Photosensitive resin composition, cured product, laminate, method for producing cured product, method for producing laminate, method for producing semiconductor device, and semiconductor device

Abstract

Provided are: a photosensitive resin composition containing at least one resin selected from the group consisting of polyimides and polyimide precursors, and a compound A represented by formula (A-1) or (A-2); a cured product; a laminate; a method for producing a cured product; a method for producing a laminate; a method for producing a semiconductor device; and a semiconductor device. In formula (A-1) or (A-2), each Ar1 independently represents an aromatic group optionally having a substituent.

Description

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

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

[0002] Resin materials produced from photosensitive resin compositions containing resins are now being utilized in a variety of fields. For example, heterocycle-containing polymers such as polyimides have excellent heat resistance and insulating properties and are therefore used in a variety of applications. Examples of such applications include, but are not limited to, insulating films, encapsulants, or protective films for semiconductor devices used for packaging. They are also used as base films or coverlays for flexible substrates.

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

[0004] For example, Patent Document 1 describes a negative photosensitive resin composition comprising (A) at least one resin selected from (A1) a polyimide precursor and (A2) a polyimide, (B) a flavonoid having a specific structure, (C) a photopolymerization initiator, and (D) a solvent.

[0005] Japanese Patent Application Laid-Open No. 2023-160771

[0006] When a photosensitive resin composition containing a polyimide or a precursor thereof is exposed to light and developed to produce a pattern of a cured product, there is a demand for obtaining a cured product with excellent resolution in line with the miniaturization and high integration of devices.

[0007] The present invention aims to provide a photosensitive resin composition that can give a cured product with excellent resolution, a cured product obtained by curing the photosensitive resin composition, a laminate including the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device that includes the method for producing the cured product, and a semiconductor device that includes the cured product.

[0008] Representative embodiments of the present invention are shown below: <1> A photosensitive resin composition comprising at least one resin selected from the group consisting of polyimides and polyimide precursors, and a compound A represented by formula (A-1) or (A-2). In formula (A-1) or (A-2), Ar １ each independently represents an aromatic group which may have a substituent. <2> The photosensitive resin composition according to <1>, further comprising a photopolymerization initiator and a polymerizable compound. <3> The photosensitive resin composition according to <1> or <2>, further comprising an organometallic complex. <4> The photosensitive resin composition according to any one of <1> to <3>, further comprising a base generator. <5> Ar １The photosensitive resin composition according to any one of <1> to <4>, wherein at least one of the groups is an aromatic group having a phenolic hydroxy group, an alkoxy group, or an amino group. <6> The photosensitive resin composition according to any one of <1> to <5>, wherein compound A has an aromatic amino group. <7> The photosensitive resin composition according to any one of <1> to <6>, which is used for forming an interlayer insulating film for a redistribution layer. <8> A cured product obtained by curing the photosensitive resin composition according to any one of <1> to <7>. <9> A laminate comprising two or more layers made of the cured product according to <8>, and comprising a metal layer between any two adjacent layers made of the cured products. <10> A method for producing a cured product, comprising a film-forming step of applying the photosensitive resin composition according to any one of <1> to <7> onto a substrate to form a film. <11> A method for producing a cured product according to <10>, comprising an exposure step of selectively exposing the film to light and a development step of developing the film with a developer to form a pattern. <12> A method for producing the cured product according to <10> or <11>, comprising a heating step of heating the film at 50 to 450°C. <13> A method for producing a laminate, comprising the method for producing a cured product according to any one of <10> to <12>. <14> A method for producing a semiconductor device, comprising the method for producing a cured product according to any one of <10> to <12>. <15> A semiconductor device, comprising the cured product according to <8>.

[0009] According to the present invention, there are provided a photosensitive resin composition that can give a cured product with excellent resolution, a cured product obtained by curing the photosensitive resin composition, a laminate that includes the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device that includes the method for producing the cured product, and a semiconductor device that includes the cured product.

[0010] The following describes the main embodiments of the present invention. However, the present invention is not limited to the explicitly described embodiments. In this specification, a numerical range expressed using the symbol "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits, respectively. In this specification, the term "process" refers not only to an independent process but also to a process that cannot be clearly distinguished from other processes as long as the process achieves its intended effect. In the description of a group (atomic group), a notation that does not specify whether it is substituted or unsubstituted encompasses both unsubstituted groups (atomic groups) and substituted groups (atomic groups). For example, the term "alkyl group" encompasses not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. In addition, examples of light used for exposure include actinic rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and electron beams. As used herein, "(meth)acrylate" refers to either or both of "acrylate" and "methacrylate," "(meth)acrylic" refers to either or both of "acrylic" and "methacrylic," and "(meth)acryloyl" refers to either or both of "acryloyl" and "methacryloyl." In the structural formulae herein, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. As used herein, the term "total solid content" refers to the total mass of all components of the composition excluding the solvent. Furthermore, as used herein, the term "solid content concentration" refers to the mass percentage of the components other than the solvent relative to the total mass of the composition. As used herein, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values ​​measured using gel permeation chromatography (GPC) and are defined as polystyrene equivalent values, unless otherwise specified.In this specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, by using an HLC-8220GPC (manufactured by Tosoh Corporation) and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) connected in series. Unless otherwise specified, these molecular weights are measured using NMP (N-methyl-2-pyrrolidone) as the eluent. However, when NMP is not suitable as the eluent, for example, due to low solubility, THF (tetrahydrofuran) can also be used. Furthermore, unless otherwise specified, detection in GPC measurement is assumed to be performed using a UV (ultraviolet) detector at a wavelength of 254 nm. In this specification, when the positional relationship of each layer constituting a laminate is described as "above" or "below," it is sufficient that another layer is above or below the reference layer among the multiple layers being considered. In other words, a third layer or element may be interposed between the reference layer and the other layer, and the reference layer and the other layer do not need to be in contact with each other. Unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "above." Alternatively, if a resin composition layer is present, the direction from the substrate to the resin composition layer is referred to as "above," and the opposite direction is referred to as "below." Note that such vertical directions are defined for convenience in this specification, and in actual embodiments, the "above" direction in this specification may differ from the vertically upward direction. In this specification, unless otherwise specified, the composition may contain two or more compounds corresponding to each component contained in the composition. Unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component. In this specification, unless otherwise specified, the temperature is 23° C., the atmospheric pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, a combination of preferred embodiments is a more preferred embodiment.

[0011] (Photosensitive Resin Composition) The photosensitive resin composition of the present invention (hereinafter also simply referred to as "photosensitive resin composition") contains at least one resin selected from the group consisting of polyimides and polyimide precursors, and a compound A represented by formula (A-1) or (A-2). In formula (A-1) or (A-2), Ar １ each independently represents an aromatic group which may have a substituent. Hereinafter, at least one resin selected from the group consisting of polyimides and precursors thereof may also be simply referred to as a "specific resin".

[0012] The photosensitive resin composition of the present invention is preferably used to form a photosensitive film that is subjected to exposure and development, and more preferably to form a film that is subjected to exposure and development using a developer containing an organic solvent. The photosensitive resin composition of the present invention can be used, for example, to form an insulating film for a semiconductor device, an interlayer insulating film for a redistribution layer, a stress buffer film, etc., and is preferably used to form an interlayer insulating film for a redistribution layer. Furthermore, the photosensitive resin composition of the present invention is preferably used to form a photosensitive film that is subjected to negative development. In the present invention, negative development refers to development in which unexposed areas are removed by development in exposure and development, and positive development refers to development in which exposed areas are removed by development. The exposure method, developer, and development method may, for example, be the exposure method described in the exposure step and the developer and development method described in the development step in the description of the method for producing a cured product described below.

[0013] The photosensitive resin composition of the present invention can provide a cured product with excellent resolution. The mechanism by which this effect is achieved is unknown, but is presumed to be as follows.

[0014] Compound A represented by formula (A-1) moderately absorbs the exposure light (e.g., 365 nm exposure light) used in exposing a photosensitive resin composition. Therefore, it is believed that it can absorb undesirable light, such as leakage light and reflected light, into non-exposed areas, thereby suppressing exposure by such light. Compound A represented by formula (A-2) easily changes in structure to compound represented by formula (A-1), for example, by exposure to visible light and, if necessary, heating. Therefore, for example, a composition containing a compound represented by formula (A-2) or a film formed therefrom can be easily obtained by heating while exposing it to visible light. Furthermore, compound A represented by formula (A-1) changes to a structure with low absorbance of exposure light by absorbing light of a specific wavelength. Due to this property, it is believed that the amount of light absorbed by compound A decreases in areas with sufficiently high irradiation intensity, thereby allowing the exposed area to be sufficiently exposed. In other words, it is believed that the addition of compound A improves the contrast between the amount of light irradiated to exposed and non-exposed areas, thereby improving resolution. Furthermore, it is believed that compound A decomposes at least in part upon heating at high temperatures (e.g., 170°C or higher) to generate a base. Therefore, when a polyimide precursor is used as a resin, a base is generated from compound A during heating for imidization of the polyimide precursor, and this base promotes imidization, which is presumed to result in an effect of improving the mechanical properties, such as elongation at break, or the chemical resistance of the resulting cured product. In addition, when the compound represented by formula (A-1) undergoes a structural change to the compound represented by formula (A-2) upon exposure, it is believed that the melting point will be lowered. Therefore, when the compound represented by formula (A-2) is contained, i.e., when negative development is performed and heating is then performed, it is believed that the plasticity of the cured product will temporarily increase, and the orientation of the polyimide will be improved. It is presumed that the presence of polyimide in an oriented state in the cured product will also result in an effect of improving the mechanical properties, such as elongation at break, or the chemical resistance of the cured product. Furthermore, compound A decomposes during heat curing to generate a base, and the base remains in the cured product, which is thought to inhibit corrosion of metal substrates and wiring that come into contact with the cured product of the present invention.As a result, it is presumed that, for example, the adhesion between the cured product and the metal substrate or wiring after the heat resistance test is improved.

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

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

[0017] <Specific Resin> The photosensitive resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of polyimides and polyimide precursors. The polyimide precursor refers to a resin whose chemical structure changes in response to an external stimulus to become a polyimide, preferably a resin whose chemical structure changes in response to heat to become a polyimide, and more preferably a resin whose ring structure is formed by a ring-closing reaction in response to heat to become a polyimide. In the present invention, polyimide refers to a resin having a repeating unit containing an imide group in the molecular chain, and preferably a resin having a repeating unit containing an imide ring structure in the molecular chain. Furthermore, when the polyimide is a linear resin, the polyimide is preferably a resin having a repeating unit containing an imide group in the main chain, and more preferably a resin having a repeating unit containing an imide ring structure in the main chain. In this specification, the term "main chain" refers to the relatively longest bonding chain in the resin molecule, and the term "side chain" refers to other bonding chains. As used herein, the term "imide group" refers to a structure represented by *-C(=O)N(-*)C(=O)-*, where * represents a bonding site to another structure, preferably a bonding site to a carbon atom, and more preferably a bonding site to a quaternary carbon atom. As used herein, the term "imide ring structure" refers to a ring structure containing all of the two carbon atoms and the nitrogen atom in the imide as ring members. The imide ring structure is preferably a five-membered ring. The polyimide may be a so-called polyamideimide, which has an amide group in the molecular chain in addition to the imide group. As used herein, the term "amide group" refers to a structure represented by *-C(=O)N(-#)-*, where * represents a bonding site to another structure, preferably a bonding site to a carbon atom, and more preferably a bonding site to a quaternary carbon atom. Furthermore, # represents a bonding site to another structure, preferably a bonding site to a hydrogen atom or a bonding site to a carbon atom, and more preferably a bonding site to a hydrogen atom.

[0018] The specific resin preferably has a polymerizable group, more preferably a radically polymerizable group. When the specific resin has a radically polymerizable group, the photosensitive resin composition of the present invention preferably contains a radical polymerization initiator, more preferably a radical polymerization initiator and a radical crosslinking agent. Furthermore, if necessary, a sensitizer may be included. From such a resin composition, for example, a negative-type photosensitive film is formed. Furthermore, the specific resin may have a polarity conversion group such as an acid-decomposable group. When the specific resin has an acid-decomposable group, the photosensitive resin composition preferably contains a photoacid generator. From such a photosensitive resin composition, for example, a chemically amplified positive-type photosensitive film or a negative-type photosensitive film is formed.

[0019] [Polyimide Precursor] The polyimide precursor used in the present invention is not particularly limited in type, but preferably contains a repeating unit represented by the following formula (2). In formula (2), A １ and A ２ are each independently an oxygen atom or —NR ｚ represents -, and R １１１ represents a divalent organic group, and R １１５ represents a tetravalent organic group, R １１３ and R １１４ each independently represents a hydrogen atom or a monovalent organic group; R ｚ represents a hydrogen atom or a monovalent organic group.

[0020] A in formula (2) １ and A ２ are each independently an oxygen atom or —NR ｚ -, and an oxygen atom is preferred. ｚ represents a hydrogen atom or a monovalent organic group, and preferably a hydrogen atom. １１１represents a divalent organic group. Examples of the divalent organic group include groups containing a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, and a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferred, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferred. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a heteroatom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a heteroatom. R in formula (2) １１１ Examples of the group include groups represented by -Ar- and -Ar-L-Ar-, and the group represented by -Ar-L-Ar- is preferred, where each Ar is independently an aromatic group, L is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO ２ - or -NHCO-, or a group consisting of a combination of two or more of the above. The preferred ranges for these are as described above.

[0021] R １１１ is preferably derived from a diamine. Examples of diamines used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used. Specifically, R １１１ is preferably a diamine containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a heteroatom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a heteroatom. Examples of groups containing an aromatic group include the following.

[0022] In the formula, A represents a single bond or a divalent linking group, and is selected from the group consisting of a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —C(═O)—, —S—, and —SO ２ -, -NHCO-, or a group selected from a combination thereof, and is preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, or -SO ２ - is more preferably a group selected from -CH ２ -, -O-, -S-, -SO ２ -, -C(CF ３ ) ２ - or -C(CH ３ ) ２ In the formula, * represents a bonding site to another structure.

[0023] Specific examples of diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3-, or 1,4-diaminocyclohexane, 1,2-, 1,3-, or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane, and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3 ,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane parafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoparaterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether fluorene, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,At least one diamine selected from 4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolidine, and 4,4'-diaminoquaterphenyl can be mentioned.

[0024] Also preferred are the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of WO 2017 / 038598.

[0025] Also preferably used are diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of WO 2017 / 038598.

[0026] R １１１ is preferably represented by -Ar-L-Ar- from the viewpoint of flexibility of the resulting organic film, wherein each Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO ２ Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO ２ The aliphatic hydrocarbon group here is preferably an alkylene group.

[0027] Also, R １１１From the viewpoint of i-line transmittance, it is preferable that is a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-line transmittance and ease of availability, it is more preferable that is a divalent organic group represented by formula (61). Formula (51) In formula (51), R ５０ ~R ５７ are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and R ５０ ~R ５７ At least one of R is a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site with the nitrogen atom in formula (2). ５０ ~R ５７ Examples of the monovalent organic group include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). In formula (61), R ５８ and R ５９ are each independently a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site with the nitrogen atom in formula (2). Examples of diamines that give the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These may be used alone or in combination of two or more.

[0028] Also, R １１１ is also preferably a group represented by the following formula (71). １１１ is more preferably a group represented by the following formula (72). In formula (71), A １ ~A ３are each independently a single bond or a divalent linking group, * represents a bonding site with the nitrogen atom in formula (2), and the four benzene rings described in formula (71) may each have a hydrogen atom substituted with a substituent. In this specification, a bond crossing a side of a ring structure means that one of the hydrogen atoms in the ring structure is substituted. In formula (72), * represents a bonding site with the nitrogen atom in formula (2).

[0029] In formula (71), A １ ~A ３ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —C(═O)—, —S—, —S(═O) ２ Preferably, it is -, -NHC(=O)-, or a group consisting of a combination of two or more thereof, more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, or a group consisting of a combination of two or more thereof, and even more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom or -O-. In particular, A １ and A ３ is preferably —O—. ２ is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom. １ and A ３ is —O—, and A ２ -C(CH ３ ) ２ The number of carbon atoms in the aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom is not particularly limited, but is preferably 1 to 6, and more preferably 1 to 4. Specific examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom include -CH ２ -, -C(CH ３ ) ２ -, -C(CF ３ ) ２ -, among which -C(CH ３ ) ２- is preferred. Examples of the substituents on the four benzene rings described in formula (71) include a fluorine atom and a hydrocarbon group having 1 to 10 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom. An embodiment in which all of the four benzene rings described in formula (71) are unsubstituted is also one of the preferred embodiments of the present invention.

[0030] Also, R １１１ is also preferably a group represented by the following formula (81). １１１ is more preferably a group represented by the following formula (82). In formula (81), A １ and A ２ are each independently a single bond or a divalent linking group, * represents a bonding site to the nitrogen atom in formula (2), and in the three benzene rings described in formula (81), each hydrogen atom may be substituted with a substituent. In formula (82), * represents a bonding site to the nitrogen atom in formula (2).

[0031] In formula (81), A １ and A ２ each independently represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —C(═O)—, —S—, —S(═O) ２ -, -NHC(=O)-, or a group consisting of a combination of two or more thereof is preferred, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, or a group consisting of a combination of two or more thereof is more preferred, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom or -O- is even more preferred, and -C(CH ３ ) ２ It is particularly preferred that -.

[0032] R in formula (2) １１５ represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is more preferred. In formula (5) or formula (6), * each independently represents a bonding site to another structure. In formula (5), R １１２represents a single bond or a divalent linking group, and is a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ２ -, -NHCO-, and a group selected from a combination thereof are preferred, and a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, and -SO ２ - is more preferably a group selected from -CH ２ -, -C(CF ３ ) ２ -, -C(CH ３ ) ２ -, -O-, -CO-, -S- and -SO ２ It is more preferably a divalent group selected from the group consisting of -.

[0033] Also, R １１５ is also preferably a group represented by the following formula (7). １１５ is more preferably a group represented by the following formula (7-2). In formula (7), A １ ~A ３ are each independently a single bond or a divalent linking group, * represents a bonding site with the carbonyl group in formula (2), and the hydrogen atoms of each of the four benzene rings described in formula (7) may be substituted with a substituent. In formula (7-2), * represents a bonding site with the carbonyl group in formula (2).

[0034] In formula (7), A １ ~A ３ and a preferred embodiment of the substituent on the benzene ring is A in the above formula (71). １ ~A ３ and the preferred embodiments of the substituents on the benzene ring are the same as those.

[0035] R １１５ Specifically, R may be a tetracarboxylic acid residue remaining after removal of the anhydride group from a tetracarboxylic dianhydride. １１５The tetracarboxylic acid dianhydride may contain only one kind or two or more kinds of tetracarboxylic acid dianhydride residues as a structure corresponding to the formula (I). The tetracarboxylic acid dianhydride is preferably represented by the following formula (O). In formula (O), R １１５ represents a tetravalent organic group. １１５ The preferred range of R in formula (2) is １１５ The same applies to the preferred range.

