon group. Therefore, if the carbon atom bonded to the trivalent nitrogen atom is a carbon atom that constitutes a carbonyl group, that is, if it forms an amide group together with the nitrogen atom, it is not a tertiary amine structure.

[0247] In formulas (B1) and (B2), Rb １ , Rb ２ and Rb ３ Preferably, at least one of these components contains a cyclic structure, and more preferably, at least two contain cyclic structures. The cyclic structure may be a monoring or a fused ring, with a monoring or a fused ring formed by the fusion of two monorings being preferred. The monoring is preferably a five-membered ring or a six-membered ring, with a six-membered ring being more preferred. The monoring is preferably a cyclohexane ring or a benzene ring, with a cyclohexane ring being more preferred.

[0248] More specifically, Rb １ and Rb ２ The group is preferably a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 25 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12 carbon atoms). These groups may have substituents. Rb １ and Rb ２ These may be bonded to each other to form a ring. The ring formed is preferably a 4- to 7-membered nitrogen-containing heterocycle. Rb １ and Rb ２The group is preferably a substituted linear, branched, or cyclic alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), more preferably a substituted cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably 3 to 18, and even more preferably 3 to 12 carbon atoms), and even more preferably a substituted cyclohexyl group.

[0249] Rb ３ Examples include alkyl groups (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), aryl groups (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), alkenyl groups (preferably with 2 to 24 carbon atoms, more preferably 2 to 12, and even more preferably 2 to 6), arylalkyl groups (preferably with 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12), arylalkenyl groups (preferably with 8 to 24 carbon atoms, more preferably 8 to 20, and even more preferably 8 to 16), alkoxy groups (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), aryloxy groups (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12), or arylalkyloxy groups (preferably with 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12). Among these, cycloalkyl groups (preferably with 3 to 24 carbon atoms, more preferably with 3 to 18 carbon atoms, and even more preferably with 3 to 12 carbon atoms), arylalkenyl groups, and arylalkyloxy groups are preferred. Rb ３ It may have further substituents.

[0250] The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or formula (B1-2).

[0251] In the formula, Rb １１ and Rb １２ , and Rb ３１ and Rb ３２ These are Rb in equation (B1), respectively. １ and Rb ２ It is the same as Rb １３The group is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12 carbon atoms), and may have substituents. Among these, Rb １３ An aryl alkyl group is preferred.

[0252] Rb ３３ and Rb ３４ Each of these is independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 8, and even more preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10 carbon atoms), and an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11 carbon atoms), with the hydrogen atom being preferred.

[0253] Rb ３５ The group is an alkyl group (preferably with 1 to 24 carbon atoms, more preferably with 1 to 12, and even more preferably with 3 to 8 carbon atoms), an alkenyl group (preferably with 2 to 12 carbon atoms, more preferably with 2 to 10, and even more preferably with 3 to 8 carbon atoms), an aryl group (preferably with 6 to 22 carbon atoms, more preferably with 6 to 18, and even more preferably with 6 to 12 carbon atoms), and an aryl alkyl group (preferably with 7 to 23 carbon atoms, more preferably with 7 to 19, and even more preferably with 7 to 12 carbon atoms), with the aryl group being preferred.

[0254] The compound represented by formula (B1-1) is preferably the compound represented by formula (B1-1a).

[0255] Rb １１ and Rb １２ Rb in equation (B1-1) １１ and Rb １２ This is synonymous with Rb. １５ and Rb １６Rb is a hydrogen atom, an alkyl group (preferably with 1 to 12 carbon atoms, more preferably with 1 to 6 carbon atoms, and even more preferably with 1 to 3 carbon atoms), an alkenyl group (preferably with 2 to 12 carbon atoms, more preferably with 2 to 6 carbon atoms, and even more preferably with 2 to 3 carbon atoms), an aryl group (preferably with 6 to 22 carbon atoms, more preferably with 6 to 18 carbon atoms, and even more preferably with 6 to 10 carbon atoms), and an arylalkyl group (preferably with 7 to 23 carbon atoms, more preferably with 7 to 19 carbon atoms, and even more preferably with 7 to 11 carbon atoms), with hydrogen atoms or methyl groups being preferred. １７ The group is an alkyl group (preferably with 1 to 24 carbon atoms, more preferably with 1 to 12, and even more preferably with 3 to 8 carbon atoms), an alkenyl group (preferably with 2 to 12 carbon atoms, more preferably with 2 to 10, and even more preferably with 3 to 8 carbon atoms), an aryl group (preferably with 6 to 22 carbon atoms, more preferably with 6 to 18, and even more preferably with 6 to 12 carbon atoms), and an arylalkyl group (preferably with 7 to 23 carbon atoms, more preferably with 7 to 19, and even more preferably with 7 to 12 carbon atoms), with the aryl group being the most preferred.

[0256]

[0257] In formula (B3), L represents a divalent hydrocarbon group having a saturated hydrocarbon group on the linking chain pathway connecting adjacent oxygen atoms and carbon atoms, and having three or more atoms on the linking chain pathway. Ｎ１ and R Ｎ２ Each of these independently represents a monovalent organic group.

[0258] In this specification, "linking chain" refers to the atomic chain on the path connecting two atoms or groups of atoms to be linked, specifically the one that connects these linked atoms in the shortest possible time (minimum number of atoms). For example, in the compound represented by the following formula, L is composed of a phenyleneethylene group and has an ethylene group as a saturated hydrocarbon group, the linking chain is composed of four carbon atoms, and the number of atoms on the path of the linking chain (i.e., the number of atoms constituting the linking chain, hereinafter also referred to as "linking chain length" or "length of the linking chain") is 4.

[0259] The number of carbon atoms in L in formula (B3) (including carbon atoms other than those in the linking chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, even more preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of rapidly carrying out the above intramolecular cyclization reaction, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, even more preferably 6 or less, and particularly preferably 5 or less. In particular, the linking chain length of L is preferably 4 or 5, and most preferably 4. Specific preferred compounds for the base generator include, for example, the compounds described in paragraphs 0102 to 0168 of International Publication No. 2020 / 066416 and the compounds described in paragraphs 0143 to 0177 of International Publication No. 2018 / 038002.

[0260] Furthermore, the base generator may also preferably contain a compound represented by the following formula (N1).

[0261] In formula (N1), R Ｎ１ and R Ｎ２ Each of these independently represents a monovalent organic group, R Ｃ１ represents a hydrogen atom or protecting group, and L represents a divalent linking group.

[0262] L is a divalent linking group, preferably a divalent organic group. The linking chain length of the linking group is preferably 1 or more, more preferably 2 or more. The upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The linking chain length is the number of atoms in the shortest path between the two carbonyl groups in the formula.

[0263] In formula (N1), R Ｎ１ and R Ｎ２Each independently represents a monovalent organic group (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), and is preferably a hydrocarbon group (preferably with 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 10 carbon atoms). Specifically, examples include an aliphatic hydrocarbon group (preferably with 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 10 carbon atoms) or an aromatic hydrocarbon group (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10 carbon atoms), with aliphatic hydrocarbon groups being preferred. Ｎ１ and R Ｎ２ Using an aliphatic hydrocarbon group is preferable because it results in a base with high basicity. The aliphatic hydrocarbon group and aromatic hydrocarbon group may have substituents, and they may also have oxygen atoms in the aliphatic hydrocarbon chain, aromatic ring, or substituent. In particular, an embodiment in which the aliphatic hydrocarbon group has oxygen atoms in the hydrocarbon chain is exemplified.

