Production method for cured product, production method for semiconductor device, processing liquid, and resin composition

Abstract

Provided are: a production method for a cured product including a film-forming step for using a resin composition including a solvent and a polyimide precursor which includes a repeating unit represented by formula (1) on a base material to form a film, a processing step for putting a processing liquid and the film in contact, and a heating step for heating the film after the processing step, wherein the processing liquid includes at least one compound selected from the group consisting of a basic compound and a base generating agent; a production method for a semiconductor device including the cured product; and the processing liquid used in the production method for the cured product.

Description

Method for manufacturing a cured product, method for manufacturing a semiconductor device, treatment liquid, and resin composition

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

[0002] Resins such as polyimide are used in a variety of applications due to their excellent heat resistance and insulating properties. Examples of such applications include, but are not limited to, the use of patterns containing these resins as insulating film or encapsulant materials, or protective films in semiconductor devices for mounting. Furthermore, patterns containing these resins are also used as base films or coverlays for flexible substrates.

[0003] For example, in the above-mentioned applications, a cyclized resin such as polyimide is used in the form of a resin composition containing a precursor of the cyclized resin, such as a polyimide precursor. Such a resin composition can be applied to a substrate, for example, by coating, and then, as necessary, exposed to light, developed, heated, or the like, to form a cured product containing the cyclized resin (e.g., a resin in which a polyimide precursor is imidized) on the substrate. The resin composition can be applied by known coating methods, and can form fine patterns, complex patterns, and the like by development, which means that the cured product has a high degree of freedom in design, and thus has excellent adaptability in manufacturing. In view of the high performance of polyimides and the like, as well as their excellent adaptability in manufacturing, industrial application development of a method for manufacturing a cured product using a resin composition containing a polyimide precursor is increasingly expected.

[0004] For example, Patent Document 1 describes a method for forming a negative image of a polyimide on a substrate, the method comprising the steps of: (a) coating a substrate with a film containing a polyamic acid ester in which an ester substituent has a crosslinkable functional group, and a photoinitiator; (b) imagewise exposing the film to radiation to crosslink the polyamic acid ester; (c) developing the image; (d) contacting the film with a base; and (e) heating the film to imidize the polyamic acid ester.

[0005] Japanese Patent Application Publication No. 6-083049

[0006] In a method for producing a cured product containing polyimide, it is desirable that the resulting cured product have excellent elongation at break and a small coefficient of thermal expansion (coefficient of linear thermal expansion, CTE).

[0007] The present invention aims to provide a method for producing a cured product that provides a cured product with excellent elongation at break and a small CTE, a method for producing a semiconductor device that includes the cured product, a treatment liquid used in the method for producing the cured product, and a resin composition used in the method for producing the cured product.