[0036] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfidetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2 2,3,3',4'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and alkyl and alkoxy derivatives having 1 to 6 carbon atoms thereof.

[0037] Further, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017 / 038598 are also preferred examples.

[0038] In formula (2), R １１１ and R １１５ At least one of R may have an OH group. １１１Examples of the amino acid residue include residues of bisaminophenol derivatives.

[0039] R in formula (2) １１３ and R １１４ each independently represents a hydrogen atom or a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. １１３ and R １１４ Preferably, at least one of R contains a polymerizable group, and more preferably, both of R １１３ and R １１４ It is also preferable that at least one of the groups contains two or more polymerizable groups. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, radicals, or the like, and a radically polymerizable group is preferred. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. The radically polymerizable group possessed by the polyimide precursor is preferably a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., a vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III), with a group represented by the following formula (III) being preferred.

[0040]

[0041] In formula (III), R ２００ represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, and is preferably a hydrogen atom or a methyl group. In formula (III), * represents a bonding site with another structure. In formula (III), R ２０１ represents an alkylene group having 2 to 12 carbon atoms, —CH ２ CH(OH)CH ２ -, a cycloalkylene group or a polyalkyleneoxy group. ２０１Examples of the alkylene group include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, and a dodecamethylene group; a 1,2-butanediyl group, a 1,3-butanediyl group; a —CH ２ CH(OH)CH ２ alkylene groups such as ethylene and propylene; ２ CH(OH)CH ２More preferred are alkylene groups such as ethylene and propylene, or polyalkyleneoxy groups. In the present invention, a polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the multiple alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different. When a polyalkyleneoxy group contains multiple alkyleneoxy groups with different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, a block arrangement, or an arrangement having an alternating pattern. The number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent if the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 6, even more preferably 2 to 5, even more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2. The alkylene group may also have a substituent. Preferred substituents include alkyl groups, aryl groups, and halogen atoms. The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoint of solvent solubility and solvent resistance, the polyalkyleneoxy group is preferably a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, more preferably a polyethyleneoxy group or a polypropyleneoxy group, and even more preferably a polyethyleneoxy group. In the group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, the ethyleneoxy groups and propyleneoxy groups may be arranged randomly, in blocks, or in an alternating pattern. The preferred embodiments of the number of repeating ethyleneoxy groups and the like in these groups are as described above.

[0042] In formula (2), R １１３is a hydrogen atom, or R １１４ When is a hydrogen atom, the polyimide precursor may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

[0043] In formula (2), R １１３ and R １１４ At least one of the groups may be a polarity conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxy group. Preferred examples include an acetal group, a ketal group, a silyl group, a silyl ether group, and a tertiary alkyl ester group. From the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferred. Specific examples of the acid-decomposable group include a tert-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tert-butoxycarbonylmethyl group, and a trimethylsilyl ether group. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.

[0044] The polyimide precursor preferably contains fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more and 20% by mass or less.

[0045] Furthermore, for the purpose of improving adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specific examples include embodiments using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, or the like as the diamine.

[0046] The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having a repeating unit represented by formula (2-A). When the polyimide precursor contains a repeating unit represented by formula (2-A), it becomes possible to further widen the width of the exposure latitude. Formula (2-A) In formula (2-A), A １ and A ２ represents an oxygen atom, R １１１ and R １１２ each independently represents a divalent organic group; R １１３ and R １１４ each independently represents a hydrogen atom or a monovalent organic group; R １１３ and R １１４ At least one of the groups is a group containing a polymerizable group, and it is preferred that both of the groups are groups containing a polymerizable group.

[0047] A １ , A ２ , R １１１ , R １１３ and R １１４ are each independently A in formula (2). １ , A ２ , R １１１ , R １１３ and R １１４ The same definition and preferred range are also true. １１２ is R in formula (5). １１２ The same applies to the preferred range.

[0048] The polyimide precursor may contain one type of repeating unit represented by formula (2), or may contain two or more types. It may also contain a structural isomer of the repeating unit represented by formula (2). The polyimide precursor may also contain other types of repeating units in addition to the repeating unit of formula (2).

[0049] In one embodiment of the polyimide precursor of the present invention, the content of the repeating unit represented by formula (2) is 50 mol% or more of all repeating units. The total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the polyimide precursor except for the terminal repeating units may be repeating units represented by formula (2).

[0050] -Imidization rate- From the viewpoint of the film strength, insulating properties, etc. of the resulting organic film, the imidization rate of the polyimide precursor is preferably less than 70%, more preferably 60% or less, even more preferably 50% or less, still more preferably 40% or less, and particularly preferably 30% or less. The lower limit of the imidization rate is not particularly limited, and it is sufficient as long as it is 0% or more.

[0051] In the present invention, the imidization rate is a value calculated by the following method. The 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. Examples of such solvents include solvents contained in the resin composition, such as NMP. The viscosity may also be adjusted as appropriate within an adjustable range. The silicon wafer to which the resulting resin layer is applied is dried on a hot plate at 110°C for 5 minutes to obtain a resin layer on the silicon wafer with a uniform thickness of approximately 15 μm after film formation. Here, if only a resin solution with a low viscosity is obtained and it is difficult to obtain a resin layer with a thickness of 15 μm, the film thickness may be adjusted as appropriate. For example, if the film thickness is 5 μm or greater, a similar imidization rate value can be obtained. The resin layer was measured by the ATR method using NicoletiS20 (manufactured by Thermofisher) in the measurement range of 4000 to 700 cm －１ , the measurement is performed 50 times. －１ Around (1350-1450 cm －１(If there are multiple peaks, the peak with the greatest intensity) and 1500 cm －１ Around (1460-1550 cm －１ The imidization index A of the resin is calculated by dividing the imidization index B by the peak height of the peak (or the peak with the greatest intensity if there are multiple peaks) in a nitrogen atmosphere at a heating rate of 10°C / min and heated at 350°C for 1 hour. The imidization index B is calculated in the same manner for a film that has been heated at a heating rate of 10°C / min under a nitrogen atmosphere and heated at 350°C for 1 hour. The imidization index A is then divided by the imidization index B to calculate the imidization rate of the resin. In measuring the imidization rate, the resin whose imidization rate is to be measured 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 to cause crystallization, and the resin is precipitated and filtered. The residue is recovered and dissolved in 3.0 g of THF (tetrahydrofuran), and this is added to 50 g of methanol or water to cause crystallization. The solution is filtered and dried at 40°C for 20 hours to obtain a resin.

[0052] The weight-average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. The number-average molecular weight (Mn) of the polyimide precursor is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The molecular weight dispersity of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyimide precursor is not particularly specified, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. In this specification, the molecular weight dispersity is a value calculated by dividing the weight-average molecular weight by the number-average molecular weight. When the photosensitive resin composition contains multiple polyimide precursors as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide precursor are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated by treating the multiple polyimide precursors as a single resin are each within the above-mentioned ranges.

[0053] [Polyimide] The polyimide used in the present invention may be an alkali-soluble polyimide, or may be a polyimide soluble in a developer containing an organic solvent as a main component. In this specification, alkali-soluble polyimide refers to a polyimide that dissolves at 0.1 g or more in 100 g of a 2.38 mass % aqueous tetramethylammonium solution at 23°C. From the viewpoint of pattern formability, a polyimide that dissolves at 0.5 g or more is preferred, and a polyimide that dissolves at 1.0 g or more is even more preferred. The upper limit of the solubility is not particularly limited, but is preferably 100 g or less. From the viewpoint of the film strength and insulating properties of the resulting organic film, the polyimide is preferably a polyimide having multiple imide structures in its main chain.

[0054] -Fluorine Atom- From the viewpoint of the film strength of the obtained organic film, it is also preferable that the polyimide contains a fluorine atom. The fluorine atom is, for example, R １３２ or R in the repeating unit represented by formula (4) described below １３１ and R in the repeating unit represented by formula (4) described below is preferably included. １３２ or R in the repeating unit represented by formula (4) described below １３１ It is more preferable that the fluorine atoms are contained as fluorinated alkyl groups in the polyimide. The amount of fluorine atoms relative to the total mass of the polyimide is preferably 5% by mass or more, and preferably 20% by mass or less. From the viewpoint of adhesion, it is also preferable that the polyimide is substantially free of fluorine atoms. Here, "substantially free" means that the amount of fluorine atoms relative to the total mass of the polyimide is less than 5% by mass, preferably less than 1% by mass, more preferably less than 0.1% by mass, and even more preferably less than 0.01% by mass. The lower limit of the amount of fluorine atoms is not particularly limited, and may be 0% by mass.

[0055] -Silicon Atom- From the viewpoint of the film strength of the obtained organic film, it is also preferable that the polyimide contains a silicon atom. The silicon atom is, for example, R in the repeating unit represented by formula (4) described later. １３１and R in the repeating unit represented by formula (4) described below is preferably included. １３１ It is more preferable that the silicon atom or the organic modified (poly)siloxane structure described below is contained in the polyimide. The silicon atom or the organic modified (poly)siloxane structure may be contained in a side chain of the polyimide, but is preferably contained in the main chain of the polyimide. The amount of silicon atoms relative to the total mass of the polyimide is preferably 1 mass % or more and 20 mass % or less.

[0056] - Ethylenically unsaturated bond - From the viewpoint of the film strength of the obtained organic film, it is preferable that the polyimide has an ethylenically unsaturated bond. The polyimide may have the ethylenically unsaturated bond at the end of the main chain or in a side chain, but it is preferable that the ethylenically unsaturated bond is in a side chain. The ethylenically unsaturated bond is preferably radically polymerizable. The ethylenically unsaturated bond is formed by the R １３２ or R １３１ and R １３２ or R １３１ Among these, the ethylenically unsaturated bond is more preferably contained as a group having an ethylenically unsaturated bond in R １３１ and R １３１ Examples of the group having an ethylenically unsaturated bond include a group having an optionally substituted vinyl group directly bonded to an aromatic ring, such as a vinyl group, an allyl group, or a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (IV):

[0057]

[0058] In formula (IV), R ２０ represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and is preferably a hydrogen atom or a methyl group.

[0059] In formula (IV), R ２１ represents an alkylene group having 2 to 12 carbon atoms, —O—CH ２ CH(OH)CH２ -, -C(=O)O-, -O(C=O)NH-, a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and particularly preferably 2 or 3 carbon atoms; the number of repeating alkyleneoxy groups is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3 carbon atoms), or a group combining two or more of these. The alkylene group having 2 to 12 carbon atoms may be any of linear, branched, and cyclic alkylene groups, or alkylene groups represented by a combination thereof. The alkylene group having 2 to 12 carbon atoms is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.

[0060] Among these, R ２１ is preferably a group represented by any one of the following formulae (R1) to (R3), and more preferably a group represented by formula (R1). In formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group in which two or more of these are bonded together; X represents an oxygen atom or a sulfur atom; * represents a bonding site with another structure; and ● represents R ２１ In formulas (R1) to (R3), a preferred embodiment of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms as L is R in formula (IV). ２１The preferred embodiments are the same as those of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms. In formula (R1), X is preferably an oxygen atom. In formulas (R1) to (R3), * has the same meaning as * in formula (IV), and the preferred embodiments are also the same. The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having an isocyanato group and an ethylenically unsaturated bond (e.g., 2-isocyanatoethyl methacrylate). The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (e.g., 2-hydroxyethyl methacrylate). The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (e.g., glycidyl methacrylate).

[0061] In formula (IV), * represents a bonding site to another structure, and is preferably a bonding site to the main chain of the polyimide.

[0062] The amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.0005 to 0.05 mol / g.

[0063] -Polymerizable group other than a group having an ethylenically unsaturated bond- The polyimide may have a polymerizable group other than a group having an ethylenically unsaturated bond. Examples of the polymerizable group other than a group having an ethylenically unsaturated bond include an epoxy group, a cyclic ether group such as an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a methylol group. Examples of the polymerizable group other than a group having an ethylenically unsaturated bond include R in the repeating unit represented by formula (4) below. １３１ The amount of polymerizable groups other than groups having an ethylenically unsaturated bond relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0064] - Polarity conversion group - The polyimide may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the polyimide is R １１３ and R １１４ The polarity conversion group is, for example, R in the repeating unit represented by formula (4) described later. １３１ , R １３２ , contained in the terminals of polyimides, etc.

[0065] -Acid Value- When the polyimide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of the polyimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and even more preferably 70 mgKOH / g or more. The acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and even more preferably 200 mgKOH / g or less. When the polyimide is subjected to development using a developer containing an organic solvent as a main component (e.g., "solvent development"), the acid value of the polyimide is preferably 1 to 35 mgKOH / g, more preferably 2 to 30 mgKOH / g, and even more preferably 5 to 20 mgKOH / g. The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. From the viewpoint of achieving both storage stability and developability, the acid group contained in the polyimide preferably has a pKa of 0 to 10, more preferably 3 to 8. pKa refers to the equilibrium constant Ka of a dissociation reaction in which a hydrogen ion is released from an acid, expressed as its negative common logarithm, pKa. In this specification, pKa refers to a value calculated using ACD / ChemSketch (registered trademark) unless otherwise specified. For pKa, reference may be made to the value listed in the "Revised 5th Edition Chemistry Handbook: Basics" compiled by the Chemical Society of Japan. When the acid group is a polyvalent acid such as phosphoric acid, the pKa is the first dissociation constant. As such an acid group, the polyimide preferably contains at least one selected from the group consisting of a carboxy group and a phenolic hydroxy group, and more preferably a phenolic hydroxy group.

[0066] -Phenol Hydroxy Group- From the viewpoint of ensuring an appropriate development rate with an alkaline developer, the polyimide preferably has a phenolic hydroxy group. The polyimide may have the phenolic hydroxy group at the end of the main chain or on a side chain. The phenolic hydroxy group can be, for example, R in the repeating unit represented by formula (4) described below. １３２ or R １３１ The amount of phenolic hydroxy groups relative to the total mass of the polyimide is preferably 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.

[0067] The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but it is preferable that it contains a repeating unit represented by the following formula (4). In formula (4), R １３１ represents a divalent organic group, and R １３２ represents a tetravalent organic group. When the compound has a polymerizable group, the polymerizable group is １３１ and R １３２ or may be located at the end of the polyimide as shown in the following formula (4-1) or formula (4-2): In formula (4-1), R １３３ is a polymerizable group, and the other groups have the same meanings as in formula (4). In formula (4-2), R １３４ and R １３５ At least one of the groups is a polymerizable group, and if it is not a polymerizable group, it is an organic group, and the other group has the same meaning as in formula (4).

[0068] Examples of the polymerizable group include the above-mentioned group containing an ethylenically unsaturated bond and a crosslinkable group other than the above-mentioned group having an ethylenically unsaturated bond. １３１ represents a divalent organic group. The divalent organic group is R １１１ The same examples as those listed above are given, and the preferred ranges are also the same. １３１The diamine residues include those remaining after removal of the amino groups of the diamine. Examples of the diamine include aliphatic, cycloaliphatic, and aromatic diamines. Specific examples include R in the formula (2) of the polyimide precursor. １１１ Examples include:

[0069] R １３１ is preferably a diamine residue having at least two alkylene glycol units in the main chain, in order to more effectively suppress the occurrence of warping during firing, more preferably a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and even more preferably a diamine residue of the above diamine that does not contain an aromatic ring.

[0070] Examples of diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule include, but are not limited to, Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, and D-4000 (all trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.

[0071] Also, R １３１ is preferably a group containing a group represented by formula (2-1), and more preferably a group represented by formula (2-1). In formula (2-1), R １ and R ２ each independently represents a group having an ethylenically unsaturated bond, L represents a single bond or a divalent linking group not containing an imide bond, and * represents a bonding site to another structure.

[0072] In formula (2-1), R １ and R ２ are each preferably independently a group represented by the following formula (R1-1): In formula (R1-1), L Ｒ１represents an (n+1)-valent linking group, R Ｒ１ R each independently represents an aromatic group directly bonded to a vinyl group, a maleimide group, a (meth)acryloxy group, or a (meth)acrylamide group, n represents an integer of 1 to 10, and * represents the bonding site with the oxygen atom in formula (2-1). Ｒ１ are each independently preferably an aromatic group or a maleimide group directly bonded to a vinyl group, and more preferably a vinylphenyl group. Ｒ１ is a hydrocarbon group, or a hydrocarbon group and —O—, —C(═O)—, —S—, —S(═O) ２ - and -NR Ｎ - is preferably a group represented by a bond to at least one group selected from the group consisting of a hydrocarbon group, * １ -C(=O)-L Ｒ２ -* ２ Or, * １ -C(=O)NR Ｎ -L Ｒ２ -* ２ The above L is preferably a group represented by the formula: Ｒ１ The hydrocarbon group in the above L is preferably an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. Ｒ２ represents a hydrocarbon group, preferably an alkylene group, more preferably an alkylene group having 2 to 10 carbon atoms, and even more preferably an alkylene group having 2 to 6 carbon atoms. Ｎ is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, still more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom. １ has the same meaning as * in formula (R1-1), ２ is R in formula (R1-1) Ｒ１ represents the binding site with R Ｒ１ is a vinylphenyl group, L Ｒ１ is preferably an alkylene group having 1 to 4 carbon atoms, and more preferably a methylene group. Ｒ１ is a maleimide group, L Ｒ１ is an alkylene group having 1 to 4 carbon atoms or * １ -C(=O)-L Ｒ２ -*２ It is preferable that R Ｒ１ is a (meth)acryloxy group or a (meth)acrylamide group, L Ｒ１ teeth* １ -C(=O)NR Ｎ -L Ｒ２ -* ２ n is preferably an integer of 1 to 4, more preferably 1 or 2, and more preferably 1.

[0073] In formula (2-1), L is a single bond, —C(CH ３ ) ２ -, -C(CF ３ ) ２ -, -S(=O) ２ - or a 9,9-fluorenediyl group is preferred. ３ ) ２ -, or -C(CF ３ ) ２ The embodiment in which - is also one of the preferred embodiments of the present invention.

[0074] R １３２ represents a tetravalent organic group. The tetravalent organic group is R １１５ Examples of the group R are the same as those of the group R, and the preferred ranges are also the same. １１５ The four bonds of the tetravalent organic group exemplified by: are bonded to the four —C(═O)— moieties in formula (4) to form a condensed ring.

[0075] R １３２ Examples of the tetracarboxylic acid residues include those remaining after removal of the anhydride groups from tetracarboxylic dianhydrides. １１５ From the viewpoint of the strength of the organic film, R １３２ is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

[0076] R １３１ and R １３２ It is also preferable that at least one of R １３１Preferred examples of R include 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18). １３２ As the above, (DAA-1) to (DAA-5) are more preferred examples.

[0077] The polyimide preferably contains fluorine atoms in its structure, and the content of fluorine atoms in the polyimide is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0078] To improve adhesion to the substrate, the polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specific examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0079] In order to improve the storage stability of the photosensitive resin composition, it is preferable that the main chain terminals of the polyimide are blocked with a terminal blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound. Among these, it is more preferable to use a monoamine, and preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, and 1-carboxy 2-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, and multiple different terminal groups may be introduced by reacting multiple terminal-capping agents.