[0264] R Ｎ１ and R Ｎ２Examples of aliphatic hydrocarbon groups that constitute the group include linear or branched linear alkyl groups, cyclic alkyl groups, groups including combinations of linear and cyclic alkyl groups, and alkyl groups having an oxygen atom in the chain. Linear or branched linear alkyl groups preferably have 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12. Examples of linear or branched linear alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, isobutyl, secondary butyl, tertiary butyl, isopentyl, neopentyl, tertiary pentyl, and isohexyl groups. Cyclic alkyl groups preferably have 3 to 12 carbon atoms, and more preferably 3 to 6. Examples of cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups. Groups containing a combination of a linear alkyl group and a cyclic alkyl group preferably have 4 to 24 carbon atoms, more preferably 4 to 18, and even more preferably 4 to 12 carbon atoms. Examples of groups containing a combination of a linear alkyl group and a cyclic alkyl group include cyclohexylmethyl group, cyclohexylethyl group, cyclohexylpropyl group, methylcyclohexylmethyl group, and ethylcyclohexylethyl group. Alkyl groups having an oxygen atom in the chain preferably have 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4 carbon atoms. Alkyl groups having an oxygen atom in the chain may be linear or cyclic, and may be linear or branched. In particular, from the viewpoint of increasing the boiling point of the base generating agent described later, R Ｎ１ and R Ｎ２ A C5 to C12 alkyl group is preferred. However, in formulations where adhesion to a metal (e.g., copper) layer is important, a cyclic alkyl group or a C1 to C8 alkyl group is preferred.

[0265] R Ｎ１ and R Ｎ２ These may be linked together to form a cyclic structure. The cyclic structure may have oxygen atoms, etc., in the chain. Also, R Ｎ１ and R Ｎ２The cyclic structure formed may be a monoring or a fused ring, but a monoring is preferred. The cyclic structure formed is preferably a five-membered or six-membered ring containing the nitrogen atom in formula (N1), and examples include a pyrrole ring, imidazole ring, pyrazole ring, pyrroline ring, pyrrolidine ring, imidazolidine ring, pyrazolidine ring, piperidine ring, piperazine ring, and morpholine ring, with pyrroline ring, pyrrolidine ring, piperidine ring, and morpholine ring being preferred.

[0266] R Ｃ１ represents a hydrogen atom or a protecting group, with a hydrogen atom being preferred. Preferred protecting groups are those that decompose upon the action of an acid or base, with acid-decomposed protecting groups being particularly preferred. Specific examples of protecting groups include linear or cyclic alkyl groups or linear or cyclic alkyl groups having an oxygen atom in the chain. Examples of linear or cyclic alkyl groups include methyl, ethyl, isopropyl, tert-butyl, and cyclohexyl groups. Examples of linear alkyl groups having an oxygen atom in the chain include alkyloxyalkyl groups, with methyloxymethyl (MOM) and ethyloxyethyl (EE) groups being preferred. Examples of cyclic alkyl groups having an oxygen atom in the chain include epoxy, glycidyl, oxetanyl, tetrahydrofuranyl, and tetrahydropyranyl (THP) groups.

[0267] In formula (N1), the divalent linking group constituting L is not particularly limited, but a hydrocarbon group is preferred, and an aliphatic hydrocarbon group is more preferred. The hydrocarbon group may have substituents and may have atoms other than carbon atoms in the hydrocarbon chain. The divalent linking group is more preferably a divalent hydrocarbon linking group which may have an oxygen atom in the chain, and even more preferably a group which includes a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain, a divalent aromatic hydrocarbon group, or a combination of a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group, and even more preferably a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain. These groups may not have an oxygen atom. The divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12, and even more preferably 2 to 6. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. The group containing a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (e.g., arylene alkyl group) preferably has 7 to 22 carbon atoms, more preferably 7 to 18, and even more preferably 7 to 10.

[0268] The linking group L is preferably a linear or branched linear alkylene group, a cyclic alkylene group, a group including a combination of a linear alkylene group and a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a linear or branched linear alkenylene group, a cyclic alkenylene group, an arylene group, or an arylenealkylene group. The linear or branched linear alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The cyclic alkylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6. The group including a combination of a linear alkylene group and a cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12, and even more preferably 4 to 6. The alkylene group having an oxygen atom in the chain may be linear or cyclic, and may be linear or branched. The alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3 carbon atoms.

[0269] Linear or branched alkenylene groups preferably have 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3. Linear or branched alkenylene groups preferably have 1 to 10 C=C bonds, more preferably 1 to 6, and even more preferably 1 to 3. Cyclic alkenylene groups preferably have 3 to 12 carbon atoms, more preferably 3 to 6. Cyclic alkenylene groups preferably have 1 to 6 C=C bonds, more preferably 1 to 4, and even more preferably 1 to 2. Arylene groups preferably have 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. Arylene alkylene groups preferably have 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11. Among these, linear alkylene groups, cyclic alkylene groups, alkylene groups having oxygen atoms in the chain, linear alkenylene groups, arylene groups, and arylenealkylene groups are preferred, and 1,2-ethylene groups, propanediyl groups (especially 1,3-propanediyl groups), cyclohexanediyl groups (especially 1,2-cyclohexanediyl groups), vinylene groups (especially cisvinylene groups), phenylene groups (1,2-phenylene groups), phenylenemethylene groups (especially 1,2-phenylenemethylene groups), and ethyleneoxyethylene groups (especially 1,2-ethyleneoxy-1,2-ethylene groups) are more preferred.

[0270] The following commercially available products can be suitably used as photobase generators. For example, WPBG-300, WPBG-345, WPBG-266, WPBG-018, WPBG-027, WPBG-140, WPBG-165 (all WPBG series manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 1,5,7-triazabicyclo[4.4.0]deca-5-ene 2-(9-oxoxanthene-2-yl)propionic acid, 1,5-diazabicyclo[4.3.0]nona-5-ene 2-(9-oxoxanthene-2-yl)propionic acid, and 1,8-diazabicyclo[5.4.0]undeca-7-ene 2-(9-oxoxanthene-2-yl)propionic acid (all manufactured by Tokyo Chemical Industry Co., Ltd.).

[0271] Commercially available thermal base generators such as U-CAT SA1, U-CAT SA102, U-CAT SA603, U-CAT SA810, U-CAT SA506, U-CAT 1102, U-CAT 881, U-CAT 891, U-CAT 5003, U-CAT 5050, U-CAT 3512T, U-CAT 3513N, U-CAT 660M, U-CAT 2024, and U-CAT 18X ​​(all manufactured by Sunapro Co., Ltd.) can also be suitably used.

[0272] Examples of base-generating agents include, but are not limited to, the following compounds.

[0273]

[0274] 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.

[0275] Specific preferred compounds for ionic base generators include, for example, the compounds described in paragraphs 0148-0163 of International Publication No. 2018 / 038002.

[0276] Specific examples of ammonium salts include, but are not limited to, the following compounds.