[0008] Representative embodiments of the present invention are shown below: <1> A method for producing a cured product, comprising: a film-forming step of applying a resin composition containing a polyimide precursor having a repeating unit represented by formula (1) and a solvent onto a substrate to form a film; a treatment step of contacting the film with a treatment liquid; and a heating step of heating the film after the treatment step, wherein the treatment liquid contains at least one compound selected from the group consisting of basic compounds and base generators. In formula (1), R １ and R ２ are each independently a hydrogen atom or a monovalent organic group, and R １ and R ２ At least one of X is a monovalent organic group having an ethylenically unsaturated bond. １ is a group containing a structure represented by the following formula (X-1), and Y １ is a divalent organic group represented by the following general formula (Y-1). In formula (X-1), Ar １ and Ar ２ each independently represents an aromatic ring structure, and X is -CR Ｘ１ ２ -, -C(=CR Ｘ２ ２ ) - or -S(=O) ２ represents -, and R Ｘ１ each independently represents a hydrogen atom, an aromatic hydrocarbon group which may have a substituent, or a hydrocarbon group which may be substituted with a halogen atom, and two R Ｘ１ may be bonded to form a ring structure, and R Ｘ２represents a halogen atom, n represents an integer of 1 or more, m represents an integer of 1 or more, and * represents a bonding site to another structure. In formula (Y-1), R ３ ~R １０ are each independently a hydrogen atom or a monovalent group, and R ３ ~R １０ at least one of R is a fluorine atom, an alkyl group which may have a substituent, a substituent which has a fluorine atom, or an alkoxy group which may have a substituent, ５ and R ７ , R ６ and R ８ may bond to form a ring structure, and * represents a bonding site with the nitrogen atom in formula (1). １ is a structure represented by the following formula (X-2): In formula (X-2), X is -CR Ｘ１ ２ -, -C(=CR Ｘ２ ２ ) - or -S(=O) ２ represents -, and R Ｘ１ each independently represents a hydrogen atom, an aromatic hydrocarbon group which may have a substituent, or a hydrocarbon group which may be substituted with a halogen atom, and two R Ｘ１ may be bonded to form a ring structure, and R Ｘ２ represents a halogen atom, and # represents a bonding site with the carbonyl group in formula (1). １ <4> The method for producing a cured product according to <1>, wherein X in formula (1) has a bisphenol structure including a structure represented by formula (X-1). １ is a structure represented by the following formula (X-3): In formula (X-3), X is -CR Ｘ１ ２ -, -C(=CR Ｘ２ ２ ) - or -S(=O) ２ represents -, and R Ｘ１each independently represents a hydrogen atom, an aromatic hydrocarbon group which may have a substituent, or a hydrocarbon group which may be substituted with a halogen atom, and two R Ｘ１ may be bonded to form a ring structure, and R Ｘ２represents a halogen atom, and # represents a bonding site with the carbonyl group in formula (1). <5> The method for producing a cured product according to any one of <1> to <4>, wherein the base contained in the treatment liquid is a secondary amine or a tertiary amine, and the base generator is a compound that generates a secondary amine or a tertiary amine. <6> The method for producing a cured product according to any one of <1> to <5>, wherein the base and the base generator contained in the treatment liquid are compounds having an amide group. <7> The method for producing a cured product according to any one of <1> to <6>, wherein the base or the base generator contained in the treatment liquid is a compound having an acrylamide group or a methacrylamide group. <8> The method for producing a cured product according to any one of <1> to <7>, wherein the heating temperature in the heating step is 180°C or less, and the heating time is 3 hours or less. <9> The method for producing a cured product according to any one of <1> to <8>, further comprising, between the film-forming step and the treatment step, an exposure step of selectively exposing the film to light, and a development step of developing the exposed film with a developer to form a patterned film. <10> The method for producing a cured product according to <9>, wherein the treatment step is a rinsing step of washing the patterned film with the treatment liquid. <11> The method for producing a cured product according to <9>, wherein the treatment step is carried out after washing the patterned film by contacting it with a rinse liquid. <12> The method for producing a cured product according to any one of <1> to <8>, further comprising, between the film-forming step and the treatment step, an exposure step of selectively exposing the film to light, wherein the treatment step is a step of developing the film using the treatment liquid as a developer to form a patterned film. <13> The method for producing a cured product according to any one of <9> to <12>, wherein the development is negative development. <14> The method for producing a cured product according to any one of <1> to <13>, comprising, after the treatment step and before the heating step, a heating and cooling step of heating the film at a temperature of 80 to 120°C and cooling it. <15> The method for producing a cured product according to any one of <1> to <14>, in which the resin composition contains a photopolymerization initiator. <16> The method for producing a cured product according to any one of <1> to <15>, in which the obtained cured product has a linear thermal expansion coefficient of 50 ppm / K or less in the range of 25°C to 125°C.<17> A method for producing a cured product according to any one of <1> to <16>, wherein the resulting cured product has an elongation at break of 50% or more. <18> A method for producing a cured product according to any one of <1> to <17>, wherein the absolute value of the viscosity change rate, expressed by the following formula, of the viscosity of the resin composition after storage at 23°C for 14 days after preparation relative to the viscosity of the resin composition on the day of preparation is 10% or less: Viscosity change rate (%) = {(viscosity of resin composition on the day of preparation) - (viscosity of resin composition after the storage)} / (viscosity of resin composition on the day of preparation) × 100. <19> A method for producing a semiconductor device, comprising the method for producing a cured product according to any one of <1> to <18>. <20> A treatment liquid used in a method for producing a cured product, the method including: a film-forming step of applying a resin composition containing a polyimide precursor having a repeating unit represented by formula (1) and a solvent onto a substrate to form a film; a treatment step of bringing the film into contact with a treatment liquid; and a heating step of heating the film after the treatment step, the treatment liquid including at least one compound selected from the group consisting of a basic compound and a base generator. In formula (1), R １ and R ２ are each independently a hydrogen atom or a monovalent organic group, and R １ and R ２ At least one of X is a monovalent organic group having an ethylenically unsaturated bond. １ is a group containing a structure represented by the following formula (X-1), and Y １ is a divalent organic group represented by the following general formula (Y-1). In formula (X-1), Ar １ and Ar ２ each independently represents an aromatic ring structure, and X is -CR Ｘ１ ２ -, -C(=CR Ｘ２ ２ ) - or -S(=O) ２ represents -, and R Ｘ１ each independently represents a hydrogen atom, an aromatic hydrocarbon group which may have a substituent, or a hydrocarbon group which may be substituted with a halogen atom, and two R Ｘ１ may be bonded to form a ring structure, and R Ｘ２represents a halogen atom, n represents an integer of 1 or more, m represents an integer of 1 or more, and * represents a bonding site to another structure. In formula (Y-1), R ３ ~R １０ are each independently a hydrogen atom or a monovalent group, and R ３ ~R １０ at least one of R is a fluorine atom, an alkyl group which may have a substituent, a substituent which has a fluorine atom, or an alkoxy group which may have a substituent, ５ and R ７ , R ６ and R ８ may bond to form a ring structure, and * each represents a bonding site with a nitrogen atom in formula (1). <21> A resin composition comprising a polyimide precursor including a repeating unit represented by formula (1), which is used in a method for producing a cured product, the method including a film formation step of applying the resin composition onto a substrate to form a film, a treatment step of bringing the film into contact with a treatment liquid, and a heating step of heating the film after the treatment step, wherein the treatment liquid contains at least one compound selected from the group consisting of a basic compound and a base generator. In formula (1), R １ and R ２ are each independently a hydrogen atom or a monovalent organic group, and R １ and R ２ At least one of X is a monovalent organic group having an ethylenically unsaturated bond. １ is a group containing a structure represented by the following formula (X-1), and Y １ is a divalent organic group represented by the following general formula (Y-1). In formula (X-1), Ar １ and Ar ２ each independently represents an aromatic ring structure, and X is -CR Ｘ１ ２ -, -C(=CR Ｘ２ ２ ) - or -S(=O) ２ represents -, and R Ｘ１ each independently represents a hydrogen atom, an aromatic hydrocarbon group which may have a substituent, or a hydrocarbon group which may be substituted with a halogen atom, and two R Ｘ１may be bonded to form a ring structure, and R Ｘ２ represents a halogen atom, n represents an integer of 1 or more, m represents an integer of 1 or more, and * represents a bonding site to another structure. In formula (Y-1), R ３ ~R １０ are each independently a hydrogen atom or a monovalent group, and R ３ ~R １０ at least one of R is a fluorine atom, an alkyl group which may have a substituent, a substituent which has a fluorine atom, or an alkoxy group which may have a substituent, ５ and R ７ , R ６ and R ８ may bond to form a ring structure, and * represents a bonding site with the nitrogen atom in formula (1).