[0080] -Imidization rate (ring closure rate)- The imidization rate of the polyimide (also referred to as "ring closure rate") is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, from the viewpoint of the film strength, insulating properties, etc. of the resulting organic film. There is no particular upper limit to the imidization rate, and it is sufficient if it is 100% or less. The imidization rate is measured by the method described above.

[0081] Polyimide is a polymer in which all repeating units are R １３１ and R １３２The repeating unit may contain the repeating unit represented by the above formula (4) in which the combination of R １３１ and R １３２ The polyimide may contain a repeating unit represented by the formula (4) above, which contains two or more different combinations of repeating units. In addition to the repeating unit represented by the formula (4), the polyimide may contain other types of repeating units. Examples of other types of repeating units include the repeating unit represented by the formula (2) above.

[0082] Polyimides can be synthesized by, for example, reacting a tetracarboxylic dianhydride with a diamine (partially substituted with a monoamine end-capping agent) at low temperature, reacting a tetracarboxylic dianhydride with a diamine (partially substituted with an acid anhydride, monoacid chloride compound, or monoactive ester compound end-capping agent) at low temperature, preparing a diester from a tetracarboxylic dianhydride with an alcohol and then reacting it with a diamine (partially substituted with a monoamine end-capping agent) in the presence of a condensing agent, preparing a diester from a tetracarboxylic dianhydride with an alcohol and then converting the remaining dicarboxylic acid to an acid chloride and reacting it with a diamine (partially substituted with a monoamine end-capping agent), or by completely imidizing the resulting polyimide precursor using a known imidization reaction method, or by terminating the imidization reaction midway to introduce a partial imide structure, or by blending a fully imidized polymer with the polyimide precursor to introduce a partial imide structure. Other known polyimide synthesis methods can also be used.

[0083] The weight-average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. By setting the weight-average molecular weight to 5,000 or more, the fold resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties (e.g., breaking elongation), the weight-average molecular weight is particularly preferably 15,000 or more. The number-average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The molecular weight dispersity of the polyimide is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyimide is not particularly specified, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. When the photosensitive resin composition contains multiple types of polyimides as specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one type of polyimide are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple types of polyimides as one resin are each within the above ranges.

[0084] [Content] The content of the specific resin in the photosensitive resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the photosensitive resin composition. Furthermore, the content of the resin in the photosensitive resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the photosensitive resin composition. The photosensitive resin composition of the present invention may contain only one type of specific resin, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0085] The photosensitive resin composition of the present invention preferably contains at least two types of resins. Specifically, the photosensitive resin composition of the present invention may contain a total of two or more types of the specific resin and other resins described later, or may contain two or more types of specific resins, but preferably contains two or more types of specific resins. When the photosensitive resin composition of the present invention contains two or more types of specific resins, for example, a polyimide precursor having a structure derived from a dianhydride (R in the above formula (2) １１５ ) preferably contains two or more different polyimide precursors.

[0086] <Other Resins> The photosensitive resin composition of the present invention may contain the specific resin described above and another resin (hereinafter simply referred to as "other resin") different from the specific resin. Examples of other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins. For example, by further adding a (meth)acrylic resin, a photosensitive resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained. For example, instead of or in addition to the polymerizable compound described below, a polymerizable compound having a high polymerizable group value and a weight average molecular weight of 20,000 or less (for example, a polymerizable group content of 1×10 per 1 g of resin) can be used. －３ By adding a (meth)acrylic resin (having a molecular weight of 1000 to 1000 mol / g or more) to a photosensitive resin composition, the coatability of the photosensitive resin composition and the solvent resistance of the pattern (cured product) can be improved.

[0087] When the photosensitive resin composition of the present invention contains another resin, the content of the other resin 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 photosensitive resin composition. When the photosensitive resin composition of the present invention contains another resin, the content of the other resin 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 photosensitive resin composition. A preferred embodiment of the photosensitive resin composition of the present invention may also be an embodiment in which the content of the other resin is low. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the photosensitive resin composition. The lower limit of the content is not particularly limited, and may be 0% by mass or more. The photosensitive resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more types are contained, it is preferable that the total amount is in the above range.

[0088] <Compound A> The photosensitive resin composition of the present invention contains a compound A represented by formula (A-1) or (A-2). In formula (A-1) or (A-2), Ar １ each independently represents an aromatic group which may have a substituent.

[0089] Ar １may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, but is preferably an aromatic hydrocarbon group. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have a substituent; a phenyl group or a naphthyl group, which may have a substituent, is more preferred, and a phenyl group, which may have a substituent, is even more preferred. The aromatic heterocyclic group is preferably a group formed from a 5-membered ring, a 6-membered ring, or a ring formed by condensing two or more ring structures corresponding to either a 5-membered ring or a 6-membered ring. Examples of heteroatoms in the aromatic heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom, with a nitrogen atom being preferred. Among these, the aromatic heterocyclic group is preferably a group formed from an azole ring, which may have a substituent, more preferably a group formed from a triazole ring, which may have a substituent, or a pyrazole ring, which may have a substituent, and is preferably a group represented by the following structure: In the following structure, hydrogen atoms may be substituted with a substituent such as a methyl group, and * indicates a bonding site to another structure.

[0090] Ar １ The substituent in Ar is not particularly limited, but examples thereof include an alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, an alkenyl group, an alkynyl group, a carboxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an amino group, a cyano group, and a halogen atom. １may have only one or two or more of the above-mentioned substituents, and preferably has, for example, one or two. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. The alkyl group may further have a substituent, and examples of the substituent include a hydroxy group. An example of an embodiment having such a substituent is a hydroxyethyl group. The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 8 carbon atoms, and even more preferably an alkoxy group having 1 to 6 carbon atoms. The alkoxy group may further have a substituent, and examples of the substituent include a hydroxy group, an alkylcarbonyl group, and the like. Examples of an embodiment having such a substituent include a hydroxyethyloxy group and a methylcarbonylmethoxy group. The aryloxy group is preferably an aryloxy group having 1 to 20 carbon atoms, and more preferably a phenoxy group. The aryloxy group may further have a substituent, and examples of the substituent include an amino group. An example of an embodiment having such a substituent is an aminophenoxy group. In addition, examples of the substituent of such an aryloxy group include -N=N-Ar ２ The above Ar may also have a group represented by the formula: ２ A preferred embodiment of is Ar １The preferred embodiments are the same as those described above. The alkenyl group is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 4 carbon atoms, and even more preferably an alkenyl group having 2 carbon atoms. The alkenyl group may further have a substituent. The alkynyl group is preferably an alkynyl group having 2 to 10 carbon atoms, more preferably an alkynyl group having 2 to 4 carbon atoms, and even more preferably an alkynyl group having 2 carbon atoms. The alkynyl group may further have a substituent. The alkylthio group is preferably an alkylthio group having 1 to 4 carbon atoms, more preferably a methylthio group or an ethylthio group, and even more preferably a methylthio group. The alkylthio group may further have a substituent. The arylthio group is preferably an arylthio group having 1 to 20 carbon atoms, and more preferably a phenylthio group. The arylthio group may further have a substituent, and examples of the substituent include an amino group. Examples of embodiments having such a substituent include an aminophenylthio group. Examples of the substituent of such an arylthio group include -N=N-Ar ２ The above Ar may also have a group represented by the formula: ２ A preferred embodiment of is Ar １ The preferred embodiments are the same as those in the above. The alkylsulfonyl group is preferably an alkylsulfonyl group having 1 to 4 carbon atoms, more preferably a methylsulfonyl group or an ethylsulfonyl group, and even more preferably a methylsulfonyl group. The alkylsulfonyl group may further have a substituent. The amino group may be an unsubstituted amino group or a substituted amino group. Examples of the substituted amino group include a monoalkylamino group, a dialkylamino group, a monoarylamino group, a diarylamino group, and an alkylarylamino group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred.

[0091] Among these, Ar １ Preferably, at least one of Ar is an aromatic group having a phenolic hydroxy group, an alkoxy group, or an amino group. １It may be a hydroxy group bonded to Ar by a single bond without a linking group, or １ For example, Ar may be a phenolic hydroxy group bonded to an aromatic ring contained in the substituent in １ a hydroxy group bonded to Ar by a single bond without a linking group, or １ Preferably, the aryloxy group is a hydroxy group that is bonded to the aromatic ring structure of the aryloxy group bonded as a substituent to Ar via a single bond without a linking group. Preferred embodiments of the aryloxy group are as described above. In this specification, the embodiment of bonding via a single bond without a linking group is also referred to as "directly bonded." The alkoxy group is preferably a hydroxy group that is bonded to the aromatic ring structure of Ar via a single bond without a linking group. １ It may be an alkoxy group bonded to Ar by a single bond without a linking group, or １ However, Ar may be an alkoxy group bonded to a substituent in １ Even in the case of an alkoxy group bonded to a substituent in the formula (I), it is preferable that the alkoxy group be directly bonded to the aromatic group in the substituent without a linking group. １ The amino group is preferably an alkoxy group that is bonded to Ar by a single bond without a linking group. The preferred embodiment of the alkoxy group is as described above. １ It may be an amino group bonded to Ar by a single bond without a linking group, or １ For example, Ar may be an amino group bonded to a substituent in １ an amino group bonded to Ar by a single bond without a linking group, or １ It is preferably an amino group that is bonded by a single bond, without a linking group, to the aromatic ring structure of the aryloxy group that is bonded as a substituent to the amino group. The preferred embodiments of the amino group and the aryloxy group are as described above.

[0092] Among these, Ar １ It is preferable that at least one of the groups is an aromatic group having a phenolic hydroxy group, an alkoxy group directly bonded to an aromatic ring, or an amino group directly bonded to an aromatic ring. In this manner, it is possible to adjust the absorption wavelength of compound A.

[0093] From the viewpoint of making the absorption wavelength of compound A close to the photosensitive wavelength of the photopolymerization initiator, compound A preferably has an aromatic amino group. In this specification, the aromatic amino group refers to an amino group bonded to an aromatic ring by a single bond without a linking group, and may be a substituted amino group or an unsubstituted amino group. A preferred embodiment of such an amino group is the above-mentioned Ar １ The preferred embodiments of the amino group are the same as those described as the substituent of Ar. Among these, an unsubstituted amino group or a dialkylamino group is preferred. The aromatic amino group is Ar １ It may be an amino group bonded to Ar by a single bond without a linking group, or １ It may be an amino group bonded to the aromatic ring contained in the substituent in the formula (I) by a single bond without a linking group. For example, Ar １ an amino group bonded to Ar by a single bond without a linking group, or １ It is preferably an amino group that is bonded by a single bond to the aromatic ring structure of the aryloxy group that is bonded as a substituent to the above without a linking group.

[0094] The compound represented by formula (A-1) preferably has an absorption maximum in the wavelength range of 300 to 500 nm, more preferably 320 to 450 nm, and even more preferably 340 to 400 nm. The absorption maximum wavelength can be measured, for example, using a spectrophotometer.

[0095] The compound represented by formula (A-2) is preferably a compound that is converted to the compound represented by formula (A-1) by irradiation with light having a wavelength of 300 to 800 nm and heating. The wavelength is more preferably 350 to 750 nm, and even more preferably 400 to 700 nm. Whether a certain compound is a compound that is converted to the compound represented by formula (A-1) by irradiation with light having a wavelength of 300 to 800 nm and heating can be determined by the following method: An NMP solution (1 mmol / L) of the compound is heated to 20°C and irradiated with broadband light having a wavelength of 300 to 800 nm at an exposure dose of 100 mJ / cm. ２When the compound represented by formula (A-1) is generated in an amount of 1 mol % or more relative to the molar amount of the original compound, the compound is determined to be a compound that can be converted to the compound represented by formula (A-1) by irradiation with light having a wavelength of 300 to 800 nm and heating. １ This can be confirmed by H-NMR or the like.

[0096] The compound represented by formula (A-2) is a compound represented by the formula (A-3) １ In many cases, the melting point is lower than that of the compound represented by formula (A-1), which has the same structure. Therefore, by including the compound represented by formula (A-2), a temporary plasticizing effect is exerted, which promotes the orientation of the polyimide, and the mechanical properties may be improved.

[0097] Here, compound A may be a compound represented by formula (A-3). In formula (A-3), Ar １ each independently represents an aromatic group which may have a substituent, and when n+m is 2, L １ represents a single bond or a linking group having a valence of n+m, and when n+m is 3 or more, L １ represents a linking group having a valence of n+m, n represents an integer of 0 or more, m represents an integer of 0 or more, and n+m represents an integer of 2 or more.

[0098] In formula (A-3), Ar １ A preferred embodiment of the formula (A-1) is Ar １ In addition, when n is 2 or more, or when m is 2 or more, 2×n Ar １ may be the same or different, and 2 × m Ar １ may be the same or different.

[0099] In formula (A-3), L １ represents a single bond, or a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O) ２ -, -NR Ｎ - or a group in which two or more of these are bonded together is preferred. The hydrogen atoms in the hydrocarbon group may be substituted with other structures such as halogen atoms.Ｎ is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, still more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom. １ is preferably a single bond or the following structure: In the following structure, * represents Ar １ represents the binding site with １ represents a hydrocarbon group in which a hydrogen atom may be substituted with a fluorine atom; n1 represents an integer of 0 to 4;

[0100] In formula (A-3), n+m is preferably an integer of 2 to 4, more preferably 2 or 3, and even more preferably 2. n is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and particularly preferably 2. m is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0.

[0101] [Molecular Weight] The molecular weight of compound A is preferably 180 to 1,500, more preferably 190 to 1,000, and even more preferably 195 to 800.

[0102] [Synthesis Method] Compound A can be synthesized, for example, by the method described in the Examples below. Alternatively, other known synthesis methods may be used, and the synthesis method is not particularly limited. Alternatively, compounds marketed by Tokyo Chemical Industry Co., Ltd. or the like may also be used.

[0103] [Specific Examples] Specific examples of Compound A are not particularly limited, but include the compounds used in the examples described below.

[0104] [Content] The content of compound A relative to the total solid content of the photosensitive resin composition of the present invention is preferably 0.05 to 20% by mass. The lower limit is more preferably 0.08% by mass or more, and even more preferably 0.10% by mass or more. The upper limit is more preferably 18% by mass or less, even more preferably 15% by mass or less, and particularly preferably 10% by mass or less. Furthermore, when the content of the specific resin is taken as 100 parts by mass, the content of compound A is preferably 0.05 to 30 parts by mass, more preferably 0.08 to 20 parts by mass, even more preferably 0.10 to 18 parts by mass, and particularly preferably 0.12 to 15 parts by mass. One type of compound A may be used alone, or two or more types may be used in combination. When two or more types are used in combination, the total amount thereof preferably falls within the above range.

[0105] <Organometallic Complex> The photosensitive resin composition of the present invention preferably contains an organometallic complex. The organometallic complex is preferably a compound containing a Group 4 element. The compound containing a Group 4 element is preferably a compound containing titanium, zirconium, or hafnium, and more preferably a compound containing titanium. Furthermore, the compound containing a Group 4 element is more preferably an organotitanium complex.

[0106] Specific examples of titanium-containing compounds are shown below in I) to VII): I) Titanium chelate compounds: Among these, titanium chelates having two or more alkoxy groups are more preferred because they provide a negative photosensitive resin composition with good storage stability and a good pattern. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), etc.

[0107] II) Tetraalkoxytitanium compounds: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], etc.

[0108] III) Titanocene compounds: for example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η ５ -2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η ５ -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like.

[0109] IV) Monoalkoxytitanium compounds: For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc.

[0110] V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc.

[0111] VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate.

[0112] VII) Titanate coupling agents: for example, isopropyl tridodecylbenzenesulfonyl titanate.

[0113] Among the above I) to VII), it is preferable that the titanium-containing compound is at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, from the viewpoint of exhibiting better chemical resistance. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η ５ 3-(1H-pyrrol-1-yl)phenyl)titanium is preferred.

[0114] Furthermore, the organometallic complex is preferably a metal complex having one or more π-conjugated moieties containing a nitrogen atom (hereinafter also referred to as a "specific metal complex"). Here, the nitrogen atom is preferably directly bonded to a metal atom in the specific metal complex. The bond is not particularly limited, but is preferably a coordinate bond. Furthermore, the π-conjugated moiety may have only one nitrogen atom or may have two or more nitrogen atoms. When two or more nitrogen atoms are present, it is preferable that one of the nitrogen atoms is directly bonded to a metal atom in the specific metal complex. Here, the specific metal complex may have only one or two or more π-conjugated moieties containing a nitrogen atom, but it is preferable that the specific metal complex has one to two π-conjugated moieties.

[0115] The π-conjugated moiety containing a nitrogen atom preferably has a structure represented by the following formula (Co-1). In formula (Co-1), X １ ~X ３ each independently represents -C(-*)= or -N=, * represents a bonding site to another structure, and # represents a bonding site to a metal atom.

[0116] In formula (Co-1), X １ ~X ３ each independently represents -C(-*)= or -N=, and it is preferable that at least one represents -C(-*)=, and it is more preferable that at least two represent -C(-*)=.

[0117] In formula (Co-1), at least two structures bonded to * may be bonded to form a ring structure. The ring structure may be an aliphatic ring structure or an aromatic ring structure, but is preferably an aromatic ring structure.

[0118] It is also preferable to include a compound represented by the following formula (T-1) as the specific metal complex. In formula (T-1), M is titanium, zirconium, or hafnium, l1 is an integer of 0 to 2, l2 is 0 or 1, l1 + l2 × 2 is an integer of 0 to 2, m is an integer of 0 to 4, n is an integer of 0 to 2, l1 + l2 + m + n × 2 = 4, and R １１ are each independently a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenoxy group; R １２ are each independently a substituted or unsubstituted hydrocarbon group, R ２ are each independently a group containing a structure represented by the following formula (T-2), and R ３ are each independently a group containing a structure represented by the following formula (T-2), Ａ are each independently an oxygen atom or a sulfur atom. In formula (T-2), X １ ~X ３ each independently represents -C(-*)= or -N=, * represents a bonding site to another structure, and # represents a bonding site to a metal atom.

[0119] In formula (T-1), from the viewpoint of storage stability of the composition, M is preferably titanium. In formula (T-1), an embodiment in which l1 and l2 are 0 is also one of the preferred embodiments of the present invention. In formula (T-1), m is preferably 2 or 4, and more preferably 2. In formula (T-1), n ​​is preferably 1 or 2, and more preferably 1. Here, it is also preferable that in formula (T-1), l1 and l2 are 0, and m is 0, 2, or 4.

[0120] In formula (T-1), from the viewpoint of the stability of the specific metal complex, R １１ is preferably a substituted or unsubstituted cyclopentadienyl ligand. １１The cyclopentadienyl group, alkoxy group and phenoxy group in the formula (I) may be substituted, but an embodiment in which they are unsubstituted is also one of the preferred embodiments of the present invention.