[0277] Specific examples of iminium salts include, but are not limited to, the following compounds.

[0278] 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.

[0279] 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.

[0280] When the photocurable resin composition contains a base generator, the amount of base generator is preferably 0.1 to 50 parts by mass per 100 parts by mass of resin in the photocurable resin composition. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less. One or more types of base generators can be used. When two or more types are used, it is preferable that the total amount is within the above range.

[0281] <Solvent> The photocurable 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.

[0282] 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.).

[0283] 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.

[0284] Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucocenone, and dihydrolevoglucocenone.

[0285] Suitable cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0286] As an example of a sulfoxide, dimethyl sulfoxide is a suitable choice.

[0287] 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.

[0288] Suitable ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0289] 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.

[0290] From the viewpoint of improving the properties of the coated surface, it is also preferable to use a mixture of two or more solvents.

[0291] 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 photocurable 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 should be determined by considering the solubility of specific resins and other components contained in the photocurable 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.

[0292] From the viewpoint of coatability, the solvent content is preferably such that the total solid content concentration of the photocurable 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.

[0293] <Metal Adhesion Modifying Agent> The photocurable resin composition of the present invention preferably contains a metal adhesion modifying agent from the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc. Examples of metal adhesion modifying agents 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.

[0294] [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 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 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.).

[0295]

[0296] 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). 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.).

[0297] [Aluminum-based adhesive aids] Examples of aluminum-based adhesive aids include aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), and ethyl acetate aluminum diisopropylate.

[0298] 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.

[0299] 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.

[0300] <Migration Inhibitor> The photocurable resin composition of the present invention preferably further contains a migration inhibitor. By including a migration inhibitor, for example, when the photocurable 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.

[0301] 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.

[0302] As migration inhibitors, ion trapping agents that capture anions such as halogen ions can also be used.

[0303] 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.

[0304] Specific examples of migration inhibitors include the following compounds.

[0305]

[0306] When the photocurable 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 photocurable resin composition.

[0307] 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.

[0308] <Light Absorbers> The photocurable 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.

[0309] <Polymerization Inhibitor> The photocurable 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.

[0310] 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.

[0311] If the photocurable 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 photocurable resin composition.

[0312] 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.

[0313] <Other Additives> The photocurable 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 can be 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 0101-0104, 0107-0109 of Japanese Patent Application Publication No. 2008-250074, and the contents of these documents 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 photocurable resin composition of the present invention.

[0314] [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.

[0315] By incorporating a surfactant into the photocurable 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 improved. 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.

[0316] 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.

[0317] 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.

[0318] 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.

[0319] 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.

[0320] 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.

[0321] [Inorganic Particles] 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.

[0322] 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.

[0323] [Organotitanium Compounds] By including organotitanium compounds in the photocurable resin composition, a resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

[0324] 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 photocurable resin compositions 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), and titanium diisopropoxidebis(ethylacetoacetate). 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.

[0325] 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.

[0326] 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. 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. In formula (T-2), X １ ~X ３ Each of these independently represents -C(-*)= or -N=, where * represents a bonding site with another structure, and # represents a bonding site with a metal atom.

[0327] 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.

[0328] 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.

[0329] 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. １２ The phenylene group in this is preferably a 1,2-phenylene group.

[0330] 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 R２ 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.

[0331] 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(-*)=.

[0332] Specific examples of compounds represented by formula (T-1) include, but are not limited to, the compounds used in the examples.

[0333] 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.

[0334] When an organotitanium 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. 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.

[0335] <Characteristics of the Photocurable Resin Composition> The viscosity of the photocurable resin composition of the present invention can be adjusted by the solid content concentration of the photocurable 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.

[0336] When a film with a thickness of 10 μm is formed using the photocurable resin composition of the present invention, the transmittance of the film at a wavelength of 365 nm is preferably 15% or more, more preferably 20% or more, and even more preferably 25% or more. The upper limit of the transmittance is not particularly limited and may be 100%. The film can be obtained, for example, by coating a silicon wafer with the photocurable resin composition of the present invention and then drying it at 100°C for 5 minutes.

[0337] <Restrictions on the substances contained in the photocurable resin composition> The water content of the photocurable 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 photocurable resin composition is improved. Methods for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.

[0338] From the viewpoint of insulating properties, the metal content of the photocurable resin composition of the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but excludes metals included as complexes between organic compounds and metals. If multiple metals are included, it is preferable that the sum of these metals is within the above range.

[0339] Furthermore, methods for reducing metal impurities unintentionally included in the photocurable resin composition of the present invention include selecting raw materials with a low metal content as the raw materials constituting the photocurable resin composition of the present invention, performing filter filtration on the raw materials constituting the photocurable 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.

[0340] When considering its use as a semiconductor material, the photocurable resin composition of the present invention preferably contains less than 500 ppm by mass of halogen atoms, 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. 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.

[0341] Conventional containers can be used as containers for the photocurable resin composition of the present invention. To suppress the incorporation of impurities into the raw materials and the photocurable 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.

[0342] <Cured product of photocurable resin composition> A cured product of the photocurable resin composition can be obtained by curing the photocurable resin composition of the present invention. The cured product of the present invention is a cured product obtained by curing the photocurable resin composition. The curing of the photocurable 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 photocurable 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 photocurable 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 of the photocurable resin composition of the present invention upon curing 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 photocurable resin composition before and after curing, and can be calculated using the following formula: Shrinkage rate [%] = 100 - (Volume after curing ÷ Volume before curing) × 100

[0343] <Characteristics of the Cured Product of the Photocurable Resin Composition> The imidization reaction rate of the cured product of the photocurable resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, the cured product may have excellent mechanical properties. The elongation at break of the cured product of the photocurable resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more. The glass transition temperature (Tg) of the cured product of the photocurable 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.

[0344] <Preparation of Photocurable Resin Composition> The photocurable 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.

[0345] For the purpose of removing foreign matter such as dust and fine particles from the photocurable 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 photocurable resin composition filled in a bottle may be subjected to a step of degassing under reduced pressure.

[0346] (Method for Manufacturing Cured Products) The method for manufacturing cured products of the present invention preferably includes a film-forming step of applying a photocurable 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.

[0347] <Film Formation Process> The photocurable resin composition of the present invention can be used in a film 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 film formation process in which the photocurable resin composition is applied to a substrate to form a film.

[0348] [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.

[0349] When a photocurable 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.

[0350] Coating is a preferred method for applying the photocurable 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 both uniformity of film thickness and productivity, spin coating and slit coating are more preferred. By adjusting the solid content concentration of the photocurable 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 also be employed in which various solvents are applied to the substrate before applying the photocurable resin composition to the substrate to improve the wettability of the substrate, and then the photocurable resin composition is applied.

[0351] <Drying Process> After the film formation process (layer formation process), the film may be subjected to a drying process to remove the solvent from the formed film (layer). That is, the method for producing a cured product of the present invention may include a drying process for drying the film formed in the film formation process. The drying process is preferably performed after the film formation process and before the exposure process. The drying temperature of the film in the drying process 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.

[0352] <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 photocurable 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.

[0353] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, with 240 to 550 nm being preferred.

[0354] 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 exposure methods 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 photocurable 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 photocurable resin composition of the present invention is exposed is acceptable, but examples include exposure using a photomask and exposure by laser direct imaging.