[0009] According to the present invention, there are provided a method for producing a cured product that provides a cured product with excellent elongation at break and a small CTE, a method for producing a semiconductor device that includes the cured product, a treatment liquid used in the method for producing the cured product, and a resin composition used in the method for producing 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 THF (tetrahydrofuran) as the eluent. However, when THF is not suitable as the eluent, for example, due to low solubility, NMP (N-methyl-2-pyrrolidone) can also be used. Furthermore, unless otherwise specified, detection in GPC measurement is assumed to be performed using a UV (ultraviolet) detector at a wavelength of 254 nm. In this specification, when the positional relationship of each layer constituting a laminate is described as "above" or "below," it is sufficient that another layer is above or below the reference layer among the multiple layers being considered. In other words, a third layer or element may be interposed between the reference layer and the other layer, and the reference layer and the other layer do not need to be in contact with each other. Unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "above." Alternatively, if a resin composition layer is present, the direction from the substrate to the resin composition layer is referred to as "above," and the opposite direction is referred to as "below." Note that such vertical directions are defined for convenience in this specification, and in actual embodiments, the "above" direction in this specification may differ from the vertically upward direction. In this specification, unless otherwise specified, the composition may contain two or more compounds corresponding to each component contained in the composition. Furthermore, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component. In this specification, unless otherwise specified, the temperature is 23° C., the atmospheric pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, a combination of preferred embodiments is a more preferred embodiment.