[0121] In formula (T-1), R １２ is preferably a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrocarbon group having 2 to 10 carbon atoms. １２ The hydrocarbon group in may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but an aromatic hydrocarbon group is preferred. The aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, but a saturated aliphatic hydrocarbon group is preferred. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and even more preferably a phenylene group. R １２ The substituent in R is preferably a monovalent substituent, such as a halogen atom. １２ When R is an aromatic hydrocarbon group, it may have an alkyl group as a substituent. １２ is preferably an unsubstituted phenylene group. １２ The phenylene group in is preferably a 1,2-phenylene group.

[0122] In formula (T-1), m is 2 or more, and R ２ If two or more are included, ２ In formula (T-1), n ​​is 2 or more, and R ３ If two or more are included, ３ The structures may be the same or different.

[0123] In formula (T-2), X １ ~X ３ each independently represents -C(-*)= or -N=, and it is preferable that at least one represents -C(-*)=, and it is more preferable that at least two represent -C(-*)=.

[0124] When the photosensitive resin composition contains an organometallic complex, the content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the specific resin. When the content is 0.05 parts by mass or more, heat resistance and chemical resistance are improved, and when it is 10 parts by mass or less, storage stability is improved.

[0125] The photosensitive resin composition of the present invention preferably further contains a photopolymerization initiator and a polymerizable compound, each of which will be described below.

[0126] <Polymerizable Compound> The photosensitive resin composition of the present invention preferably contains a polymerizable compound. Examples of the polymerizable compound include a radical crosslinking agent and other crosslinking agents.

[0127] [Radical Crosslinking Agent] The photosensitive resin composition of the present invention preferably contains a radical crosslinking agent. The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group containing an ethylenically unsaturated bond. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group. Among these, a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferred, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferred.

[0128] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds. The radical crosslinking agent may have three or more ethylenically unsaturated bonds. The compound having two or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and even more preferably a compound having 2 to 6 ethylenically unsaturated bonds. From the viewpoint of the film strength of the obtained pattern (cured product), it is also preferable that the photosensitive resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and the compound having three or more ethylenically unsaturated bonds.

[0129] 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.

[0130] Specific examples of radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, and amides. Preferred are esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. Also suitable are addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxyl group, amino group, or sulfanyl group with monofunctional or polyfunctional isocyanates or epoxies, and dehydration condensation reaction products of monofunctional or polyfunctional carboxylic acids. Also suitable are addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as a halogeno group or a tosyloxy group with monofunctional or polyfunctional alcohols, amines, or thiols. As another example, it is also possible to use a group of compounds in which the above-mentioned unsaturated carboxylic acids are replaced with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc. Specific examples can be found in paragraphs 0113 to 0122 of JP 2016-027357 A, the contents of which are incorporated herein by reference.

[0131] The radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples of compounds having a boiling point of 100°C or higher under normal pressure include the compounds described in paragraph 0203 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0132] Other preferred radical crosslinking agents include the radical polymerizable compounds described in paragraphs 0204 to 0208 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0133] Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available products include KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available products include KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available products include KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), and dipentaerythritol hexa(meth)acrylate (commercially available products include KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)), and structures in which the (meth)acryloyl group is bonded via an ethylene glycol residue or a propylene glycol residue. Oligomers of these agents can also be used.

[0134] Commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, SR-209, 231, and 239, which are difunctional methacrylates having four ethyleneoxy chains (all manufactured by Sartomer Corporation), DPCA-60, a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, a trifunctional acrylate having three isobutyleneoxy chains (all manufactured by Nippon Kayaku Co., Ltd.), and urethane oligomers such as Examples of such an ester include UAS-10 and UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, and UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), and Blenmar PME400 (manufactured by NOF Corporation).

[0135] Suitable radical crosslinking agents include urethane acrylates such as those described in JP-B No. 48-041708, JP-A No. 51-037193, JP-B No. 02-032293, and JP-B No. 02-016765, and urethane compounds having an ethylene oxide skeleton such as those described in JP-B No. 58-049860, JP-B No. 56-017654, JP-B No. 62-039417, and JP-B No. 62-039418. Compounds having an amino structure or a sulfide structure in the molecule, such as those described in JP-A Nos. 63-277653, 63-260909, and JP-A No. 01-105238, can also be used as radical crosslinking agents.

[0136] The radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphate group. The radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent obtained by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound to provide an acid group. Particularly preferred is a radical crosslinking agent obtained by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound to provide an acid group, in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include polybasic acid-modified acrylic oligomers M-510 and M-520 manufactured by Toagosei Co., Ltd.

[0137] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH / g, more preferably 1 to 100 mgKOH / g. When the acid value of the radical crosslinking agent is within the above range, the agent has excellent handleability in production and developability. Furthermore, the agent has good polymerizability. The acid value is measured in accordance with the description of JIS K 0070:1992.

[0138] The radical crosslinking agent is preferably a radical crosslinking agent having at least one selected from the group consisting of a urea bond and a urethane bond (hereinafter also referred to as "crosslinking agent U"). Compound A has high compatibility with crosslinking agent U, and the use of crosslinking agent U may result in compound A being more likely to exist in a nearly uniform state in the composition, which may facilitate improvement in resolution, and may also provide effects such as making the surface condition during application more stable. In the present invention, the urea bond refers to a radical crosslinking agent having at least one selected from the group consisting of *-NR Ｎ —C(═O)—NR Ｎ - is a bond represented by *, and R Ｎ each independently represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom. In the present invention, the urethane bond is *—O—C(═O)—NR Ｎ - is a bond represented by *, and R Ｎ represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom. When the photosensitive resin composition contains crosslinker U, chemical resistance, resolution, etc. may be improved. Crosslinker U may have only one urea bond or urethane bond, may have one or more urea bonds and one or more urethane bonds, may have no urethane bonds and two or more urea bonds, or may have no urea bonds and two or more urethane bonds. The total number of urea bonds and urethane bonds in crosslinker U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2. When crosslinker U does not have a urethane bond, the number of urea bonds in crosslinker U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2. When crosslinker U does not have a urea bond, the number of urethane bonds in crosslinker U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0139] The radical polymerizable group in the crosslinking agent U is not particularly limited, but examples thereof include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, and a maleimide group. A (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group is preferred, and a (meth)acryloxy group is more preferred. When the crosslinking agent U has two or more radical polymerizable groups, the structures of the respective radical polymerizable groups may be the same or different. The number of radical polymerizable groups in the crosslinking agent U may be only one or may be two or more, preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4. The radical polymerizable group value (mass of the compound per mole of radical polymerizable group) in the crosslinking agent U is preferably 150 to 400 g / mol. From the viewpoint of chemical resistance of the cured product, the lower limit of the radical polymerizable group value is more preferably 200 g / mol or more, even more preferably 210 g / mol or more, even more preferably 220 g / mol or more, even more preferably 230 g / mol or more, still more preferably 240 g / mol or more, and particularly preferably 250 g / mol or more. From the viewpoint of developability, the upper limit of the radical polymerizable group value is more preferably 350 g / mol or less, even more preferably 330 g / mol or less, and particularly preferably 300 g / mol or less. In particular, the polymerizable group value of crosslinking agent U is preferably 210 to 400 g / mol, and more preferably 220 to 400 g / mol.

[0140] The crosslinking agent U preferably has a structure represented by the following formula (U-1): In formula (U-1), R Ｕ１ represents a hydrogen atom or a monovalent organic group, and A represents —O— or —NR Ｎ - and R Ｎ is a hydrogen atom or a monovalent organic group, Z Ｕ１ is an m-valent organic group, and Z Ｕ２ is an (n+1)-valent organic group, X is a radical polymerizable group, n is an integer of 1 or more, and m is an integer of 1 or more.

[0141] R Ｕ１ R is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and more preferably a hydrogen atom. Ｎ is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, more preferably a hydrogen atom. Ｕ１ represents a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O) ２ -, -NR Ｎ - or a group in which two or more of these are bonded is preferred, and a hydrocarbon group, or a hydrocarbon group and -O-, -C(=O)-, -S-, -S(=O) ２ - and -NR Ｎ - is more preferred. The hydrocarbon group is preferably a hydrocarbon group having 20 or less carbon atoms, more preferably a hydrocarbon group having 18 or less carbon atoms, and even more preferably a hydrocarbon group having 16 or less carbon atoms. Examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by a combination of these. R Ｎ represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom or a methyl group. Ｕ２ represents a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O) ２ -, -NR Ｎ - or a group in which two or more of these are bonded is preferred, and a hydrocarbon group, or a hydrocarbon group and -O-, -C(=O)-, -S-, -S(=O) ２ - and -NR Ｎ A group bonded to at least one group selected from the group consisting of - is more preferred. Ｕ１Examples of the groups include those listed in 1. and preferred embodiments are also the same. X is not particularly limited, but examples include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, and a maleimide group, with a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group being preferred, and a (meth)acryloxy group being more preferred. n is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, even more preferably 1 or 2, and particularly preferably 1. m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and even more preferably 1 or 2.

[0142] It is also preferable that the crosslinking agent U has at least one of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group. From the viewpoint of the chemical resistance of the resulting cured film, the hydroxy group may be an alcoholic hydroxy group or a phenolic hydroxy group, but an alcoholic hydroxy group is preferred. From the viewpoint of the chemical resistance of the resulting cured film, the alkyleneoxy group is preferably an alkyleneoxy group having 2 to 20 carbon atoms, more preferably an alkyleneoxy group having 2 to 10 carbon atoms, even more preferably an alkyleneoxy group having 2 to 4 carbon atoms, even more preferably an ethyleneoxy group or a propyleneoxy group, and particularly preferably an ethylene group. The alkyleneoxy group may be contained in the crosslinking agent U as a polyalkyleneoxy group. In this case, the number of repeating alkyleneoxy groups is preferably 2 to 10, more preferably 2 to 6. The amide group is represented by -C(=O)-NR Ｎ - refers to a bond represented by R Ｎ When the crosslinking agent U has an amide group, the crosslinking agent U may be, for example, R—C(═O)—NR Ｎ - a group represented by *, or *-C(=O)-NR ＮIt can be contained as a group represented by -R. R represents a hydrogen atom or a monovalent substituent, and is preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group. Crosslinking agent U may have two or more structures selected from the group consisting of a hydroxy group, an alkyleneoxy group (however, when a polyalkyleneoxy group is formed, a polyalkyleneoxy group), an amide group, and a cyano group in the molecule, but an embodiment in which only one structure is present in the molecule is also preferred. The hydroxy group, alkyleneoxy group, amide group, and cyano group may be present at any position in crosslinking agent U, but from the viewpoint of chemical resistance, it is also preferred that at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group is linked to at least one radically polymerizable group contained in crosslinking agent U via a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-1"). In particular, when crosslinking agent U contains only one radically polymerizable group, it is preferred that the radically polymerizable group contained in crosslinking agent U and at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group are linked via a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-2"). When crosslinking agent U contains an alkyleneoxy group (however, when it constitutes a polyalkyleneoxy group, it is a polyalkyleneoxy group) and has the linking group L2-1 or the linking group L2-2, the structure bonded to the side of the alkyleneoxy group (however, when it constitutes a polyalkyleneoxy group, it is a polyalkyleneoxy group) opposite to the linking group L2-1 or the linking group L2-2 is not particularly limited, but is preferably a hydrocarbon group, a radically polymerizable group, or a group represented by a combination thereof. As the hydrocarbon group, a hydrocarbon group having 20 or fewer carbon atoms is preferred, a hydrocarbon group having 18 or fewer carbon atoms is more preferred, and a hydrocarbon group having 16 or fewer carbon atoms is even more preferred. Examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by a combination thereof. Preferred embodiments of the radical polymerizable group are the same as those of the radical polymerizable group in the crosslinking agent U.When crosslinking agent U contains an amide group and has the linking group L2-1 or L2-2, the structure bonded to the side of the amide group opposite the linking group L2-1 or L2-2 is not particularly limited, but is preferably a hydrocarbon group, a radically polymerizable group, or a group represented by a combination thereof. The hydrocarbon group is preferably a hydrocarbon group having 20 or fewer carbon atoms, more preferably a hydrocarbon group having 18 or fewer carbon atoms, and even more preferably a hydrocarbon group having 16 or fewer carbon atoms. Examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by a combination thereof. Preferred aspects of the radically polymerizable group are the same as those of the radically polymerizable group in crosslinking agent U described above. In the above aspect, the carbon atom side of the amide group may be bonded to the linking group L2-1 or L2-2, or the nitrogen atom side of the amide group may be bonded to the linking group L2-1 or L2-2. Among these, from the viewpoints of adhesion to the substrate, chemical resistance, and suppression of Cu voids, it is preferable that crosslinking agent U have a hydroxy group.

[0143] From the viewpoint of compatibility with the specific resin, etc., the crosslinking agent U preferably contains an aromatic group. The aromatic group is preferably directly bonded to a urea bond or urethane bond contained in the crosslinking agent U. When the crosslinking agent U contains two or more urea bonds or urethane bonds, it is preferable that one of the urea bonds or urethane bonds is directly bonded to the aromatic group. The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, or may have a structure in which these form a condensed ring, but is preferably an aromatic hydrocarbon group. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and even more preferably a group in which two or more hydrogen atoms have been removed from a benzene ring structure. The aromatic heterocyclic group is preferably a 5- or 6-membered aromatic heterocyclic group. Examples of the aromatic heterocycle in such an aromatic heterocyclic group include pyrrole, imidazole, triazole, tetrazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, etc. These rings may be condensed with other rings, for example, indole or benzimidazole. The heteroatom contained in the aromatic heterocyclic group is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. The aromatic group is preferably contained in a linking group that links two or more radical polymerizable groups and contains a urea bond or a urethane bond, or a linking group that links at least one selected from the group consisting of the above-mentioned hydroxy group, alkyleneoxy group, amide group, and cyano group to at least one radical polymerizable group contained in the crosslinking agent U.

[0144] The number of atoms (linking chain length) between the urea bond or urethane bond and the radical polymerizable group in crosslinking agent U is not particularly limited, but is preferably 30 or less, more preferably 2 to 20, and even more preferably 2 to 10. When crosslinking agent U contains a total of two or more urea bonds or urethane bonds, when it contains two or more radical polymerizable groups, or when it contains two or more urea bonds or urethane bonds and two or more radical polymerizable groups, the minimum number of atoms (linking chain length) between the urea bond or urethane bond and the radical polymerizable group may be within the above range. In this specification, the "number of atoms (linking chain length) between the urea bond or urethane bond and the polymerizable group" refers to the atomic chain on the path connecting the two atoms or atomic groups to be linked that connects these objects via the shortest distance (minimum number of atoms). For example, in the structure represented by the following formula, the number of atoms (linking chain length) between the urea bond and the radical polymerizable group (methacryloyloxy group) is 2.

[0145] [Axis of symmetry] It is also preferable that the crosslinking agent U is a compound having a structure that does not have an axis of symmetry. The fact that the crosslinking agent U does not have an axis of symmetry means that the crosslinking agent U is a bilaterally asymmetric compound that does not have an axis that would produce a molecule identical to the original molecule by rotating the entire compound. Furthermore, when the structural formula of the crosslinking agent U is written on paper, the fact that the crosslinking agent U does not have an axis of symmetry means that the structural formula of the crosslinking agent U cannot be written in a form that has an axis of symmetry. It is believed that the fact that the crosslinking agent U does not have an axis of symmetry suppresses aggregation of the crosslinking agent U molecules in the composition film.

[0146] [Molecular Weight] The molecular weight of the crosslinking agent U is preferably 100 to 2,000, more preferably 150 to 1,500, and even more preferably 200 to 900.

[0147] The method for producing the crosslinking agent U is not particularly limited, but it can be obtained, for example, by reacting a radical polymerizable compound and a compound having an isocyanate group with a compound having at least one of a hydroxy group and an amino group.

[0148] Specific examples of the crosslinking agent U are shown below, but the crosslinking agent U is not limited to these.

[0149] From the viewpoints of pattern resolution and film stretchability, the photosensitive resin composition preferably uses a bifunctional methacrylate or acrylate. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6- Hexanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, ethylene oxide (EO) adduct diacrylate of bisphenol A, propylene oxide (PO) adduct dimethacrylate of bisphenol A, propylene oxide (PO) adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, and other bifunctional acrylates and bifunctional methacrylates having a urethane bond can be used. Two or more of these can be mixed and used as needed. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a polyethylene glycol chain formula weight of approximately 200. From the viewpoint of suppressing warpage of the pattern (cured product), a monofunctional radical crosslinking agent can preferably be used as the radical crosslinking agent in the photosensitive resin composition of the present invention.Preferred examples of monofunctional radical crosslinking agents include (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate; N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam; and allyl glycidyl ether. Preferred monofunctional radical crosslinking agents include compounds having a boiling point of 100°C or higher under normal pressure in order to suppress volatilization before exposure. Other examples of bifunctional or higher radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0150] When a radical crosslinking agent is contained, the content of the radical crosslinking agent is preferably more than 0% by mass and not more than 60% by mass, more preferably 5% by mass or more, and more preferably 50% by mass or less, and even more preferably 30% by mass or less, based on the total solid content of the photosensitive resin composition.

[0151] The radical crosslinking agent may be used alone or in combination of two or more. When two or more types are used in combination, the total amount thereof is preferably within the above range.

[0152] [Other Crosslinking Agents] The photosensitive resin composition of the present invention preferably contains another crosslinking agent different from the radical crosslinking agent described above. The other crosslinking agent refers to a crosslinking agent other than the radical crosslinking agent described above. It is preferably a compound having multiple groups in its molecule that promote the reaction of forming a covalent bond with other compounds in the composition or their reaction products upon exposure to light by the photoacid generator or photobase generator described above. It is preferable that the compound have multiple groups in its molecule that promote the reaction of forming a covalent bond with other compounds in the composition or their reaction products under the action of an acid or base. The acid or base is preferably an acid or base generated from a photoacid generator or photobase generator during the exposure step. Examples of other crosslinking agents include the compounds described in paragraphs 0179 to 0207 of WO 2022 / 145355. The above descriptions are incorporated herein by reference.

[0153] [Polymerization initiator] The photosensitive resin composition of the present invention preferably contains a polymerization initiator. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable to contain a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible region is preferred. Alternatively, the photosensitive resin composition may be an activator that reacts with a photoexcited sensitizer to generate active radicals.

[0154] The photoradical polymerization initiator has a capacity of at least about 50 L·mol within a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). －１ ・cm －１ The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to measure the molar absorption coefficient using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g / L using ethyl acetate as a solvent.

[0155] Any known compound can be used as the photoradical polymerization initiator. Examples include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organic boron compounds, and iron arene complexes. For details of these compounds, please refer to paragraphs

[0165] to

[0182] of JP 2016-027357 A and paragraphs

[0138] to

[0151] of WO 2015 / 199219 A, the contents of which are incorporated herein by reference. Further, paragraphs 0065 to 0111 of JP 2014-130173 A, compounds described in Japanese Patent No. 6301489, MATERIAL STAGE 37 to 60p, vol. 19, No. 3,2019 described peroxide-based photopolymerization initiators, photopolymerization initiators described in WO 2018 / 221177, photopolymerization initiators described in WO 2018 / 110179, photopolymerization initiators described in JP 2019-043864 A, photopolymerization initiators described in JP 2019-044030 A, peroxide-based initiators described in JP 2019-167313 A can be mentioned, the contents of which are incorporated herein by reference.