[0355] <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.

[0356] <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.

[0357] [Developer] Developers used in the developing process include alkaline aqueous solutions or developers containing organic solvents.

[0358] 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.

[0359] 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.

[0360] When the developer contains an organic solvent, one or more organic solvents may 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.

[0361] 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.

[0362] The developing solution may further contain other components. Examples of other components include known surfactants and known defoamers.

[0363] [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.

[0364] 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.

[0365] 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.

[0366] [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.

[0367] 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.

[0368] If the rinsing solution contains an organic solvent, one or more organic solvents may be used in mixture form. The organic solvents are preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME, more preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME, and even more preferably cyclohexanone and PGMEA.

[0369] 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.

[0370] The rinse solution may further contain other components. Examples of other components include known surfactants and known defoaming agents.

[0371] [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.

[0372] 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.

[0373] <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, resins such as polyimide precursors are cyclized to become 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.

[0374] 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.

[0375] 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.

[0376] 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 photocurable 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 photocurable resin composition.

[0377] 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.

[0378] 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.

[0379] 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 the film while irradiating it with ultraviolet light, as described in U.S. Patent No. 9,159,547. Such a pretreatment process can improve the properties of the film. The pretreatment process 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 process 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, the film may be cooled after heating, and in this case, the cooling rate is preferably 1 to 5°C / min.

[0380] 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.

[0381] <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.

[0382] <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).

[0383] 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.

[0384] 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. 7,888,181, and U.S. Patent No. 9,177,926 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 plating include electroplating using copper sulfate or copper cyanide plating solutions.

[0385] The thickness of the metal layer is preferably 0.01 to 50 μm at the thickest part, and more preferably 1 to 10 μm.

[0386] <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.

[0387] 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.

[0388] (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.

[0389] 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.

[0390] 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 of forming a metal layer on a layer made of cured material, which is performed multiple times during the manufacturing process of the cured material. 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 photocurable resin composition of the present invention used to form the first layer made of cured material and the photocurable 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.

[0391] <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.

[0392] 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.

[0393] 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.

[0394] In the present invention, it is particularly preferable to form a cured product (resin layer) of the photocurable 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 photocurable resin composition layer (resin layer) of the present invention and the metal layer formation step, the photocurable resin composition layer (resin layer) and the metal layer of the present invention can be alternately stacked.

[0395] (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 photocurable 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 photocurable 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 photocurable resin composition layer after exposure, or on at least a portion of both the metal layer and the photocurable resin composition layer after exposure. 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 photocurable resin composition layer is formed. By performing the surface activation treatment on the surface of the metal layer in this way, the adhesion with the photocurable 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 photocurable resin composition layer (resin layer) after exposure. Thus, by performing a surface activation treatment on the surface of a photocurable resin composition layer, the adhesion between the surface-activated layer and metal or resin layers provided on the surface-activated layer can be improved. In particular, when the photocurable resin composition layer is cured, such as when performing negative type development, it is less susceptible to damage from the surface treatment and adhesion is easily improved. The surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of International Publication No. 2021 / 112189. This content is incorporated herein by reference.

[0396] (Semiconductor Devices and Methods for Manufacturing the Same) The present invention also discloses semiconductor devices including the cured product or laminate of the present invention. The present invention also discloses methods for manufacturing semiconductor devices including a method for manufacturing the cured product or laminate of the present invention. Specific examples of semiconductor devices in which the photocurable 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.

[0397] (Base Generating Agent) The base generating agent of the present invention is a base generating agent represented by formula (A-1). In formula (A-1), Ar represents an aromatic ring structure, or a structure in which two or more aromatic ring structures are linked by a linking group, and R １ is a monovalent organic group or halogen atom, n1 is an integer from 1 to 4, and all n1 structures are bonded to the aromatic ring structure of Ar by a single bond without a linking group, m1 is an integer from 0 to 4, X is a countercation containing a positively charged nitrogen atom, nx1 is an integer of 1 or more, and if X is an a-valent cation, then (a × nx1) is the same number as n1, and if X is a quaternary alkylammonium cation, then m1 is 1 to 4, or n1 is 2 or more, or Ar is a substituted phenyl group or an aromatic ring structure other than a phenyl group.

[0398] The base-generating agent of the present invention exhibits basicity when a cation containing a nitrogen atom represented by X becomes electrically neutral due to external stimuli such as heat or light. Although the decomposition mechanism is not clear, it is presumed that a one-electron reduction from the glyoxylate anion to the countercation X, followed by decarboxylation of the glyoxyl radical, generates an acyl radical, and the acyl radical captures a hydrogen radical, leading to the release of the base through the electrically neutralization of X. In the case of heat, basicity is preferably exhibited at 80 to 250°C, more preferably at 100 to 220°C, even more preferably at 120 to 200°C, and most preferably at 140 to 180°C. Examples of light include g-line (436 nm), h-line (405 nm), i-line (365 nm), LED lamp (270-450 nm), excimer laser (KrF (248 nm), ArF (193 nm)), and ultrashort ultraviolet (EUV) (13.5 nm), with h-line (405 nm), i-line (365 nm), and LED lamp (270-450 nm) being more preferred. The wavelength is preferably 270-450 nm, more preferably 310-410 nm, and more preferably 330-380 nm. To promote photodegradation, the above-mentioned sensitizers and sensitizing aids (amines, etc.) can also be used in combination. For base generation, thermal decomposition and photodegradation may be performed individually or in combination, with photodegradation being more preferred. When generating bases by photodegradation, the base generating agent of the present invention functions as a photobase generating agent.

[0399] A preferred embodiment of the base generator of the present invention is the same as that of compound A described above.

[0400] In particular, the base generating agent of the present invention is preferably represented by the following formula (A-2a) or formula (A-2b). In equations (A-2a) and (A-2b), R １２ represents an acyl group or a nitro group, m2 represents 0 or 1, L ａ１ These are single bonds, -O-, -S-, -NR Ｎ２ -, -C(R ｘ１ R ｘ２ ) -, -C (=O) -, L ａ２ These are single bonds, -O-, -S-, -NR Ｎ２ -, -C(R ｘ１ R ｘ２) represents either - or -C (=O)-, R Ｎ２ , R ｘ１ and R ｘ２ Each of these independently represents a monovalent organic group, and y indicates either 0 or 1, where 0 is L ａ２ It does not exist, R ｙ１ and R ｙ２ Each independently represents a monovalent organic group, y1 and y2 independently represent integers from 0 to 3, and if y1 and y2 are 2 or greater, adjacent R ｙ１ R's mutual or adjacent R's ｙ２ They may bond with each other to form a ring, and X is a countercation, a cation containing a positively charged nitrogen atom.

[0401] A preferred embodiment of formula (A-2a) or formula (A-2b) is the same as a preferred embodiment of formula (A-2a) or formula (A-2b) in compound A described above.

[0402] In the base generator of the present invention, X in formula (A-1), formula (A-2a), or formula (A-2b) is preferably a cation represented by the following formulas (X-1) to (X-4). In formulas (X-1) to (X-4), R １０１ ~R １１９ Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and R １０１ ~R １１９ Adjacent groups may form a ring via any linking group. Preferred embodiments of formulas (X-1) to (X-4) are the same as preferred embodiments of formulas (X-1) to (X-4) in compound A described above.