[0011] (Method for Producing a Cured Product) The method for producing a cured product of the present invention includes a film-forming step of applying a resin composition containing a polyimide precursor having a repeating unit represented by formula (1) and a solvent onto a substrate to form a film, a treatment step of contacting the film with a treatment liquid, and a heating step of heating the film after the treatment step, wherein the treatment liquid contains at least one compound selected from the group consisting of basic compounds and base generators. In formula (1), R １ and R ２ are each independently a hydrogen atom or a monovalent organic group, and R １ and R ２ At least one of X is a monovalent organic group having an ethylenically unsaturated bond. １ is a group containing a structure represented by the following formula (X-1), and Y １ is a divalent organic group represented by the following general formula (Y-1). In formula (X-1), Ar １ and Ar ２ each independently represents an aromatic ring structure, and X is -CR Ｘ１ ２ -, -C(=CR Ｘ２ ２ ) - or -S(=O) ２ represents -, and R Ｘ１ each independently represents a hydrogen atom, an aromatic hydrocarbon group which may have a substituent, or a hydrocarbon group which may be substituted with a halogen atom, and two R Ｘ１ may be bonded to form a ring structure, and R Ｘ２ represents a halogen atom, n represents an integer of 1 or more, m represents an integer of 1 or more, and * represents a bonding site to another structure. In formula (Y-1), R ３ ~R １０ are each independently a hydrogen atom or a monovalent group, and R ３ ~R １０ at least one of R is a fluorine atom, an alkyl group which may have a substituent, a substituent which has a fluorine atom, or an alkoxy group which may have a substituent, ５ and R ７ , R ６ and R ８may bond to form a ring structure, and * represents a bonding site with the nitrogen atom in formula (1).

[0012] The method for producing a cured product of the present invention can provide a cured product with excellent elongation at break and a small CTE. The mechanism by which these effects are achieved is unknown, but is presumed to be as follows.

[0013] The polyimide precursor contains a specific repeating unit represented by formula (1), and thus the elongation at break is improved. １ It is presumed that this is because the repeating unit represented by formula (1) has a structure that is easily bent within the molecular chain. １ Since R has a rigid structure, the rigid structure remains in the final cured product. As a result, the resin also has a rigid structure, which is thought to reduce the thermal expansion coefficient of the resin. In particular, ３ ~R １０ It has been found that when either of the repeating units represented by formula (1) has a fluorine atom or a substituent having a fluorine atom, the thermal expansion coefficient tends to be small. １ and R ２It is believed that the inclusion of an ethylenically unsaturated bond in at least one of the groups promotes polymerization between resins or between a resin and another polymerizable compound, resulting in a low coefficient of thermal expansion. Furthermore, the inclusion of a treatment step allows at least one of a base and a base generator to penetrate into the film. This is believed to promote cyclization of the polyimide precursor during the heating step, resulting in even better elongation at break. Here, since polyimide precursors containing specific repeating units represented by formula (1) have a rigid structure as described above, imidization does not progress easily during curing by heating, and the imidization rate after heating tends to be lower than that of conventional polyimide precursors. Therefore, it is believed that by using a polyimide precursor containing specific repeating units represented by formula (1) and including the above-mentioned treatment step to promote cyclization of the polyimide precursor, the imidization rate after heating can be increased. In particular, when cured at low temperatures (e.g., 180°C or below), the inclusion of the above-mentioned treatment step to promote cyclization is believed to enable sufficient curing (i.e., the imidization rate of the polyimide in the cured product can be improved). In addition, by including the above treatment step, the composition can be made to be free of compounds that generate bases, and therefore it is believed that the storage stability of the composition is also excellent.