[0156] Examples of ketone compounds include the compounds described in paragraph 0087 of JP 2015-087611 A, the contents of which are incorporated herein by reference. As a commercially available product, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

[0157] In one embodiment of the present invention, a hydroxyacetophenone compound, an aminoacetophenone compound, or an acylphosphine compound can be suitably used as the photoradical polymerization initiator. More specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 or an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, the contents of which are incorporated herein by reference.

[0158] Examples of α-hydroxyketone initiators that can be used include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF).

[0159] Examples of α-aminoketone initiators that can be used include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins B.V.), and IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF).

[0160] As the aminoacetophenone initiator, acylphosphine oxide initiator, and metallocene compound, for example, compounds described in paragraphs 0161 to 0163 of WO 2021 / 112189 can also be suitably used. The contents of this specification are incorporated herein by reference.

[0161] As the photoradical polymerization initiator, an oxime compound is more preferably used. Use of an oxime compound makes it possible to more effectively improve the exposure latitude. An oxime compound is particularly preferred because it has a wide exposure latitude (exposure margin) and also functions as a photocuring accelerator. In addition, compound A has high compatibility with the oxime compound, and use of the oxime compound may facilitate compound A to exist in a nearly uniform state in the composition, thereby facilitating improved resolution, and may also provide other effects such as making the surface condition during application smooth.

[0162] Specific examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), compounds described in J. C. S. Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232) described compounds, compounds described in JP-A-2000-066385, compounds described in JP-T-2004-534797, compounds described in JP-A-2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in WO 2015 / 152153, compounds described in WO 2017 / 051680, compounds described in JP-A-2017-198865, compounds described in paragraphs 0025 to 0038 of WO 2017 / 164127, compounds described in WO 2013 / 167515 and the like, the contents of which are incorporated herein.

[0163] Preferred oxime compounds include, for example, compounds having the following structure: 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one. In photosensitive resin compositions, it is particularly preferred to use an oxime compound as a photoradical polymerization initiator. The oxime compound as a photoradical polymerization initiator has a linking group of >C=N-O-C(=O)- in the molecule.

[0164]

[0165] Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (manufactured by BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in JP 2012-014052 A), TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA ARCLES NCI-730, NCI-831, and ADEKA ARCLES NCI-930 (manufactured by ADEKA Corporation), DFI-091 (manufactured by Daito ChemiX Co., Ltd.), and SpeedCure PDO (SARTOMER Also, an oxime compound having the following structure can be used.

[0166] Examples of photoradical polymerization initiators include oxime compounds having a fluorene ring, oxime compounds having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring, and oxime compounds having a fluorine atom, as described in paragraphs 0169 to 0171 of WO 2021 / 112189. Also usable are oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds in which a substituent having a hydroxy group is bonded to a carbazole skeleton, as described in paragraphs 0208 to 0210 of WO 2021 / 020359. The contents of these compounds are incorporated herein by reference.

[0167] In addition, compounds described in paragraphs 0113 to 0117 of JP-A No. 2023-058585 can also be used as the photopolymerization initiator, the disclosure of which is incorporated herein by reference.

[0168] When the photosensitive resin composition contains a photopolymerization initiator, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass, based on the total solid content of the photosensitive resin composition. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more types of photopolymerization initiators are contained, the total amount is preferably within the above range. Note that the photopolymerization initiator may also function as a thermal polymerization initiator, and therefore crosslinking by the photopolymerization initiator may be further promoted by heating in an oven, hot plate, or the like.

[0169] [Sensitizer] The photosensitive resin composition may contain a sensitizer. The sensitizer absorbs specific actinic radiation and becomes electronically excited. The electronically excited sensitizer comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and undergoes electron transfer, energy transfer, heat generation, and other actions. This causes the thermal radical polymerization initiator or the photoradical polymerization initiator to undergo a chemical change and decompose, generating a radical, acid, or base. Usable sensitizers include benzophenone-based, Michler's ketone-based, coumarin-based, pyrazole azo-based, anilino azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, and indigo-based compounds.Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylideneindanone, p-dimethylaminobenzylideneindanone, and Non, 2-(p-dimethylaminophenylbiphenylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin Phosphorus, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (ethyl 7-(diethylamino)coumarin-3-carboxylate), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate Examples of sensitizing dyes include soamyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, and 3',4'-dimethylacetanilide. Other sensitizing dyes may also be used. For details of sensitizing dyes, please refer to the descriptions in paragraphs 0161 to 0163 of JP-A-2016-027357, the contents of which are incorporated herein by reference.

[0170] When the photosensitive resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20 mass %, more preferably 0.1 to 15 mass %, and still more preferably 0.5 to 10 mass %, based on the total solid content of the photosensitive resin composition. The sensitizer may be used alone or in combination of two or more types.

[0171] [Chain Transfer Agent] The photosensitive resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pages 683-684. Examples of chain transfer agents include those having -S-S-, -SO ２ Examples of compounds that can be used include compounds having -S-, -N-O-, SH, PH, SiH, and GeH, and dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthate compounds having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These compounds can donate hydrogen to low-activity radicals to generate radicals, or can be oxidized and then deprotonated to generate radicals. Thiol compounds are particularly preferred.

[0172] In addition, the chain transfer agent may be a compound described in paragraphs 0152 to 0153 of WO 2015 / 199219, the contents of which are incorporated herein by reference.

[0173] When the photosensitive resin composition contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the total solid content of the photosensitive resin composition. Only one type of chain transfer agent may be used, or two or more types may be used. When two or more types of chain transfer agents are used, the total content thereof is preferably within the above range.

[0174] In another preferred embodiment of the present invention, the photosensitive resin composition of the present invention contains two or more polymerization initiators. Specifically, the photosensitive resin composition of the present invention preferably contains a photopolymerization initiator and a thermal polymerization initiator described below, or the photoradical polymerization initiator and a photoacid generator described above.

[0175] By including a photopolymerization initiator and a thermal polymerization initiator described below, pattern formation by exposure becomes possible, and radical polymerization also proceeds more easily during curing by a heating step described below, which may improve performance such as chemical resistance. When a photopolymerization initiator and a thermal polymerization initiator described below are included, the content 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.

[0176] 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 relative to the total content of the photopolymerization initiator and the photoacid generator is preferably 20 to 70 mass %, more preferably 30 to 60 mass %.

[0177] [Thermal Polymerization Initiator] Examples of the thermal polymerization initiator include a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or promotes the polymerization reaction of a polymerizable compound. Addition of a thermal radical polymerization initiator can also promote the polymerization reaction of the resin and the polymerizable compound, thereby further improving solvent resistance.

[0178] Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated herein by reference.

[0179] When a thermal polymerization initiator is contained, the content thereof is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, and even more preferably 0.5 to 15 mass %, relative to the total solid content of the photosensitive resin composition. The photosensitive resin composition may contain only one type of thermal polymerization initiator, or may contain two or more types. When two or more types of thermal polymerization initiators are contained, the total amount is preferably in the above range.

[0180] <Base Generator> The resin composition of the present invention may contain a base generator. Here, the base generator is a compound capable of generating a base by physical or chemical action. Preferred base generators include thermal base generators and photobase generators. In particular, when the resin composition contains a polyimide precursor, the resin composition preferably contains a base generator. By containing a thermal base generator in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties and chemical resistance of the cured product can be improved, resulting in excellent performance as an interlayer insulating film for a rewiring layer included in a semiconductor package. The base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines. The base generator is not particularly limited, and known base generators can be used. Examples of known base generators include carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, α-lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, and acyloxyimino compounds. Specific examples of non-ionic base generators include the compounds described in paragraphs 0249 to 0275 of WO 2022 / 145355. The above descriptions are incorporated herein by reference.

[0181] Examples of the base generator include, but are not limited to, the following compounds:

[0182]

[0183] 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.

[0184] Specific preferred compounds for the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of WO 2018 / 038002.

[0185] Specific examples of ammonium salts include, but are not limited to, the following compounds:

[0186] Specific examples of iminium salts include, but are not limited to, the following compounds:

[0187] The base generator is preferably an amine in which the amino group is protected with a t-butoxycarbonyl group, from the viewpoints of storage stability and generating a base by deprotection during curing.

[0188] Examples of amine compounds protected by a t-butoxycarbonyl group include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, and 2-amino-1,3-propanediol. alcohol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzyl alcohol, diethanolamine diamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidyl)-2-propanol, 1,4-butanolbis(3-aminopropyl)ethanol ter, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybis(ethylamine), 1,14-diamino-3,6,9,12-tetraoxatetradecane, 1-aza-15-crown-5-ether, diethylene glycol bis(3-aminopropyl)ether, 1,11-diamino-3,6,9-trioxaundecane, or compounds in which the amino group of an amino acid or a derivative thereof is protected with a t-butoxycarbonyl group, but are not limited to these.

[0189] When the resin composition contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass per 100 parts by mass of the resin in the resin composition. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less. One or more types of base generators can be used. When two or more types are used, the total amount is preferably within the above range.

[0190] <Solvent> The photosensitive resin composition of the present invention preferably contains a solvent. Any known solvent can be used as the solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0191] Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, γ-valerolactone, alkyl alkyloxyacetates (for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionic acid alkyl esters (for example, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters ...alkyloxypropionate, ethyl 3-alkyloxypropionate, 2-alkyloxypropionic acid alkyl esters (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (for example, methyl 3-alkyloxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (for example, methyl 3- Preferred examples thereof include alkyl esters of alkyloxypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, and diethyl malonate.

[0192] Suitable examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0193] Suitable examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0194] Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0195] A preferred example of the sulfoxides is dimethyl sulfoxide.

[0196] Preferred examples of the amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0197] Preferred examples of ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0198] Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.

[0199] From the viewpoint of improving the properties of the coated surface, it is also preferable to mix two or more kinds of solvents.

[0200] In the present invention, one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, levoglucosenone, and dihydrolevoglucosenone, or a mixed solvent composed of two or more solvents, is preferred. Particularly preferred are a combination of dimethyl sulfoxide and γ-butyrolactone, a combination of dimethyl sulfoxide and γ-valerolactone, a combination of 3-methoxy-N,N-dimethylpropionamide and γ-butyrolactone, a combination of 3-methoxy-N,N-dimethylpropionamide, γ-butyrolactone and dimethyl sulfoxide, or a combination of N-methyl-2-pyrrolidone and ethyl lactate. An embodiment in which toluene is further added to these combined solvents in an amount of approximately 1 to 10% by mass, based on the total mass of the solvent, is also a preferred embodiment of the present invention. In particular, from the viewpoint of the storage stability of the photosensitive resin composition, an embodiment in which γ-valerolactone is included as a solvent is also a preferred embodiment of the present invention. In such an embodiment, the content of γ-valerolactone relative to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. The upper limit of the above content is not particularly limited and may be 100% by mass. The content may be determined in consideration of the solubility of the components, such as the specific resin, contained in the photosensitive resin composition.Furthermore, when dimethyl sulfoxide and γ-valerolactone are used in combination, the solvent preferably contains 60 to 90% by mass of γ-valerolactone and 10 to 40% by mass of dimethyl sulfoxide, more preferably 70 to 90% by mass of γ-valerolactone and 10 to 30% by mass of dimethyl sulfoxide, and even more preferably 75 to 85% by mass of γ-valerolactone and 15 to 25% by mass of dimethyl sulfoxide, relative to the total mass of the solvent.

[0201] From the viewpoint of coatability, the content of the solvent is preferably an amount such that the total solids concentration of the photosensitive resin composition of the present invention is 5 to 80 mass %, more preferably an amount such that the total solids concentration is 5 to 75 mass %, even more preferably an amount such that the total solids concentration is 10 to 70 mass %, and even more preferably an amount such that the total solids concentration is 20 to 70 mass %. The solvent content may be adjusted depending on the desired thickness of the coating film and the coating method. When two or more solvents are contained, the total content of the solvents is preferably within the above range.

[0202] <Metal Adhesion Improver> The photosensitive resin composition of the present invention preferably contains a metal adhesion improver from the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc. Examples of the metal adhesion improver include a silane coupling agent having an alkoxysilyl group, an aluminum-based adhesion aid, a titanium-based adhesion aid, a compound having a sulfonamide structure, a compound having a thiourea structure, a phosphoric acid derivative compound, a β-ketoester compound, and an amino compound.

[0203] [Silane Coupling Agent] Examples of silane coupling agents include the compounds described in paragraph 0316 of WO 2021 / 112189 and the compounds described in paragraphs 0067 to 0078 of JP 2018-173573 A, the contents of which are incorporated herein by reference. It is also preferable to use two or more different silane coupling agents, as described in paragraphs 0050 to 0058 of JP 2011-128358 A. It is also preferable to use the following compounds as the silane coupling agent. In the formula below, Me represents a methyl group, and Et represents an ethyl group. Furthermore, the following R represents a structure derived from a blocking agent in a blocked isocyanate group. The blocking agent may be selected depending on the desorption temperature, and examples include alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, and active methylene compounds. For example, caprolactam is preferred from the viewpoint of achieving a desorption temperature of 160 to 180°C. Commercially available products of such compounds include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0204]

[0205] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- Examples of suitable silane coupling agents include (aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride. These may be used alone or in combination of two or more. Furthermore, oligomeric compounds having multiple alkoxysilyl groups may also be used as silane coupling agents. Examples of such oligomeric compounds include compounds containing a repeating unit represented by the following formula (S-1): In formula (S-1), R Ｓ１ represents a monovalent organic group, R Ｓ２ represents a hydrogen atom, a hydroxy group or an alkoxy group, and n represents an integer of 0 to 2. Ｓ１is preferably a structure containing a polymerizable group. Examples of the polymerizable group include a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group), a (meth)acrylamide group, and a (meth)acryloyloxy group. A vinylphenyl group, a (meth)acrylamide group, or a (meth)acryloyloxy group is preferred, a vinylphenyl group or a (meth)acryloyloxy group is more preferred, and a (meth)acryloyloxy group is even more preferred. R Ｓ２ is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. n represents an integer of 0 to 2, preferably 1. Here, the structures of the multiple repeating units represented by formula (S-1) contained in the oligomer-type compound may be the same. Here, of the multiple repeating units represented by formula (S-1) contained in the oligomer-type compound, it is preferable that n is 1 or 2 in at least one, more preferably that n is 1 or 2 in at least two, and even more preferably that n is 1 in at least two. Such oligomer-type compounds can be commercially available products, and an example of a commercially available product is KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0206] [Aluminum-Based Adhesion Aid] Examples of aluminum-based adhesion aids include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0207] Other metal adhesion improvers that can be used include the compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP-A-2013-072935, the contents of which are incorporated herein by reference.

[0208] The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the specific resin. By ensuring that the content is equal to or greater than the above lower limit, the adhesion between the pattern and the metal layer is improved, and by ensuring that the content is equal to or less than the above upper limit, the heat resistance and mechanical properties of the pattern are improved. Only one type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above range.

[0209] <Compound X1> The photosensitive resin composition of the present invention may contain compound X1. Compound X1 is a compound having at least one structure selected from the group consisting of a 1,3-dicarbonyl structure and a β-hydroxycarbonyl structure, and having a molecular weight of 1,000 or less. Here, the 1,3-dicarbonyl structure refers to a structure represented by formula (DC-1) below, and the β-hydroxycarbonyl structure refers to a structure represented by formula (HC-1) below.

[0210] In formula (DC-1) or formula (HC-1), * and # each represent a bonding site with another structure. Here, * is preferably a bonding site with a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom. Also, # is preferably a bonding site with a hydrogen atom or a carbon atom. Here, the structure represented by (DC-1) above may be an enol type as shown in formula (DC-2) below. Also, the structure represented by (HC-1) above may be an enol type as shown in formula (HC-2) below. In formula (DC-2) or formula (HC-2), * and # each represent a bonding site to another structure. * is preferably a bonding site to a carbon atom, oxygen atom, nitrogen atom, or sulfur atom. Also, # is preferably a bonding site to a hydrogen atom or carbon atom.

[0211] It is preferable that compound X1 does not contain a metal atom in its structure. The metal atom here does not include metalloid atoms such as silica atoms. Furthermore, it is preferable that compound X1 is not coordinated to a metal atom in the photosensitive resin composition.

[0212] [Molecular Weight] The molecular weight of compound X1 is 1,000 or less, preferably 100 to 500, more preferably 100 to 400, even more preferably 100 to 350, particularly preferably 100 to 300, and even more preferably 100 to 250.

[0213] [Specific Examples] Specific examples of compound X1 include, but are not limited to, compounds having the following structures.

[0214] [Content] The content of compound X1 relative to the total solid content of the photosensitive resin composition of the present invention is preferably 0.01 to 30% by mass. The lower limit is more preferably 0.02% by mass or more, even more preferably 0.05% by mass or more, and particularly preferably 0.10% by mass or more. The upper limit is more preferably 20% by mass or less, even more preferably 10% by mass or less, and particularly preferably 5% by mass or less. An embodiment in which the upper limit is 1% by mass or less is also one of the preferred embodiments of the present invention. One type of compound X1 may be used alone, or two or more types may be used in combination. When two or more types are used in combination, the total amount thereof preferably falls within the above range.

[0215] <Migration Inhibitor> The photosensitive resin composition of the present invention preferably further contains a migration inhibitor. By including a migration inhibitor, for example, when the photosensitive resin composition is applied to a metal layer (or metal wiring) to form a film, migration of metal ions derived from the metal layer (or metal wiring) into the film can be effectively inhibited.

[0216] The migration inhibitor is not particularly limited, but examples thereof include compounds having a heterocycle (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring), thioureas and compounds having a sulfanyl group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole are preferably used.

[0217] As the migration inhibitor, an ion trapping agent that traps anions such as halogen ions can also be used.

[0218] Other migration inhibitors include the rust inhibitors described in paragraph 0094 of JP-A-2013-015701, the compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, the compounds described in paragraph 0052 of JP-A-2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of JP-A-2012-194520, and the compounds described in paragraph 0166 of WO 2015 / 199219. The contents of this specification are incorporated herein by reference.

[0219] Specific examples of the migration inhibitor include the following compounds.

[0220]

[0221] When the photosensitive resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass %, more preferably 0.05 to 2.0 mass %, and even more preferably 0.1 to 1.0 mass %, based on the total solid content of the photosensitive resin composition.

[0222] The migration inhibitor may be one kind or two or more kinds. When two or more kinds of migration inhibitors are used, the total amount thereof is preferably within the above range.

[0223] <Polymerization Inhibitor> The photosensitive resin composition of the present invention preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

[0224] Specific examples of the polymerization inhibitor include the compounds described in paragraph 0310 of WO 2021 / 112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenoxazine, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N-dioxide, and the like, the contents of which are incorporated herein by reference.

[0225] When the photosensitive resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20 mass %, more preferably 0.02 to 15 mass %, and even more preferably 0.05 to 10 mass %, relative to the total solid content of the photosensitive resin composition.