[0403] In the base generator of the present invention, X in formula (A-1), formula (A-2a), or formula (A-2b) is one of the above X to H ＋ In dimethyl sulfoxides with an electrically neutral structure excluding the specified component, the acid dissociation constant pKa at 25°C is preferably 10 to 45. The preferred embodiment of the above acid dissociation constant is the same as the preferred embodiment of the acid dissociation constant of X in compound A described above.

[0404] 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.

[0405] <Synthesis Example> ・Method for producing compound (A-1) 18.4 g of toluene and 300 mL of methylene chloride were added to a three-necked flask and cooled to 5°C on an ice bath. 40.8 g of ethyl chloroglyoxalate was added, followed by the addition of 53.2 g of aluminum chloride in five separate additions. The mixture was stirred at 5°C for 30 minutes, then the temperature was raised to 25°C and stirred for a further 2 hours. The resulting reaction mixture was added to 500 mL of ice water to quench the reaction, and the organic layer was extracted with 200 mL of methylene chloride. The organic layer was concentrated under reduced pressure to obtain 35.5 g of intermediate (A-1-a) as a pale yellow liquid. 19.2 g of intermediate (A-1-a) was added to a three-necked flask and dissolved in 100 mL of tetrahydrofuran, 100 mL of pure water, and 8.0 g of sodium hydroxide. This mixture was heated and stirred at 50°C for 2 hours, then cooled to 25°C, and the alkaline aqueous layer was extracted by washing twice with 100 mL of toluene. This alkaline aqueous layer was cooled to 5°C, and 18 mL of concentrated hydrochloric acid was slowly added dropwise to obtain the resulting crystals, which were then filtered off. The crystals were washed twice with 50 mL of cold water and dried under reduced pressure to obtain 13.3 g of intermediate (A-1-b) as a white solid. 8.2 g of intermediate (A-1-b) was added to a three-necked flask and dissolved in 50 mL of tetrahydrofuran. 7.6 g of 1,8-diazabicyclo[5.4.0]-7-undecene (abbreviated as DBU) was added dropwise over 5 minutes to carry out the acid-base neutralization reaction. After stirring at 25°C for 30 minutes, the reaction mixture was concentrated under reduced pressure to obtain 15.8 g of compound (A-1) as a white solid. The UV absorption spectrum, observed at 25°C in acetonitrile, showed a maximum absorption wavelength of 275 nm and a molar extinction coefficient of 6800 L mol at the maximum absorption wavelength. －１ cm －１ The molar extinction coefficient at 365 nm is 60 L mol. －１ cm －１ That was the case. １H-NMR (heavy DMSO): 1.5-1.8 (m, 8H), 2.38 (t, 2H), 2.41 (s, 3H), 3.2-3.4 (m, 6H), 7.38 (d, 2H), 7.97 (d, 2H)

[0406] • Manufacturing method of (A-4) Compound (A-4) was synthesized using the same method as compound (A-1), except that toluene was replaced with phenyl acetate. The UV absorption spectrum was obtained in acetonitrile at 25°C, with a maximum absorption wavelength of 330 nm and a molar extinction coefficient of 5000 L mol at the maximum absorption wavelength. －１ cm －１ The molar extinction coefficient at 365 nm is 300 L mol. －１ cm －１ That was the case. １ H-NMR (heavy DMSO): 1.5-1.8 (m, 8H), 2.36 (t, 2H), 3.2-3.4 (m, 6H), 6.96 (d, 1H), 7.45 (d, 2H), 8.18 (d, 1H), 9.2 (brs, 2H)

[0407] • Manufacturing method of (A-48) Compound (A-48) was synthesized using the same method as compound (A-1), except that toluene was replaced with diphenyl ether. The UV absorption spectrum was obtained in acetonitrile at 25°C, with a maximum absorption wavelength of 311 nm and a molar extinction coefficient of 7900 L mol at the maximum absorption wavelength. －１ cm －１ The molar extinction coefficient at 365 nm is 950 L mol. －１ cm －１ That was the case. １ H-NMR (heavy DMSO): 1.5-1.8 (m, 8H), 2.39 (t, 2H), 3.2-3.4 (m, 6H), 7.0-7.4 (m, 5H), 7.45 (d, 2H), 8.05 (d, 2H)

[0408] • Manufacturing method of (A-66) 9.3 g of diphenyl sulfide and 300 mL of chlorobenzene were added to a three-necked flask and cooled to 5°C on an ice bath. 6.7 g of aluminum chloride was added and stirred for 10 minutes to dissolve, then 7.7 g of orthotoluyl chloride was added dropwise over 10 minutes. The reaction mixture was raised to 25°C and stirred for another hour. Next, 8.3 g of ethyl chloroglyoxalate was added, followed by 13.4 g of aluminum chloride, which was added in five separate additions. The mixture was stirred at 5°C for 30 minutes, then raised to 25°C and stirred for another 2 hours. The resulting reaction mixture was added to 500 mL of ice water to quench the reaction, and the organic layer was extracted with 200 mL of methylene chloride. The organic layer was concentrated under reduced pressure to obtain 13.4 g of intermediate (A-66-a) as a pale yellow solid. Subsequently, compound (A-66) was obtained as a pale yellow solid by the same method, except that intermediate (A-66-a) was used instead of intermediate (A-1-a) in the method for producing compound (A-1). The UV absorption spectrum was obtained in acetonitrile at 25°C, with a maximum absorption wavelength of 326 nm and a molar extinction coefficient of 22,000 L mol at the maximum absorption wavelength. －１ cm －１ The molar extinction coefficient at 365 nm is 3600 L mol. －１ cm －１ That was the case. １ H-NMR (heavy DMSO): 1.5-1.8 (m, 8H), 2.40 (t, 2H), 2.48 (s, 3H), 3.2-3.4 (m, 6H), 7.16 (d, 1H), 7.45 (m, 3H) 7.54 (m, 5H), 7.65 (d, 2H), 8.34 (d, 1H)

[0409] • Manufacturing method of (A-89) Compound (A-89) was synthesized in the same manner as compound (A-1), except that toluene was replaced with diphenyl sulfide in the manufacturing method of compound (A-1), and 1,8-diazabicyclo[5.4.0]-7-undecene was replaced by an equimolar amount with 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)phosphoranylideneamino]-2λ5,4λ5-catenadi(phosphazene) (trade name: Phosphazene-based P4-t-Bu solution (manufactured by Sigma-Aldrich Co., Ltd.), hexane solution concentration 0.8 M). The UV absorption spectrum was obtained in acetonitrile at 25°C, with a maximum absorption wavelength of 320 nm, a molar extinction coefficient of 18000 L mol-1 cm-1 at the maximum absorption wavelength, and a molar extinction coefficient of 1500 L mol at 365 nm. －１ cm －１ That was the case. １ H-NMR (heavy DMSO): 0.9 (s, 9H), 2.62 (d, 54H), 2.48 (s, 3H), 7.0-7.4 (m, 5H), 7.55 (d, 2H), 7.65 (d, 2H)