[0226] The polymerization inhibitor may be one kind or two or more kinds. When two or more kinds of polymerization inhibitors are used, the total amount thereof is preferably within the above range.

[0227] [Urea Compound, Carbodiimide Compound, Isourea Compound] From the viewpoint of elongation at break and adhesion to a metal or resin layer, the photosensitive resin composition of the present invention may contain at least one compound selected from the group consisting of a compound having a urea bond (urea compound), a compound having a carbodiimide structure (carbodiimide compound), and a compound having an isourea bond (isourea compound) (hereinafter also referred to as "urea compound, etc."). Among these, it is preferable that the photosensitive resin composition of the present invention further contains a compound having a urea bond. The urea compound, etc. referred to here does not include the above-mentioned compound A, the above-mentioned polymerizable compound, or a compound corresponding to a silane coupling agent. Examples of urea compounds include the compounds described in paragraphs 0334 to 0339 of WO 2022 / 070730.

[0228] Specific examples of the urea compound include, but are not limited to, dicyclohexylurea, diisopropylurea, dicyclohexylcarbodiimide, diisopropylcarbodiimide, dicyclohexylisourea, and diisopropylisourea.

[0229] The total content of the urea compounds and the like is preferably 0.1 to 10.0 parts by mass, more preferably 0.5 to 8.0 parts by mass, and even more preferably 1.0 to 6.0 parts by mass, per 100 parts by mass of the specific resin. The urea compounds and the like may be used alone or in combination of two or more types. When two or more types of bases are used in combination in the base-containing treatment liquid, it is preferable that the total content thereof be within the above range.

[0230] <Light absorber> The photosensitive resin composition of the present invention preferably contains a compound (light absorber) whose absorbance at the exposure wavelength decreases upon exposure. The light absorber referred to here does not include compounds corresponding to the above-mentioned compound A. Examples of light absorbers include the compounds described in paragraphs 0159 to 0183 of WO 2022 / 202647 and the compounds described in paragraphs 0088 to 0108 of JP 2019-206689 A. The contents of these compounds are incorporated herein by reference.

[0231] It is also preferable to include a compound having the following structure as the light absorber.

[0232] The content of the light absorber relative to the total solid content of the photosensitive resin composition of the present invention is not particularly limited, but is preferably 0.1 to 20 mass%, more preferably 0.5 to 10 mass%, and even more preferably 1 to 5 mass%.

[0233] <Other Additives> The photosensitive resin composition of the present invention may contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, photoacid generators, anti-aggregation agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliary agents (e.g., antifoaming agents, flame retardants, etc.), as needed, within the scope of achieving the effects of the present invention. By appropriately incorporating these components, properties such as film physical properties can be adjusted. For details of these components, please refer to, for example, the descriptions in paragraphs 0183 and after of JP 2012-003225 A (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812 ), and the descriptions in paragraphs 0101 to 0104 and 0107 to 0109 of JP 2008-250074 A, the contents of which are incorporated herein by reference. When these additives are added, the total content thereof is preferably 3% by mass or less of the solid content of the photosensitive resin composition of the present invention.

[0234] <Characteristics of Photosensitive Resin Composition> The viscosity of the photosensitive resin composition of the present invention can be adjusted by the solid content concentration of the photosensitive resin composition. ２ / s~12,000mm ２ / s is preferred, and 2,000 mm ２ / s~10,000mm ２ / s is more preferable, and 2,500 mm ２ / s~8,000mm ２ Within the above range, it is easy to obtain a highly uniform coating film. ２ If the thickness is more than 12,000 mm / s, it is easy to apply the coating to a thickness required for an insulating film for rewiring, for example. ２If the viscosity is less than 1 / s, a coating film with excellent surface condition can be obtained.

[0235] <Restrictions on substances contained in the photosensitive resin composition> The water content of the photosensitive 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 photosensitive resin composition is improved. Methods for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the container during storage.

[0236] From the viewpoint of insulating properties, the metal content of the photosensitive resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but metals contained as complexes of organic compounds and metals are excluded. When multiple metals are contained, the total amount of these metals is preferably within the above range.

[0237] Furthermore, examples of methods for reducing metal impurities unintentionally contained in the photosensitive resin composition of the present invention include selecting raw materials with a low metal content as raw materials constituting the photosensitive resin composition of the present invention, filtering the raw materials constituting the photosensitive resin composition of the present invention through a filter, and lining the inside of an apparatus with polytetrafluoroethylene or the like to perform distillation under conditions that minimize contamination.

[0238] Considering the use of the photosensitive resin composition of the present invention as a semiconductor material, the content of halogen atoms is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass, from the viewpoint of wiring corrosion. Among these, those present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. The total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is preferably within the above-mentioned ranges. Preferred methods for adjusting the content of halogen atoms include ion exchange treatment.

[0239] A conventionally known container can be used as a container for storing the photosensitive resin composition of the present invention. For the purpose of preventing impurities from being mixed into the raw materials or the photosensitive resin composition of the present invention, it is also preferable to use a multi-layer bottle whose inner wall is made of six types of six layers of resin, or a bottle with a seven-layer structure made of six types of resin. Examples of such containers include the container described in JP 2015-123351 A.

[0240] <Cured Product of Photosensitive Resin Composition> A cured product of the photosensitive resin composition can be obtained by curing the photosensitive resin composition of the present invention. The cured product of the present invention is a cured product obtained by curing the photosensitive resin composition. The photosensitive resin composition is preferably cured by heating, with the heating temperature being more preferably 120°C to 400°C, even more preferably 140°C to 380°C, and particularly preferably 170°C to 350°C. The form of the cured product of the photosensitive resin composition is not particularly limited and can be selected depending on the application, such as a film, rod, sphere, or pellet. In the present invention, the cured product is preferably in the form of a film. By patterning the photosensitive resin composition, the shape of the cured product can be selected depending on the application, such as forming a protective film on a wall surface, forming via holes for electrical conductivity, adjusting impedance, capacitance, or internal stress, or imparting heat dissipation functionality. The film thickness of the cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less. The shrinkage percentage of the photosensitive resin composition of the present invention when cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage percentage refers to the percentage of change in volume of the photosensitive resin composition before and after curing, and can be calculated by the following formula: Shrinkage percentage [%] = 100 - (volume after curing / volume before curing) x 100

[0241] <Characteristics of the cured product of the photosensitive resin composition> The imidization reaction rate of the cured product of the photosensitive 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 breaking elongation of the cured product of the photosensitive 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 photosensitive resin composition of the present invention is preferably 180°C or more, more preferably 210°C or more, and even more preferably 230°C or more.

[0242] <Preparation of Photosensitive Resin Composition> The photosensitive resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and can be carried out by a conventionally known method. Examples of 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, more preferably 15 to 25°C.

[0243] Filtration using a filter is preferably performed to remove foreign matter such as dust and fine particles from the photosensitive resin composition of the present invention. The filter pore size is, for example, preferably 5 μm or less, more preferably 1 μm or less, even more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. When the filter material is polyethylene, HDPE (high-density polyethylene) is more preferable. The filter may be pre-washed with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or parallel. When multiple types of filters are used, filters with different pore sizes or materials may be combined. An example of a connection mode is a mode in which an HDPE filter with a pore size of 1 μm is connected in series as the first stage and an HDPE filter with a pore size of 0.2 μm is connected in series as the second stage. Various materials may also be filtered multiple times. When filtration is performed multiple times, circulating filtration may be used. Filtration may also be performed under pressure. When filtering under pressure, the pressure to be applied is preferably 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, even more preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less. In addition to filtering using a filter, a treatment to remove impurities using an adsorbent may be performed. Filter filtration and a treatment to remove impurities using an adsorbent may be combined. Known adsorbents can be used as the adsorbent. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. After filtering using a filter, the photosensitive resin composition filled in a bottle may be subjected to a degassing step by placing it under reduced pressure.

[0244] (Method for producing a cured product) The method for producing a cured product of the present invention preferably includes a film-forming step of applying a photosensitive resin composition to a substrate to form a film. The method for producing a cured product more preferably includes the film-forming step, an exposure step of selectively exposing the film formed in the film-forming step, and a development step of developing the film exposed in the exposure step using a developer to form a pattern. The method for producing a cured product particularly preferably includes the film-forming step, the exposure step, the development step, and at least one of a heating step of heating the pattern obtained in the development step and a post-development exposure step of exposing the pattern obtained in the development step. The method for producing a cured product also preferably includes the film-forming step and a step of heating the film. Details of each step are described below.

[0245] <Film Forming Step> The photosensitive resin composition of the present invention can be used in a film forming step of applying the composition to a substrate to form a film. The method for producing a cured product of the present invention preferably includes a film forming step of applying the photosensitive resin composition to a substrate to form a film.

[0246] [Substrate] The type of substrate can be appropriately determined depending on the application and is not particularly limited. Examples of substrates include semiconductor production substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metal and substrates on which a metal layer is formed by, for example, plating or vapor deposition), paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, mold substrates, and plasma display panel (PDP) electrode plates. Substrates are particularly preferably semiconductor production substrates, with silicon substrates, Cu substrates, and mold substrates being more preferred. These substrates may have a surface layer such as an adhesion layer or an oxide layer formed by hexamethyldisilazane (HMDS) or the like. The shape of the substrate is not particularly limited and may be circular or rectangular. The size of the substrate is preferably, for example, a diameter of 100 to 450 mm, more preferably 200 to 450 mm, if it is circular. If it is rectangular, the length of the short side is preferably, for example, 100 to 1000 mm, more preferably 200 to 700 mm. As the substrate, for example, a plate-shaped, preferably a panel-shaped substrate (substrate) is used.

[0247] When a film is formed by applying a photosensitive resin composition to the surface of a resin layer (for example, a layer made of a cured product) or the surface of a metal layer, the resin layer or the metal layer serves as the substrate.

[0248] Coating is preferred as a means for applying the photosensitive resin composition to a substrate. Specific application methods include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the viewpoint of film thickness uniformity, spin coating, slit coating, spray coating, and inkjet coating are preferred, and from the viewpoint of film thickness uniformity and productivity, spin coating and slit coating are more preferred. A film of the desired thickness can be obtained by adjusting the solids concentration and coating conditions of the photosensitive resin composition depending on the application method. 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, inkjet coating, etc. are preferred, while for rectangular substrates, slit coating, spray coating, inkjet coating, etc. are preferred. Spin coating can be applied, for example, at a rotation speed of 500 to 3,500 rpm for approximately 10 seconds to 3 minutes. Alternatively, a method can be used in which a coating film formed by applying the coating film to a temporary support in advance using the above-mentioned application method is transferred onto the substrate. Regarding the transfer method, the preparation methods described in paragraphs 0023 and 0036 to 0051 of JP-A No. 2006-023696 and paragraphs 0096 to 0108 of JP-A No. 2006-047592 can be suitably used. A step of removing excess film from the edge of the substrate may also be performed. Examples of such a step include edge bead rinsing (EBR) and back rinsing. A pre-wetting step may also be employed in which various solvents are applied to the substrate before applying the photosensitive resin composition to improve the wettability of the substrate, and then the photosensitive resin composition is applied.

[0249] <Drying Step> After the film-forming step (layer-forming step), the film may be subjected to a step (drying step) of drying the formed film (layer) to remove the solvent. That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film-forming step. The drying step is preferably carried out after the film-forming step and before the exposure step. The drying temperature of the film in the drying step is preferably 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. Drying may also be carried out under reduced pressure. The drying time is, for example, 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.

[0250] <Conversion Step> When the photosensitive resin composition or the film contains compound A represented by formula (A-2), the method may further include a conversion step of converting compound A represented by formula (A-2) to compound A represented by formula (A-1) by heating and exposure to visible light. The conversion step may be carried out simultaneously with the drying step. That is, compound A represented by formula (A-2) may be converted to compound A represented by formula (A-1) by carrying out the drying step in the presence of visible light.

[0251] <Exposure Step> The film may be subjected to an exposure step in which the film is selectively exposed to light. The method for producing a cured product may include an exposure step in which the film formed in the film formation step is selectively exposed to light. Selective exposure means that a portion of the film is exposed to light. Furthermore, selective exposure forms exposed regions (exposed portions) and unexposed regions (unexposed portions) in the film. The exposure dose is not particularly limited as long as it can cure the photosensitive resin composition of the present invention, but for example, it is 50 to 10,000 mJ / cm2 in terms of exposure energy at a wavelength of 365 nm. ２ is preferred, and 200 to 8,000 mJ / cm ２ is more preferred.

[0252] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

[0253] The exposure wavelengths, in relation to the light source, are: (1) semiconductor laser (wavelengths 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.); (2) metal halide lamp; (3) high-pressure mercury lamp, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, and i-line); (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ２ Examples of such light sources include excimer laser (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron beam, and (7) YAG laser second harmonic 532 nm and third harmonic 355 nm. For the photosensitive resin composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferred, and exposure with i-line is more preferred from the viewpoint of exposure sensitivity. The exposure method is not particularly limited as long as at least a part of the film made of the photosensitive resin composition of the present invention is exposed, and examples thereof include exposure using a photomask and exposure by laser direct imaging.

[0254] <Post-Exposure Bake Step> The film may be subjected to a heating step (post-exposure bake step) after exposure. That is, the method for producing a cured product of the present invention may include a post-exposure bake step in which the film exposed in the exposure step is heated. The post-exposure bake step can be carried out after the exposure step and before the development step. The heating temperature in the post-exposure bake step is preferably 50°C to 140°C, more preferably 60°C to 120°C. The heating time in the post-exposure bake step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes. The temperature rise rate in the post-exposure bake step from the temperature at the start of heating to the maximum heating temperature is preferably 1 to 12°C / min, more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. The temperature rise rate may also be changed as appropriate during heating. The heating means in the post-exposure bake step is not particularly limited, and known hot plates, ovens, infrared heaters, etc. may be used. It is also preferable to carry out the heating in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.

[0255] <Development step> The above-mentioned film after exposure may be subjected to a development step in which it is developed using a developer to form a pattern. That is, the method for producing a cured product of the present invention may include a development step in which the film exposed in the exposure step is developed using a developer to form a pattern. By carrying out development, one of the exposed and unexposed parts of the film is removed to form a pattern. Here, development in which the unexposed parts of the film are removed in the development step is called negative development, and development in which the exposed parts of the film are removed in the development step is called positive development.

[0256] [Developer] The developer used in the development step may be an aqueous alkaline solution or a developer containing an organic solvent.

[0257] When the developer is an alkaline aqueous solution, examples of the basic compound that can be contained in the alkaline aqueous solution include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferred are TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine, and more preferred is TMAH. The content of the basic compound in the developer is preferably from 0.01 to 10% by mass, more preferably from 0.1 to 5% by mass, and even more preferably from 0.3 to 3% by mass, based on the total mass of the developer.

[0258] When the developer contains an organic solvent, the organic solvent may be a compound described in paragraph

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

[0259] When the developer contains an organic solvent, the organic solvent may be used alone or in combination. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide is more preferred, and a developer containing cyclopentanone is particularly preferred.

[0260] When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Alternatively, the content may be 100% by mass.

[0261] When the developer contains an organic solvent, the developer may further contain at least one of a basic compound and a base generator. When at least one of the basic compound and the base generator in the developer permeates into the pattern, the performance of the pattern, such as breaking elongation, may be improved.

[0262] As the basic compound, from the viewpoint of reliability when it remains in the film after curing (adhesion to the substrate when the cured product is further heated), an organic base is preferred. As the basic compound, a basic compound having an amino group is preferred, and primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amides, etc. are preferred. However, to promote the imidization reaction, primary amines, secondary amines, tertiary amines, or ammonium salts are preferred, secondary amines, tertiary amines, or ammonium salts are more preferred, secondary amines or tertiary amines are even more preferred, and tertiary amines are particularly preferred. As the basic compound, from the viewpoint of the mechanical properties (elongation at break) of the cured product, it is preferred that it is difficult for the amount remaining to decrease before heating due to vaporization, etc., is preferred. Therefore, the boiling point of the basic compound is preferably 30°C to 350°C at normal pressure (101,325 Pa), more preferably 80°C to 270°C, and even more preferably 100°C to 230°C. The boiling point of the basic compound is preferably higher than the temperature obtained by subtracting 20° C. from the boiling point of the organic solvent contained in the developer, and more preferably higher than the boiling point of the organic solvent contained in the developer. For example, when the boiling point of the organic solvent is 100° C., the boiling point of the basic compound used is preferably 80° C. or higher, and more preferably 100° C. or higher. The developer may contain only one type of basic compound, or may contain two or more types.

[0263] Specific examples of the basic compound include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, butanediamine, 1,5-diamino Examples of the alkyl ester include pentane, N-methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, dimethylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, N,N,N,N-tetramethylethylenediamine, and N,N,N,N-tetramethyl-1,3-propanediamine.

[0264] The preferred embodiments of the base generator are the same as those of the base generator contained in the composition described above. In particular, the base generator is preferably a thermal base generator.

[0265] When the developer contains at least one of a basic compound and a base generator, the content of the basic compound or base generator is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the developer. The lower limit of the content is not particularly limited, but is preferably, for example, 0.1% by mass or more. When the basic compound or base generator is solid in the environment in which the developer is used, the content of the basic compound or base generator is also preferably 70 to 100% by mass, based on the total solid content of the developer. The developer may contain only one type of basic compound or base generator, or two or more types. When two or more types of at least one of the basic compound and base generator are used, the total content thereof is preferably within the above-mentioned range.

[0266] The developer may further contain other components, such as known surfactants and known defoaming agents.

[0267] [Method of Supplying Developer] The method of supplying the developer is not particularly limited as long as it can form the desired pattern, and includes a method of immersing a substrate on which a film has been formed in the developer, puddle development in which the developer is supplied to the film formed on the substrate using a nozzle, and a method of continuously supplying the developer. The type of nozzle is not particularly limited, and examples include a straight nozzle, a shower nozzle, and a spray nozzle. From the viewpoints of the permeability of the developer, the removability of non-image areas, and production efficiency, a method of supplying the developer using a straight nozzle or a method of continuously supplying the developer using a spray nozzle is preferred, and from the viewpoint of the permeability of the developer to the image areas, a method of supplying using a spray nozzle is more preferred. In addition, a process may be adopted in which the developer is continuously supplied using a straight nozzle, the substrate is spun to remove the developer from the substrate, and after spin drying, the developer is continuously supplied again using a straight nozzle, and the substrate is spun to remove the developer from the substrate, or this process may be repeated multiple times. Methods of supplying the developer in the development process include a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept substantially stationary on the substrate, a process in which the developer is vibrated on the substrate using ultrasound or the like, and a combination thereof.

[0268] The development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

[0269] In the developing step, after the treatment with the developer, the pattern may be further washed (rinsed) with a rinse liquid. Alternatively, a method may be employed in which a rinse liquid is supplied before the developer in contact with the pattern is completely dried.

[0270] [Rinse Liquid] When the developer is an alkaline aqueous solution, for example, water can be used as the rinse liquid. When the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (for example, water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinse liquid.

[0271] When the rinse solution contains an organic solvent, examples of the organic solvent include the same organic solvents as those exemplified when the developer contains an organic solvent. The organic solvent contained in the rinse solution is preferably different from the organic solvent contained in the developer, and more preferably an organic solvent that has a lower solubility for the pattern than the organic solvent contained in the developer.

[0272] When the rinse solution contains an organic solvent, the organic solvent may be used alone or in combination of two or more. The organic solvent is preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, or PGME, more preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, or PGME, and even more preferably cyclohexanone or PGMEA.

[0273] When the rinse solution contains an organic solvent, the organic solvent preferably accounts for 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more of the total mass of the rinse solution, and may also account for 100% by mass of the total mass of the rinse solution.

[0274] The rinse solution may contain at least one of a basic compound and a base generator. Although not particularly limited, when the developer contains an organic solvent, an embodiment in which the rinse solution contains the organic solvent and at least one of a basic compound and a base generator is also one of the preferred embodiments of the present invention. Examples of the basic compound and base generator contained in the rinse solution include the compounds exemplified as the basic compound and base generator that may be contained when the developer contains an organic solvent, and the same applies to preferred embodiments. The basic compound and base generator contained in the rinse solution may be selected taking into consideration the solubility in the solvent in the rinse solution, etc.

[0275] When the rinse solution contains at least one of a basic compound and a base generator, the content of the basic compound or base generator is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the rinse solution. The lower limit of the content is not particularly limited, but is preferably 0.1% by mass or more, for example. When the basic compound or base generator is solid in the environment in which the rinse solution is used, the content of the basic compound or base generator is also preferably 70 to 100% by mass, based on the total solid content of the rinse solution. When the rinse solution contains at least one of a basic compound and a base generator, the rinse solution may contain only one type of at least one of the basic compound and the base generator, or may contain two or more types. When at least one of the basic compound and the base generator is two or more types, the total content thereof is preferably within the above-mentioned range.

[0276] The rinse liquid may further contain other components, such as known surfactants and known defoaming agents.

[0277] [Method of Supplying Rinse Liquid] The method of supplying the rinse liquid is not particularly limited as long as it can form a desired pattern, and examples thereof include a method of immersing the substrate in the rinse liquid, a method of supplying the rinse liquid to the substrate by puddling, a method of supplying the rinse liquid to the substrate by showering, and a method of continuously supplying the rinse liquid onto the substrate by means of a straight nozzle or the like. From the viewpoints of the permeability of the rinse liquid, the removability of non-image areas, and production efficiency, methods of supplying the rinse liquid using a shower nozzle, straight nozzle, spray nozzle, etc. are available, and a method of continuously supplying using a spray nozzle is preferred, and from the viewpoint of the permeability of the rinse liquid into the image areas, a method of supplying using a spray nozzle is more preferred. The type of nozzle is not particularly limited, and examples include a straight nozzle, shower nozzle, spray nozzle, etc. That is, the rinsing step is preferably a step of supplying or continuously supplying the rinse liquid to the exposed film using a straight nozzle, and more preferably a step of supplying the rinse liquid using a spray nozzle. The method of supplying the rinse liquid in the rinsing step may include a step of continuously supplying the rinse liquid to the substrate, a step of keeping the rinse liquid substantially stationary on the substrate, a step of vibrating the rinse liquid on the substrate by ultrasonic waves or the like, and a combination of these steps.

[0278] The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinsing liquid during rinsing is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

[0279] The developing step may include a step of contacting the pattern with a treatment liquid after treatment with a developer or after washing the pattern with a rinse liquid. Alternatively, a method may be employed in which the treatment liquid is supplied before the developer or rinse liquid in contact with the pattern is completely dried.

[0280] The treatment liquid may include a treatment liquid containing at least one of water and an organic solvent, and at least one of a basic compound and a base generator. Preferred aspects of the organic solvent, the basic compound, and the base generator are the same as the preferred aspects of the organic solvent, the basic compound, and the base generator used in the rinse liquid described above. The treatment liquid can be supplied to the pattern using the same method as the rinse liquid described above, and preferred aspects are also the same.

[0281] The content of the basic compound or base generator in the treatment liquid is preferably 10% by mass or less, and more preferably 5% by mass or less, relative to the total mass of the treatment liquid. There is no particular limitation on the lower limit of the content, but it is preferably, for example, 0.1% by mass or more. Furthermore, when the basic compound or base generator is solid in the environment in which the treatment liquid is used, the content of the basic compound or base generator is also preferably 70 to 100% by mass, relative to the total solid content of the treatment liquid. When the treatment liquid contains at least one of a basic compound and a base generator, the treatment liquid may contain only one type of at least one of the basic compound and the base generator, or may contain two or more types. When there are two or more types of at least one of the basic compound and the base generator, it is preferable that the total amount thereof is within the above-mentioned range.

[0282] <Heating Step> The pattern obtained in the development step (or the pattern after rinsing, if a rinsing step is performed) may be subjected to a heating step in which the pattern obtained by the development step is heated. That is, the method for producing a cured product of the present invention may include a heating step in which the pattern obtained in the development step is heated. Furthermore, the method for producing a cured product of the present invention may include a heating step in which a pattern obtained by another method without performing a development step, or a film obtained in the film formation step is heated. In the heating step, a resin such as polyimide is cyclized to form a resin such as polyimide. Furthermore, crosslinking of unreacted crosslinkable groups in the specific resin or in a crosslinking agent other than the specific resin also proceeds. The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, even more preferably 150 to 250°C, even more preferably 160 to 250°C, and particularly preferably 160 to 230°C.

[0283] The heating step is preferably a step in which the cyclization reaction of the polyimide precursor is promoted within the pattern by the action of a base or the like generated from the base generator due to heating.

[0284] The heating step is preferably carried out at a temperature increase rate of 1 to 12°C / min from the temperature at the start of heating to the maximum heating temperature. The temperature increase rate is more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. By setting the temperature increase rate to 1°C / min or more, it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity, and by setting the temperature increase rate to 12°C / min or less, it is possible to alleviate residual stress in the cured product. In addition, in the case of an oven capable of rapid heating, it is preferable to increase the temperature from the temperature at the start of heating to the maximum heating temperature at a temperature increase rate of 1 to 8°C / sec, more preferably 2 to 7°C / sec, and even more preferably 3 to 6°C / sec.

[0285] The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the step of heating up to the maximum heating temperature. For example, when the photosensitive resin composition of the present invention is applied to a substrate and then dried, the temperature is the temperature of the film (layer) after this drying, and it is preferable to raise the temperature from, for example, a temperature that is 30 to 200°C lower than the boiling point of the solvent contained in the photosensitive resin composition.

[0286] The heating time (heating time at the maximum heating temperature) is preferably from 5 to 360 minutes, more preferably from 10 to 300 minutes, and even more preferably from 15 to 240 minutes.

[0287] In particular, when forming a multilayer laminate, from the viewpoint of interlayer adhesion, the heating temperature is preferably 30° C. or higher, more preferably 80° C. or higher, even more preferably 100° C. or higher, and particularly preferably 120° C. or higher. The upper limit of the heating temperature is preferably 350° C. or lower, more preferably 250° C. or lower, and even more preferably 240° C. or lower.

[0288] Heating may be performed in stages. For example, the temperature may be increased from 25°C to 120°C at a rate of 3°C / min, held at 120°C for 60 minutes, increased from 120°C to 180°C at a rate of 2°C / min, and held at 180°C for 120 minutes. It is also preferable to treat the film while irradiating it with ultraviolet light, as described in U.S. Pat. No. 9,159,547. Such a pretreatment step can improve the film's properties. The pretreatment step may be performed for a short period of time, preferably from 10 seconds to 2 hours, more preferably from 15 seconds to 30 minutes. The pretreatment step may be performed in two or more steps. For example, a first pretreatment step may be performed in the range of 100 to 150°C, followed by a second pretreatment step in the range of 150 to 200°C. Furthermore, cooling may be performed after heating. In this case, the cooling rate is preferably from 1 to 5°C / min.

[0289] The heating step is preferably carried out in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, or by carrying out the heating step under reduced pressure, in order to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less. The heating means used in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, and an infrared oven.

[0290] <Post-development exposure step> The pattern obtained in the development step (if a rinsing step is performed, the pattern after rinsing) may be subjected to a post-development exposure step in which the pattern obtained in the development step is exposed to light, instead of or in addition to the heating step. That is, the method for producing a cured product of the present invention may include a post-development exposure step in which the pattern obtained in the development step is exposed to light. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step. The post-development exposure step can promote, for example, a reaction in which cyclization of a polyimide precursor or the like progresses due to exposure of a photobase generator, or a reaction in which elimination of an acid-decomposable group progresses due to exposure of a photoacid generator. In the post-development exposure step, it is sufficient that at least a portion of the pattern obtained in the development step is exposed, but it is preferable that the entire pattern is exposed. The exposure dose in the post-development exposure step is 50 to 20,000 mJ / cm in terms of exposure energy at a wavelength to which the photosensitive compound has sensitivity. ２ is preferred, and 100 to 15,000 mJ / cm ２ The post-development exposure step can be carried out using, for example, the light source used in the exposure step described above, and it is preferable to use broadband light.

[0291] <Metal Layer Forming Step> The pattern obtained by the developing step (preferably subjected to at least one of a heating step and a post-development exposure step) may be subjected to a metal layer forming step of forming a metal layer on the pattern. That is, the method for producing a cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on the pattern obtained by the developing step (preferably subjected to at least one of a heating step and a post-development exposure step).

[0292] The metal layer is not particularly limited, and existing metal species can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are more preferred, and copper is even more preferred.

[0293] The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in JP 2007-157879 A, ​​JP 2001-521288 A, JP 2004-214501 A, JP 2004-101850 A, U.S. Patent No. 7,888,181 B2, and U.S. Patent No. 9,177,926 B2 can be used. Examples of suitable methods include photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and combinations of these. More specifically, examples include patterning methods that combine sputtering, photolithography, and etching, and patterning methods that combine photolithography and electroplating. Preferred plating methods include electroplating using a copper sulfate or copper cyanide plating solution.

[0294] The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm, at the thickest part.

[0295] <Applications> Fields to which the method for producing a cured product of the present invention or the cured product can be applied include insulating films for electronic devices, interlayer insulating films for rewiring layers, stress buffer films, etc. Other examples include sealing films, substrate materials (base films, coverlays, and interlayer insulating films for flexible printed circuit boards), and the etching of insulating films for packaging applications such as those described above. For these applications, reference can be made to, for example, Science & Technology Co., Ltd.'s "High Performance Polyimide and Application Technology" (April 2008), edited by Masaaki Kakimoto, CMC Technical Library "Fundamentals and Development of Polyimide Materials" (November 2011), and Japan Polyimide and Aromatic Polymer Research Association's "Latest Polyimide Fundamentals and Applications" (NTS, August 2010).

[0296] The method for producing the cured product of the present invention, or the cured product of the present invention, can also be used for producing printing plates such as offset printing plates or screen printing plates, for etching molded parts, for producing protective lacquers and dielectric layers in electronics, especially microelectronics, etc.

[0297] (Laminate and method for manufacturing laminate) The laminate of the present invention refers to a structure having a plurality of layers each made of the cured product of the present invention. The laminate is a laminate including two or more layers each made of the cured product, and may be a laminate including three or more layers. At least one of the two or more layers each made of the cured product contained in the laminate is a layer made of the cured product of the present invention, and from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product associated with the shrinkage, it is also preferable that all of the layers made of the cured product contained in the laminate are layers made of the cured product of the present invention.

[0298] That is, the method for producing a laminate of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes repeating the method for producing a cured product of the present invention multiple times.

[0299] The laminate of the present invention preferably includes two or more layers made of a cured product and a metal layer between any of the layers made of the cured product. The metal layer is preferably formed by the metal layer-forming step. That is, the method for producing a laminate of the present invention preferably further includes a metal layer-forming step of forming a metal layer on a layer made of a cured product between multiple cured product production processes. A preferred embodiment of the metal layer-forming step is as described above. Examples of the laminate include a laminate having at least a layer structure in which three layers are stacked in this order: a layer made of a first cured product, a metal layer, and a layer made of a second cured product. It is preferred that both the layer made of the first cured product and the layer made of the second cured product are layers made of the cured product of the present invention. The photosensitive resin composition of the present invention used to form the layer made of the first cured product and the photosensitive resin composition of the present invention used to form the layer made of the second cured product may have the same composition or different compositions. The metal layer in the laminate of the present invention is preferably used as metal wiring, such as a rewiring layer.

[0300] <Lamination Step> The method for producing a laminate of the present invention preferably includes a lamination step. The lamination step is a series of steps including performing at least one of (a) a film formation step (layer formation step), (b) an exposure step, (c) a development step, and (d) a heating step and a post-development exposure step again on the surface of the pattern (resin layer) or the metal layer in this order. However, at least one of (a) the film formation step and (d) the heating step and the post-development exposure step may be repeated. Furthermore, after at least one of (d) the heating step and the post-development exposure step, (e) a metal layer formation step may be included. It goes without saying that the lamination step may further include the above-mentioned drying step or the like as appropriate.

[0301] When a further lamination step is performed after the lamination step, a surface activation treatment step may be further performed after the exposure step, the heating step, or the metal layer forming step. An example of the surface activation treatment is a plasma treatment. Details of the surface activation treatment will be described later.

[0302] The lamination step is preferably performed 2 to 20 times, more preferably 2 to 9 times. For example, a structure having 2 to 20 resin layers, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferred, and a structure having 2 to 9 resin layers is even more preferred. Each of the layers may be the same or different in composition, shape, film thickness, etc.

[0303] In the present invention, a particularly preferred embodiment is one in which, after providing a metal layer, a cured product (resin layer) of the photosensitive resin composition of the present invention is further formed so as to cover the metal layer.Specific examples include an embodiment in which the steps of (a) film formation step, (b) exposure step, (c) development step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step are repeated in this order, or an embodiment in which the steps of (a) film formation step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step are repeated in this order.By alternately performing the lamination step of laminating the photosensitive resin composition layer (resin layer) of the present invention and the metal layer formation step, the photosensitive resin composition layer (resin layer) of the present invention and the metal layer can be alternately laminated.

[0304] (Surface Activation Treatment Step) The method for producing a laminate of the present invention preferably includes a surface activation treatment step in which at least a portion of the metal layer and the photosensitive resin composition layer are surface-activated. The surface activation treatment step is usually performed after the metal layer formation step, but after the development step (preferably after at least one of the heating step and the post-development exposure step), the photosensitive resin composition layer may be subjected to a surface activation treatment step 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 photosensitive resin composition layer after exposure, or may be performed on at least a portion of both the metal layer and the photosensitive resin composition layer after exposure. The surface activation treatment is preferably performed on at least a portion of the metal layer, and it is preferable to perform the surface activation treatment on part or all of the region of the metal layer on which the photosensitive resin composition layer is formed on the surface. In this way, by performing the surface activation treatment on the surface of the metal layer, the adhesion with the photosensitive resin composition layer (film) provided on its surface can be improved. The surface activation treatment is also preferably performed on part or all of the photosensitive resin composition layer (resin layer) after exposure. In this way, by performing a surface activation treatment on the surface of the photosensitive resin composition layer, it is possible to improve adhesion with the metal layer or resin layer provided on the surface that has been surface-activated. In particular, when performing negative development, etc., if the photosensitive resin composition layer is cured, it is less susceptible to damage due to the surface treatment and adhesion is likely to be improved. The surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of WO 2021 / 112189. The contents of this document are incorporated herein by reference.

[0305] (Semiconductor device and manufacturing method thereof) The present invention also discloses a semiconductor device comprising the cured product or laminate of the present invention. The present invention also discloses a manufacturing method for a semiconductor device comprising the manufacturing method for the cured product or the manufacturing method for the laminate of the present invention. Specific examples of semiconductor devices using the photosensitive resin composition of the present invention to form an interlayer insulating film for a rewiring layer can be found in paragraphs 0213 to 0218 and FIG. 1 of JP 2016-027357 A, the contents of which are incorporated herein by reference.

[0306] The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

[0307] <Method for producing specific resin> [Synthesis Example 1A: Synthesis of polyimide precursor (resin P-1A)] 27.71 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 18.26 g of bisphthalic dianhydride (BPDA) were placed in a separable flask, and 39.70 g of 2-hydroxyethyl methacrylate (HEMA) and 136.87 g of γ-butyrolactone were added and stirred at room temperature (25°C). 24.66 g of pyridine was added with stirring to obtain a reaction mixture. After the heat generated by the reaction had ceased, the mixture was allowed to cool to room temperature and left to stir for 16 hours. Next, under ice cooling, a solution of 62.48 g of dicyclohexylcarbodiimide (DCC) dissolved in 61.59 g of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by a solution of 27.44 g of 4,4'-diaminodiphenyl ether (DADPE) dissolved in 107.80 g of NMP, which was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 7.17 g of ethyl alcohol was added and stirred for 1 hour, followed by the addition of 136.87 g of γ-butyrolactone. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution. The resulting reaction solution was added to 717.09 g of ethyl alcohol to produce a precipitate consisting of a crude polymer. The resulting crude polymer was filtered off and dissolved in 404.40 g of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 8489.52 g of water to precipitate the polymer, and the resulting precipitate was filtered and then vacuum dried to obtain 80.7 g of powdered resin P-1A. The molecular weight of resin P-1A was measured by gel permeation chromatography (standard polystyrene equivalent) and found to be a weight average molecular weight (Mw) of 28,000. １The structure of Resin P-1A was confirmed by H-NMR to be the structure represented by the following formula (P-1): Furthermore, by appropriately adjusting the equivalent weight of 4,4'-diaminodiphenyl ether, Resins P-1A having Mw of 5,000, 8,000, 10,000, 13,000, 16,000, 18,000, 20,000, 22,000, 30,000, 35,000, 40,000, 50,000, or 80,000 were also synthesized.

[0308] Synthesis Example P-1B: Synthesis of Polyimide Precursor (Resin P-1B) 12.51 g of 4,4'-oxydiphthalic dianhydride (ODPA), 8.24 g of bisphthalic dianhydride (BPDA), 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, and 250 mL of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at 60°C for 4 hours to synthesize a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to -10°C, and 17.0 g of thionyl chloride was added over 60 minutes while maintaining the temperature at -10±5°C. After dilution with 50 mL of N-methylpyrrolidone, a solution of 12.6 g of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture over 60 minutes at -10±5°C, and the mixture was stirred at room temperature for 2 hours. Subsequently, 10.0 g of ethanol was added and stirred at room temperature for 1 hour. Next, 6000 g of water was added to precipitate a polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The precipitate (solid polyimide precursor) after stirring was collected by filtration and dissolved in 500 g of tetrahydrofuran. 6000 g of water (poor solvent) was added to the resulting solution to precipitate a polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The precipitate (solid polyimide precursor) after stirring was again filtered and dried at 45°C under reduced pressure for 3 days. After dissolving 46.6 g of the dried powder in 419.6 g of tetrahydrofuran, 2.3 g of triethylamine was added and stirred at room temperature for 35 minutes. Then, 3,000 g of ethanol was added, and the precipitate was collected by filtration. The obtained precipitate was dissolved in 281.8 g of tetrahydrofuran. 17.1 g of water and 46.6 g of ion exchange resin UP6040 (manufactured by AmberTec) were added thereto, and the mixture was stirred for 4 hours. Thereafter, the ion exchange resin was removed by filtration, and the obtained polymer solution was added to 5,600 g of water to obtain a precipitate. The precipitate was collected by filtration and dried at 45 ° C under reduced pressure for 24 hours, obtaining 45.3 g of resin P-1B. １The structure of Resin P-1B was confirmed by H-NMR to be the structure represented by the following formula (P-1): The molecular weight of Resin P-1B was measured by gel permeation chromatography (standard polystyrene equivalent) to find that the weight average molecular weight (Mw) was 28,000.