[0410] • Manufacturing method of (A-97) Compound (A-97) was obtained as a pale yellow solid by the same method as in the production method of compound (A-1), except that toluene was replaced with biphenyl propionate and 1,8-diazabicyclo[5.4.0]-7-undecene was replaced with 1,5-diazabicyclo[4.3.0]nona-5-ene (abbreviation: DBN). The UV absorption spectrum was obtained in acetonitrile at 25°C, with a maximum absorption wavelength of 310 nm and a molar extinction coefficient of 7000 L mol at the maximum absorption wavelength. －１ cm －１ The molar extinction coefficient at 365 nm is 1200 L mol. －１ cm －１ That was the case. １ H-NMR (heavy DMSO): 1.77 (m, 2H), 1.93 (m, 2H), 2.42 (t, 2H), 3.1-3.4 (m, 6H), 6.89 (d, 2H), 7.58 (d, 2H), 7.71 (d, 2H), 7.88 (d, 2H), 10.0 (brs, 1H)

[0411] • Manufacturing method of (A-115) Compound (A-115) was obtained as a pale yellow solid by the same method as in the production method of compound (A-66), except that diphenyl sulfide was replaced with N-ethylcarbazole, orthotoluyl chloride with benzoyl chloride, and 1,8-diazabicyclo[5.4.0]-7-undecene was replaced with 1,5,7-triazabicyclo[4.4.0]deca-5-ene (abbreviation: TBD). The UV absorption spectrum was obtained in acetonitrile at 25°C, with a maximum absorption wavelength of 341 nm and a molar extinction coefficient of 28,000 L mol at the maximum absorption wavelength. －１ cm －１ The molar extinction coefficient at 365 nm is 3900 L mol. －１ cm －１ That was the case. １ H-NMR (heavy DMSO): 1.51 (t, 3H), 1.7-1.9 (m, 4H), 2.9-3.1 (m, 8H), 4.44 (q, 2H), 7. 1-7.5 (m, 5H), 7.50 (d, 2H), 8.12 (d, 1H), 8.53 (d, 1H), 8.56 (s, 1H), 9.17 (s, 1H)

[0412] • Manufacturing method of (A-116) Compound (A-116) was obtained as a pale yellow solid by the same method as in the production method for compound (A-115), except that benzoyl chloride was replaced with 4-hydroxybenzoyl chloride and 1,5,7-triazabicyclo[4.4.0]deca-5-ene (abbreviated as TBD) was replaced with 7-methyl-1,5,7-triazabicyclo[4.4.0]deca-5-ene (abbreviated as MTBD). The UV absorption spectrum was obtained in acetonitrile at 25°C, with a maximum absorption wavelength of 350 nm and a molar extinction coefficient of 32,000 L mol at the maximum absorption wavelength. －１ cm －１ The molar extinction coefficient at 365 nm is 4500 L mol. －１ cm －１ That was the case. １H-NMR (heavy DMSO): 1.53 (t, 3H), 1.7-1.9 (m, 4H), 2.9-3.1 (m, 8H), 3.21 (s, 3H), 4.46 (q, 2H), 6.80 (d, 2H), 7.50 (d, 2H), 7.59 (d, 2H), 8.12 (d, 1H), 8.53 (d, 1H), 8.56 (s, 1H), 9.17 (s, 1H), 9.7 (brs, 1H)

[0413] • Manufacturing method of (A-118) Compound (A-118) was obtained as a pale yellow solid by the same method as in the method for producing compound (A-115), except that benzoyl chloride was replaced with 4-methoxynaphthoyl chloride and 1,5,7-triazabicyclo[4.4.0]deca-5-ene (abbreviated as TBD) was replaced with 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidine. The UV absorption spectrum was obtained in acetonitrile at 25°C, with a maximum absorption wavelength of 350 nm and a molar extinction coefficient of 37,000 L mol at the maximum absorption wavelength. －１ cm －１ The molar extinction coefficient at 365 nm is 8000 Lmol. －１ cm －１ That was the case. １ H-NMR (heavy DMSO): 1.53 (t, 3H), 1.0-1.8 (m, 20H), 2.57 (m, 2H), 2.83 (s, 12H), 3.79 (s, 3H), 4.46 (q, 2H), 6.2 6 (d, 1H), 7.48 (d, 2H), 7.5-7.9 (m, 3H), 8.10 (d, 1H), 8.52 (d, 1H), 8.57 (s, 1H), 9.12 (d, 1H), 9.15 (s, 1H)

[0414] • Manufacturing method of (A-119) Compound (A-119) was obtained as a pale yellow solid by the same method as in the production method for compound (A-115), except that benzoyl chloride was replaced with 2-tenoyl chloride and 1,5,7-triazabicyclo[4.4.0]deca-5-ene (abbreviated as TBD) was replaced with trans-decahydroquinoline. The UV absorption spectrum was obtained in acetonitrile at 25°C, with a maximum absorption wavelength of 352 nm and a molar extinction coefficient of 30,000 L mol at the maximum absorption wavelength. －１ cm －１The molar extinction coefficient at 365 nm is 12,000 L mol. －１ cm －１ That was the case. １ H-NMR (heavy DMSO): 1.52 (t, 3H), 1.0-2.2 (m, 10H), 3.0-3.2 (m, 6H), 4.48 (q, 2H), 7.22 (t, 1H), 7.48 (d, 2H), 7.83 (d, 1H), 8.04 (d, 1H), 8.10 (d, 1H), 8.52 (d, 1H), 8.57 (s, 1H), 9.15 (s, 1H)

[0415] • Manufacturing method of (A-124) Compound (A-124) was obtained as a pale yellow solid by the same method as in the production method of compound (A-66), except that diphenyl sulfide was replaced with 9,9-dibutylfluorene, orthotoluyl chloride with 1-naphthoyl chloride, and 1,8-diazabicyclo[5.4.0]-7-undecene (abbreviated as DBU) was replaced with 2-tert-butyl-1,1,3,3-tetramethylguanidine (abbreviated as BTMG). The UV absorption spectrum was obtained in acetonitrile at 25°C, with a maximum absorption wavelength of 342 nm and a molar extinction coefficient of 19000 Lmol at the maximum absorption wavelength. －１ cm －１ The molar extinction coefficient at 365 nm is 7600 L mol. －１ cm －１ The results were as follows: 1H-NMR (heavy DMSO): 0.88 (t, 6H), 1.01 (s, 9H), 1.29 (m, 4H), 1.83 (t, 4H), 3.09 (s, 12H), 7.5-8.2 (m, 12H), 9.30 (d, 1H)