[0309] Synthesis Example 2A: Synthesis of Polyimide Precursor (Resin P-2A) Resin P-2A having a structure represented by the following formula (P-2) was synthesized in the same manner as in Synthesis Example 1A, except that the compounds used were changed appropriately. １ By H-NMR, it was confirmed that the structure of Resin P-2A was the structure represented by the following formula (P-2): Mw of Resin P-2A was 28,000.

[0310] [Synthesis Example 2B: Synthesis of Polyimide Precursor (Resin P-2B)] Resin P-2B having a structure represented by the following formula (P-2) was synthesized in the same manner as in Synthesis Example 1B, except that the compounds used were appropriately changed. １ H-NMR confirmed that the structure of Resin P-2B was the structure represented by the following formula (P-2). The Mw of Resin P-2B was 28,000. Furthermore, by appropriately adjusting the equivalent weight of 4,4'-diaminodiphenyl ether, Resin P-2B with an Mw of 20,000 was also synthesized.

[0311] Synthesis Example 12A: Synthesis of polyimide precursor (resin P-12A) Resin P-12A having a structure represented by the following formula (P-12) was synthesized in the same manner as in Synthesis Example 1A, except that the compounds used were changed appropriately. １ By H-NMR, it was confirmed that the structure of Resin 2A was a structure represented by the following formula (P-12): Mw of Resin P-12A was 28,000.

[0312] Synthesis Example 12B: Synthesis of polyimide precursor (resin P-12B) Resin P-12B having a structure represented by the following formula (P-2) was synthesized in the same manner as in Synthesis Example 1B, except that the compounds used were changed appropriately. １ By H-NMR, it was confirmed that the structure of Resin P-12B was a structure represented by the following formula (P-12): Mw of Resin P-12B was 28,000.

[0313] [Synthesis Examples 3 to 11: Synthesis of Polyimide Precursors (Resins P-3 to P-11)] Resins P-3 to P-11, each having a structure represented by any one of the following formulas (P-3) to (P-11), were synthesized in the same manner as in Synthesis Example 1A, except that the compounds used were changed appropriately. The Mw of Resins P-3 to P-11 was all 28,000. １ By H-NMR, it was confirmed that the structures of Resin 3 to Resin 12 were structures represented by the following formulas (P-3) to (P-12), respectively.

[0314] Synthesis Example AA-1: 48.65 g (225 mmol) of 3,3'-dihydroxybenzidine and 375 mL of dimethylformamide were mixed in a flask. Under ice cooling, 98.21 g (450 mmol) of di-t-butyl dicarbonate was added dropwise. After the completion of the dropwise addition, the mixture was stirred at 60°C for 5 hours. After the reaction was completed and the mixture was cooled to room temperature, 35 mg of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 68.68 g (450 mmol) of p-chloromethylstyrene, 74.63 g (540 mmol) of potassium carbonate, and 8.96 g (54.0 mmol) of potassium iodide were added, and the mixture was stirred at 60°C for 3 hours. After the reaction was completed, the mixture was filtered by suction filtration, and the filtrate was added dropwise to 500 mL of water. White crystals precipitated, and the precipitated solid was collected by suction filtration. The obtained white solid was purified by recrystallization using 1000 mL of acetone at 60°C. 125 g (yield 85.6%) of the following intermediate AA-1a was obtained. The structure of AA-1a is shown below. １ This was confirmed by H-NMR spectrum. １ H-NMR (BRUKER, AVANCE NEO 400): δ(ppm,DMSO-d6)8.04-7.94(s,2H), 7.75-7.64(d,2H), 7.56-7.42(m,8H), 7.27-7.20(d,2H), 7.19-7.12(d,2H), 6.79-6.64(2H), 5.89-5.77(2H), 5.30-5.15(6H), 1.49-1.43(s,18H)

[0315] 75.0 g (115.6 mmol) of AA-1a and 500 mL of methylene chloride were mixed in a flask. 131.8 g (1156 mmol) of trifluoroacetic acid was added at room temperature, and then the mixture was stirred at 40°C for 5 hours. After the reaction was completed, 250 mL of methanol was added dropwise under ice cooling, followed by 117.0 g (1156 mmol) of triethylamine. Pale yellow crystals were precipitated, and the precipitated solid was collected by suction filtration. The mixture was suspended and washed in 750 mL of methanol, yielding 40.5 g (73% yield) of (AA-1). The structure of AA-1 is shown below. The following structure is １ This was confirmed by H-NMR spectrum. １ H-NMR (BRUKER, AVANCE NEO 400): δ(ppm,DMSO-d6)7.53-7.45(s,8H), 7.05-6.98(d,2H), 6.92-6.85(d,2H), 6.79-6.63(4H), 5.89-5.78(d,2H), 5.29-5.22(d,2H), 5.20-5.13(s,4H), 4.92-4.64(4H)

[0316] Synthesis Example AT-1 AT-1 was obtained in the same manner as in Synthesis Example AA-1, except that 3,3'-dihydroxybenzidine was replaced with p-methoxyphenol. The structure of AT-1 is shown below. １ This was confirmed by H-NMR spectrum. １ H-NMR (BRUKER, AVANCE NEO 400): δ(ppm,DMSO-d6)7.52-7.42(d,2H), 7.42-7.32(d,2H), 6.80-6.63(3H), 6.54-6.43(d,2H), 5.92-5.77(1H), 5.30-5.19(1H), 4.95-4.89(s,2H), 4.68-4.54(2H)

[0317] Synthesis Example 13: Synthesis of polyimide (resin P-13) 30.0 g (57.64 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride and 0.08 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical were dissolved in 120 g of N-methylpyrrolidone (NMP) to obtain a solution. Next, 9.93 g (24.2 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 10.86 g (24.2 mmol) of AA-1, and 1.30 g (5.76 mmol) of AT-1 were dissolved in 100 g of NMP and added dropwise to the above solution over 1 hour at a temperature of 0 to 10 °C. After stirring at 25 °C for 60 minutes, 18.2 g of pyridine and 14.7 g of acetic anhydride were added and reacted at 80 °C for 4 hours. After completion of the reaction, the mixture was cooled to 25 °C and diluted with 200 g of tetrahydrofuran. Next, the reaction solution was added dropwise to a mixture of 2.0 L of methanol and 0.5 L of water, stirred for 15 minutes, and then the polyimide resin was filtered. Next, the resin was reslurried in 1 L of water, filtered, and then reslurried again in 1 L of methanol, filtered, and dried under reduced pressure at 40 °C for 10 hours. Next, the dried resin was dissolved in 250 g of tetrahydrofuran, and 40 g of ion exchange resin (MB-1: manufactured by Organo Corporation) was added thereto. The mixture was stirred for 4 hours. The ion exchange resin was removed by filtration, and then the polyimide resin was precipitated in 2 L of methanol and stirred for 15 minutes. The polyimide resin was collected by filtration and dried at 45°C under reduced pressure for 1 day to obtain a polyimide resin (resin P-13). The weight average molecular weight of the obtained resin 13 was 28,000. The polyimide (resin P-13) is a resin having a repeating unit represented by the following formula (P-13). The structure of the repeating unit is: １ The molar ratio was determined from the H-NMR spectrum. In the following structure, the subscripts of the repeating units represent the molar ratio of each repeating unit, and this also applies to the following resins.

[0318] [Synthesis Examples 14 to 16: Synthesis of Polyimides (Resins P-14 to P-16)] Resins P-14 to P-16, each having a structure represented by any one of the following formulas (P-14) to (P-16), were synthesized in the same manner as in Synthesis Example P-13, except for appropriately changing the compounds used. The Mw of Resins P-14 to P-16 was all 28,000. １ By H-NMR, it was confirmed that the structures of Resin P-14 to Resin P-16 were structures represented by the following formulas (P-14) to (P-16), respectively.

[0319] Examples and Comparative Examples In each example, the components listed in the table below were mixed to obtain a photosensitive resin composition. In the comparative examples, the components listed in the table below were mixed to obtain a comparative composition. Specifically, the content (amount) of each component listed in the table other than the solvent was the amount (parts by mass) listed in the "Parts by Mass" column of each column in the table. The content (amount) of the solvent was adjusted so that the solids concentration of the composition was the value (% by mass) of "Solids Concentration" in the table, and the ratio (mass ratio) of the content of each solvent to the total mass of the solvent was the ratio listed in the "Ratio" column in the table. The obtained photosensitive resin composition and comparative composition were pressure-filtered using a polytetrafluoroethylene filter with a pore width of 0.8 μm. In the tables, "-" indicates that the composition did not contain the corresponding component.

[0320]

[0321]

[0322]

[0323]

[0324]

[0325]

[0326]

[0327]

[0328]

[0329]

[0330]

[0331] Details of each component listed in the table are as follows:

[0332] 〔resin〕・P-1A, P-1B, P-2A, P-2B, P-3 to P-11, P-12A, P-12B, P-13 to P-16: Resin P-1A, P-1B, P-2A, P-2B, P-3 to P-11, P-12A, P-12B, P-13 to P-16 obtained by the above synthesis example

[0333] [Monomers (polymerizable compounds)] M-1 to M-6: Compounds having the following structures DPHA: Dipentaerythritol hexaacrylate

[0334] [Polymerization initiators] I-1 to I-7: Compounds having the following structures

[0335] [Compound A] A-1 to A-44: Compounds having the following structures. A-1 to A-44 are compounds corresponding to Compound A.

[0336] A-3 was obtained from Tokyo Chemical Industry Co., Ltd. A-1, A-2, A-4 to A-38, and A-40 to A-42 were synthesized with reference to the description in RSC Advances (2021), 11(12), 6662-6666. A-43 was synthesized according to the description in Beilstein Journal of Organic Chemistry (2019), 15, 2753-2764. A-39 and A-44 were synthesized with reference to the description in J. Am. Chem. Soc. 2022, 144, 42, 19430-19436.

[0337] [Base Generator] F-1 to F-5: Compounds having the following structure

[0338] [Polymerization inhibitors] B-1 to B-10: Compounds having the following structures (however, B-5 ​​is a compound that also functions as a migration inhibitor)

[0339] [Silane Coupling Agents (Metal Adhesion Improvers)] C-1 to C-4: Compounds having the following structures.

[0340] [Migration inhibitors] D-1 to D-5: Compounds having the following structure

[0341] [Additives] E-1 to E-6, E-9 to E-14: Compounds having the following structures E-7: Ester of 2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-1,1'-spirobi(1H-indene)-5,5',6,6',7,7'hexanol and 1,2-naphthoquinone-(2)-diazo-5-sulfonic acid E-8: The following synthetic product

[0342] <Additive: Synthesis of Diazonaphthoquinone Compound E-8> 29.72 g (70 mmol) of 4,4'-(1-(2-(4-hydroxyphenyl)-2-propyl)phenyl)ethylidene)bisphenol (Tris-PA, manufactured by Honshu Chemical Industry Co., Ltd.) was added to a flask. Subsequently, 46.93 g (174.9 mmol) of 1,2-naphthoquinone diazide-5-sulfonic acid chloride and 17.9 g of triethylamine were dissolved in 300 g of acetone with stirring, and the solution was added dropwise to the flask using a dropping funnel over 30 minutes, followed by stirring for 30 minutes at an internal temperature of 30°C. Subsequently, hydrochloric acid was added dropwise, and the mixture was stirred for an additional 30 minutes. Next, a solution of 1,640 g of pure water and 30 g of hydrochloric acid was prepared in a beaker, and the filtrate obtained by filtering the hydrochloride salt from the reaction solution was added dropwise to the solution. The precipitate was filtered, washed with water, and vacuum-dried at 40°C for 50 hours to obtain diazonaphthoquinone compound E-8.

[0343] [Solvents] NMP: N-methyl-2-pyrrolidone EL: ethyl lactate DMSO: dimethyl sulfoxide GBL: γ-butyrolactone γ-valerolactone MDMPA: KJCMPA-100 (manufactured by KJ Chemicals Co., Ltd.) toluene: toluene

[0344] <Evaluation> [Evaluation of Resolution] The photosensitive resin composition or comparative composition prepared in each Example and Comparative Example was applied in the form of a layer on a copper substrate by spin coating, respectively, to form a resin composition layer or comparative composition layer. The copper substrate on which the obtained resin composition layer or comparative composition layer was formed was dried on a hot plate at 100°C for 5 minutes, to form a resin composition layer or comparative composition layer on the copper substrate with a uniform thickness as shown in the "Film Thickness (μm)" column in the table. The resin composition layer or comparative composition layer on the copper substrate was then spin-coated at 500 mJ / cm using a stepper as a light source, using a photomask on which a 1:1 line-and-space pattern with 1 μm increments from 5 μm to 25 μm was formed. ２The film was exposed to light having an exposure wavelength (nm) shown in the "Exposure Wavelength (nm)" column of the table, with an exposure energy of 10 ... In examples where "IR" is entered in the "Cure temperature (°C)" column, the resin film obtained in each example was heated at a rate of 10°C / min under a nitrogen atmosphere using an infrared lamp heating device (RTP-6, manufactured by Advance Riko Co., Ltd.). After reaching 230°C, the temperature was maintained for the time indicated in the "Cure time (min)" column in the table, thereby obtaining a cured product. The line pattern of the obtained cured product was observed using a scanning electron microscope (SEM) to determine the minimum line width. Evaluation was performed according to the following evaluation criteria, and the evaluation results are listed in the "Resolution" column in the table. The smaller the minimum line width formed, the better the resolution. Evaluation criteria: A: The minimum line width of the line and space pattern formed was less than 10 μm. B: The minimum line width of the line and space pattern formed was 10 μm or more but less than 20 μm. C: The minimum line width of the line and space pattern formed was 20 μm or more, or no pattern was obtained.

[0345] [Evaluation of Elongation at Break] In each example and comparative example, a cured product was obtained in the same manner as in the "Evaluation of Resolution" above, except that a photomask was used to expose a rectangular region 3 mm wide and 30 mm long. The cured resin composition layer (cured product) was immersed in a 4.9% by mass aqueous solution of hydrofluoric acid, and the cured product was peeled off from the silicon wafer. The longitudinal elongation of the peeled cured product (a test piece having a sample width of 3 mm and a sample length of 30 mm) was measured using a tensile tester (Tensilon) at a crosshead speed of 300 mm / min, 25°C, and 65% RH (relative humidity) in accordance with JIS K 6251:2017. Each measurement was performed five times, and the arithmetic mean value of the elongation at break (elongation at break) of the test piece from the five measurements was used as the index value. Evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in the "Elongation at Break" column in the table. The higher the index value, the better the film strength of the cured product. -Evaluation criteria- A: The index value was 65% or more. B: The index value was 55% or more and less than 65%. C: The index value was less than 55%.

[0346] [Evaluation of Adhesion After Heat Resistance Test] In each Example and Comparative Example, a cured product was obtained in the same manner as in the "Evaluation of Resolution" above, except that a photomask was used so that the exposed area was a 100 μm square area. The copper substrate with the obtained cured product was left in a chamber at 175°C under atmospheric pressure for 192 hours. The shear force of the 100 μm square cured product on the copper substrate was measured using a bond tester (CondorSigma, manufactured by XYZTEC Corporation) in an environment of 25°C and 65% relative humidity (RH), and evaluated according to the following evaluation criteria. The evaluation results are shown in the "Adhesion After Heat Resistance Test" column in the table. The higher the shear force, the better the adhesion of the cured film after the heat resistance test. -Evaluation Criteria- A: The shear force exceeded 30 gf. B: The shear force was greater than 20 gf but not more than 30 gf. C: The shear force was 20 gf or less. Also, 1 gf is 0.00980665 N.

[0347] From the above results, it can be seen that the photosensitive resin composition of the present invention can provide a cured product with excellent resolution. The comparative compositions of Comparative Examples 1 and 2 do not contain a compound corresponding to Compound A. It can be seen that the cured products formed from such comparative compositions have poor resolution.

[0348] Example 201 The photosensitive resin composition used in Example 1 was applied in the form of a layer by spin coating to the surface of a thin copper layer formed on a resin substrate. The layer was then dried at 100°C for 5 minutes to form a 20 μm-thick photosensitive film, which was then exposed using a stepper (Nikon Corporation, NSR1505 i6). The exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-and-space pattern and a line width of 10 μm). After the exposure, the film was developed with cyclopentanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern. The temperature was then increased at a rate of 10°C / min in a nitrogen atmosphere until it reached 230°C, at which point it was maintained at 230°C for 180 minutes to form an interlayer insulating film for a redistribution layer. This interlayer insulating film for a redistribution layer had excellent insulating properties. Furthermore, a semiconductor device was manufactured using this interlayer insulating film for a redistribution layer, and it was confirmed to operate without any problems.

Claims

1. A photosensitive resin composition comprising at least one resin selected from the group consisting of polyimide and a polyimide precursor, and a compound A represented by formula (A-1) or (A-2). In formula (A-1) or (A-2), Ar １ each independently represents an aromatic group which may have a substituent.

2. The photosensitive resin composition according to claim 1, further comprising a photoinitiator and a polymerizable compound.

3. The photosensitive resin composition according to claim 1 or 2, further comprising an organometallic complex.

4. The photosensitive resin composition according to claim 1 or 2, further comprising a base generator.

5. Ar １ The photosensitive resin composition according to claim 1 or 2, wherein at least one of １ is an aromatic group having a phenolic hydroxy group, an alkoxy group or an amino group.

6. The photosensitive resin composition according to claim 1 or 2, wherein Compound A has an aromatic amino group.

7. The photosensitive resin composition according to claim 1 or 2, which is used for forming an interlayer insulating film for a rewiring layer.

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

9. A laminate comprising two or more layers made of the cured product according to claim 8, and comprising a metal layer between any two of the layers made of the cured product.

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

11. The method for producing a cured product according to claim 10, comprising an exposure step of selectively exposing the film and a development step of developing the film with a developer to form a pattern.

12. The method for producing a cured product according to claim 10, comprising a heating step of heating the film at 50 to 450 °C.

13. A method for producing a laminate, comprising the method for producing a cured product according to claim 10.

14. A method for producing a semiconductor device, comprising the method for producing a cured product according to claim 10.

15. A semiconductor device comprising the cured product according to claim 8.

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