[0416] • Manufacturing method of (A-135) 10.0 g of indole was added to a three-necked flask and dissolved in 150 mL of diethyl ether. 16.3 g of oxalyl chloride was added dropwise to this solution over 10 minutes, and the resulting yellow suspension was stirred at 25°C for 1 hour. 20 mL of saturated sodium carbonate aqueous solution was slowly added dropwise to this reaction mixture over 10 minutes, taking care to avoid generating bubbles, and the mixture was stirred at 25°C for 16 hours. The solid precipitated in the reaction mixture was filtered, washed with 50 mL of diethyl ether, and dried to obtain 9.8 g of the intermediate (A-135-a) as a yellow solid. 9.5 g of intermediate (A-135-a) and 10.0 g of 4-fluorobenzophenone were added to a three-necked flask and dissolved in 200 mL of 1,3-dimethyl-2-imidazolidinone. 45 g of tripotassium phosphate was added to this mixture and the mixture was heated and stirred at 110°C for 24 hours. The resulting reaction solution was added dropwise to 500 mL of 1N hydrochloric acid aqueous solution cooled to 5°C, and the resulting solid was filtered off. This crude solution was recrystallized in 200 mL of isopropyl ether to obtain 8.3 g of intermediate (A-135-b) as a yellow solid. 3.7 g of the intermediate (A-135-b) was added to a three-necked flask and dissolved in 50 mL of tetrahydrofuran. 1.3 g of 1,5-diazabicyclo[4.3.0]nona-5-ene (abbreviated as DBN) was added dropwise over 5 minutes to carry out the acid-base neutralization reaction. After stirring at 25°C for 30 minutes, the reaction mixture was concentrated under reduced pressure to obtain 5.0 g of compound (A-135) as a yellow solid. The UV absorption spectrum, at 25°C in acetonitrile, showed a maximum absorption wavelength of 361 nm and a molar extinction coefficient of 7100 L mol at the maximum absorption wavelength. －１ cm －１ The molar extinction coefficient at 365 nm is 6700 L mol. －１ cm －１ That was the case. １ H-NMR (heavy DMSO): 1.76 (m, 2H), 1.91 (m, 2H), 2.44 (t, 2H), 3.1-3.4 (m, 6H), 7.0-8.2 (m, 14H)

[0417] • Manufacturing method of (A-153) 9.3 g of diphenyl sulfide and 300 mL of dichloromethane were added to a three-necked flask and dissolved at 25°C. 40.2 g of ethyl chloroglyoxalate was added to this mixture, and 41.5 g of aluminum chloride was added in five separate additions. The reaction mixture was stirred at 25°C for 4 hours, and the resulting reaction mixture was quenched by adding it to 500 mL of ice water. The organic layer was then extracted with 200 mL of methylene chloride. The organic layer was concentrated under reduced pressure to obtain 18.4 g of intermediate (A-153-a) as a pale yellow liquid. 9.7 g of intermediate (A-153-a) was added to a three-necked flask and dissolved in 100 mL of toluene, 100 mL of pure water, 8.0 g of sodium hydroxide, and 12.2 g of tetrabutylammonium bromide. This mixture was heated and stirred at 50°C for 2 hours, then cooled to 25°C, and the alkaline aqueous layer was extracted by washing twice with 100 mL of toluene. This alkaline aqueous layer was cooled to 5°C, and 18 mL of concentrated hydrochloric acid was slowly added dropwise to obtain the resulting crystals, which were then filtered off. The crystals were washed twice with 50 mL of cold water and dried under reduced pressure to obtain 6.2 g of intermediate (A-153-b) as a pale yellow solid. 3.3 g of the intermediate (A-153-b) was added to a three-necked flask and dissolved in 50 mL of 1,4-dioxane. 3.0 g of 1,8-diazabicyclo[5.4.0]-7-undecene (abbreviated as DBU) was added dropwise over 5 minutes to carry out the acid-base neutralization reaction. After stirring at 25°C for 30 minutes, the reaction mixture was concentrated under reduced pressure to obtain 6.3 g of compound (A-153) as a pale yellow solid. The UV absorption spectrum, observed at 25°C in acetonitrile, showed a maximum absorption wavelength of 320 nm and a molar extinction coefficient of 9500 L mol at the maximum absorption wavelength. －１ cm －１ The molar extinction coefficient at 365 nm is 2400 L mol. －１ cm －１ That was the case. １ H-NMR (heavy DMSO): 1.5-1.8 (m, 16H), 2.43 (t, 4H), 3.2-3.4 (m, 12H), 7.55 (d, 4H), 7.65 (d, 4H)

[0418] • Manufacturing method of (A-194) Compound (A-194) was obtained as a yellow solid by the same method as in the production method of compound (A-153), except that diphenyl sulfide was replaced with triphenylamine and 1,8-diazabicyclo[5.4.0]-7-undecene (abbreviation: DBU) was replaced with 1,2-diisopropyl-3-[bis(dimethylamino)methylene]guanidine. The UV absorption spectrum was obtained in acetonitrile at 25°C, with a maximum absorption wavelength of 350 nm and a molar extinction coefficient of 23,000 L mol at the maximum absorption wavelength. －１ cm －１ The molar extinction coefficient at 365 nm is 12,000 L mol. －１ cm －１ That was the case.１ 1H-NMR (heavy DMSO): 0.91 (d, 18H), 1.15 (d, 18H), 1.70 (m, 3H), 2.83 (s, 36H), 3.20 (m, 3H), 7.31 (d, 6H), 7.83 (d, 6H).

[0419] Compounds A-1 to A-145 are compounds in which each symbol has the structure shown in the following formula (A-1a). R in the table １１ , R １２ , R １３ all represent R １ in formula (A-1a). When m1 is 0, none of R １１ , R １２ and R １３ exist. When m1 is 1, only R １ exists as R １１ in formula (A-1a). When m1 is 2, R １ exists as R １１ and R １２ in formula (A-1a). When m1 is 3, R １ exists as R １１ , R １２ and R １３ in formula (A-1a). Here, for the carbon atoms of the aromatic rings in formulas (Ar-1) to (Ar-23), numbers are described for convenience. The numerical values described in the columns of "substitution position of R １１ ", "substitution position of R １２ ", and "substitution position of R １３ " correspond to the carbon atoms with the above numbers respectively. Also, * in formulas (Ar-1) to (Ar-23) is the bonding site of the glyoxylate group in formula (A-1a).

[0420] <>

[0421]

[0422]

[0423]

[0424] Details of the abbreviations in the table are as follows. Me: methyl group; Et: ethyl group; Bu: butyl group; iPr: isopropyl group; tBu: t-butyl group; Hex: hexyl group; CF ３ : trifluoromethyl group; Br: bromine atom; OMe: methoxy group; OCp: cyclopentyloxy group; OtBu: t-butoxy group; Ph: phenyl group; OPh: phenoxy group; SBu: thiobutyl group; NEt ２ : diethylamino v N(C ２ H ４ ); ２ O: morpholino group; OH: hydroxy group; OAc: acetyloxy group; NHAc: acetamido group; NO ２ : nitro group; CN: cyano group; OPr: propyloxy group; OBu: butyloxy group; OHex: hexyloxy group; Oallyl: allyloxy group; OEt: ethoxy group; R1-1 to R1-17: groups of the following structure; Ar-1 to Ar-23: groups of the following structure; X-1 to X-14: groups of the following structure

[0425] The pKa values of the conjugate acids of the amines used in this example were respectively (X-1): 13.1, (X-2): 13.5, (X-3): 14.8, (X-4): 14.9, (X-5): 15.1, (X-6): 15.3, (X-7): 16.9, (X-8): 17.8, (X-9): 26.1, (X-10): 10.6, (X-11): 11.1, (X-12): 8.6, (X-13): 8.3, (X-14): 7.2 in a dimethyl sulfoxide solution at 25°C.

[0426] Compo...

Claims

1. A photocurable resin composition containing a compound represented by formula (A-1) and a resin that is a polyimide precursor having polymerizable groups. In formula (A-1), Ar represents an aromatic ring structure, or a structure in which two or more single bonds or aromatic ring structures are linked by a linking group, R １ is a monovalent organic group or halogen atom, n1 is an integer from 1 to 4, and all n1 structures are bonded by a single bond to the aromatic ring structure of Ar, m1 is an integer from 0 to 4, X is a countercation containing a positively charged nitrogen atom, nx1 is an integer of 1 or more, and if X is an a-valent cation, (a × nx1) is the same number as n1, and if X is a quaternary alkylammonium cation, then m1 is 1 to 4, or n1 is 2 or more, or Ar is a substituted phenyl group or an aromatic ring structure other than a phenyl group.

2. The photocurable resin composition according to claim 1, wherein the compound represented by formula (A-1) contains a compound represented by the following formula (A-2a) or formula (A-2b). In formulas (A-2a) and (A-2b), R １２ represents an acyl group or a nitro group, m2 represents 0 or 1, and L ａ１ represents a single bond, -O-, -S-, -NR Ｎ２ -, -C(R ｘ１ R ｘ２ )-, -C(=O)-, and L ａ２ represents a single bond, -O-, -S-, -NR Ｎ２ -, -C(R ｘ１ R ｘ２ )-, -C(=O)-, and R Ｎ２ , R ｘ１ and R ｘ２ each independently represent a monovalent organic group, y represents 0 or 1, and when y is 0, L ａ２ does not exist, and R ｙ１ and R ｙ２ each independently represent a monovalent organic group, y1 and y2 each independently represent an integer from 0 to 3, and when y1 and y2 are 2 or more, adjacent R ｙ１ to each other or adjacent R ｙ２ to each other may combine to form a ring, and X is a counter cation, which is a cation containing a positively charged nitrogen atom.

3. The photocurable resin composition according to claim 1 or 2, wherein X is a cation represented by the following formulas (X-1) to (X-4). In formulas (X-1) to (X-4), R １０１ ~R １１９ Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and R １０１ ~R １１９ Adjacent groups may form a ring via any linking group.

4. The photocurable resin composition according to claim 3, wherein X is a cation represented by formula (X-2), formula (X-3), or formula (X-4).

5. The photocurable resin composition according to claim 1 or 2, wherein the acid dissociation constant pKa at 25°C in a dimethyl sulfoxide solution of the conjugate acid of the amine in X is 10 to 45.

6. The photocurable resin composition according to claim 1 or 2, further comprising a radical polymerization initiator different from the compound represented by formula (A-1).

7. The photocurable resin composition according to claim 6, wherein the radical polymerization initiator, which is different from the compound represented by formula (A-1), is a (keto)oxime ester compound.

8. The photocurable resin composition according to claim 1 or 2, wherein the resin has at least one of a substructure represented by the following formula (B-1) and a substructure represented by the following formula (B-2). In formula (B-1), X １ represents an organic group with 4+m valence, Y １ represents a 2+n valent organic group, R １ R represents a group containing a polymerizable group. ２ represents a group containing a polymerizable group, n is an integer from 0 to 6, m is an integer from 0 to 6, and n+m is an integer of 1 or more. In formula (B-2), X １ represents an organic group with 4+m valence, Y １ represents a 2+n valent organic group, A ｘ１ and A ｘ２ represents a monovalent organic group, R １ R represents a group containing a polymerizable group. ２ represents a group containing a polymerizable group, n is an integer from 0 to 6, m is an integer from 0 to 6, and n+m is an integer of 1 or more, where A ｘ１ and A ｘ２ If at least one of the components has a polymerizable group, then n+m may be 0.

9. R in formula (B-1) １ and R ２ , and also R in formula (B-2) １ , R ２ A ｘ１ and A ｘ２ The photocurable resin composition according to claim 8, wherein the group includes a group having an ethylenically unsaturated bond.

10. X in equations (B-1) and (B-2) １ The photocurable resin composition according to claim 8, wherein the group is a group having an alicyclic hydrocarbon.

11. The photocurable resin composition according to claim 1 or 2, further comprising a polymerizable compound having a molecular weight of less than 3,000.

12. The photocurable resin composition according to claim 1 or 2, further comprising an amine compound.

13. The photocurable resin composition according to claim 1 or 2, further comprising a sensitizer.

14. The photocurable resin composition according to claim 1 or 2, further comprising a chain transfer agent.

15. A cured product obtained by curing the photocurable resin composition according to claim 1 or 2.

16. A laminate comprising two or more layers made of the cured product described in claim 15, wherein a metal layer is included between any of the layers made of the cured product.

17. A method for producing a cured product, comprising a film-forming step of applying the photocurable resin composition according to claim 1 or 2 onto a substrate to form a film.

18. A method for producing a cured product according to claim 17, comprising an exposure step of selectively exposing the film and a developing step of developing the film using a developer to form a pattern.

19. A method for producing a cured product according to claim 17, comprising a heating step of heating the film to 50 to 450°C.

20. A method for manufacturing a laminate, comprising the method for manufacturing a cured product according to claim 17.

21. A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured product according to claim 17.

22. A semiconductor device comprising the cured product described in claim 15.

23. A base generator represented by the following formula (A-1). In formula (A-1), Ar represents an aromatic ring structure, or a structure in which two or more aromatic ring structures are linked by a linking group, and R １ is a monovalent organic group or halogen atom, n1 is an integer from 1 to 4, all n1 structures are bonded to the aromatic ring structure of Ar by a single bond without a linking group, m1 is an integer from 0 to 4, X is a countercation containing a positively charged nitrogen atom, nx1 is an integer of 1 or more, if X is an a-valent cation, then (a × nx1) is the same number as n1, if X is a quaternary alkylammonium cation, then m1 is 1 to 4, or n1 is 2 or more, or Ar is a substituted phenyl group or an aromatic ring structure other than a phenyl group.

24. The base generating agent according to claim 23, represented by the following formula (A-2a) or formula (A-2b). In equations (A-2a) and (A-2b), R １２ represents an acyl group or a nitro group, m2 represents 0 or 1, L ａ１ These are single bonds, -O-, -S-, -NR Ｎ２ -, -C(R ｘ１ R ｘ２ ) -, -C (=O) -, L ａ２ These are single bonds, -O-, -S-, -NR Ｎ２ -, -C(R ｘ１ R ｘ２ ) represents either - or -C (=O)-, R Ｎ２ , R ｘ１ and R ｘ２ Each of these independently represents a monovalent organic group, and y indicates either 0 or 1, where 0 is L ａ２ It does not exist, R ｙ１ and R ｙ２ Each independently represents a monovalent organic group, y1 and y2 independently represent integers from 0 to 3, and if y1 and y2 are 2 or greater, adjacent R ｙ１ R's mutual or adjacent R's ｙ２ They may bond with each other to form a ring, and X is a countercation, a cation containing a positively charged nitrogen atom.

25. The base generator according to claim 23 or 24, wherein X is a cation represented by the following formulas (X-1) to (X-4). In formulas (X-1) to (X-4), R １０１ ~R １１９ Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and R １０１ ~R １１９ Adjacent groups may form a ring via any linking group.

26. The base generating agent according to claim 23 or 24, wherein the acid dissociation constant pKa at 25°C in the dimethyl sulfoxide solution of the conjugate acid of the amine in X is 10 to 45.

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