[0014] Here, Patent Document 1 does not describe a method for producing a cured product using a resin composition containing a polyimide precursor having a specific repeating unit represented by formula (1) and including a treatment step. The method for producing a cured product of the present invention will be described in detail below.

[0015] The method for producing a cured product of the present invention includes a film-forming step of applying a resin composition containing a polyimide precursor having a repeating unit represented by formula (1) and a solvent onto a substrate to form a film. Details of the resin composition used in the present invention will be described later.

[0016] [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.

[0017] When a film is formed by applying a resin composition to the surface of a resin layer (for example, a layer made of a cured product) or the surface of a metal layer, the resin layer or the metal layer serves as the substrate.

[0018] Coating is preferred as a means for applying the resin composition to a substrate. Specific application methods include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating, or inkjet coating is preferred, and from the viewpoint of uniformity of film thickness and productivity, spin coating and slit coating are more preferred. By adjusting the solid content concentration of the resin composition and coating conditions depending on the application method, a film of the desired thickness can be obtained. In addition, the coating method can be appropriately selected depending on the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, inkjet coating, etc. are preferred, and for rectangular substrates, slit coating, spray coating, inkjet coating, etc. are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. Alternatively, a method can be used in which a coating film formed by applying the coating composition to a temporary support in advance using the above-described application method is transferred onto the substrate. Regarding the transfer method, the preparation methods described in paragraphs 0023 and 0036 to 0051 of JP-A No. 2006-023696 and paragraphs 0096 to 0108 of JP-A No. 2006-047592 can be suitably used. A step of removing excess film from the edge of the substrate may also be performed. Examples of such a step include edge bead rinsing (EBR) and back rinsing. A pre-wetting step may also be employed in which the substrate is coated with various solvents before applying the resin composition to the substrate, improving the wettability of the substrate and then applying the resin composition.

[0019] <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.

[0020] <Treatment Step> The method for producing a cured product of the present invention includes a treatment step of contacting the film with a treatment liquid.

[0021] [Treatment Liquid] The treatment liquid used in the treatment step contains at least one compound selected from the group consisting of a basic compound and a base generator. The treatment liquid of the present invention is also a treatment liquid used in the method of producing a cured product of the present invention.

[0022] The base and base generator contained in the treatment liquid are preferably compounds having an amide group. That is, the treatment liquid preferably contains at least one compound selected from the group consisting of a basic compound having an amide group and a base generator having an amide group. That is, the basic compound is preferably a basic compound having an amide group, and the base generator is preferably a base generator having an amide group. Furthermore, the base and base generator contained in the treatment liquid are preferably compounds having an acrylamide group or a methacrylamide group. That is, the treatment liquid preferably contains at least one compound selected from the group consisting of a basic compound having an acrylamide group or a methacrylamide group, and a base generator having an acrylamide group or a methacrylamide group. Here, from the viewpoint of reducing residue in the cured product, the treatment liquid of the present invention preferably contains a basic compound having a low boiling point and an amide group.

[0023] In the present invention, the amide group is *-NR ＮThe above 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. The * above all represents a bonding site with a carbon atom. The number of amide groups in the basic compound having an amide group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 4, even more preferably 1 or 2, and particularly preferably 1. The number of amide groups in the base generator having an amide group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 4, even more preferably 1 or 2, and particularly preferably 1.

[0024] The basic compound having an amide group preferably contains an acrylamide group or a methacrylamide group as the structure containing the amide group. The base generator having an amide group preferably contains an acrylamide group or a methacrylamide group as the structure containing the amide group. When the base generator having an amide group contains an acrylamide group or a methacrylamide group as the structure containing the amide group, the acrylamide group or the methacrylamide group may be present in the structure that becomes the basic compound to be generated, or may be present in the structure that becomes the residue after the basic compound is generated, but it is preferable that the acrylamide group or the methacrylamide group be present on the side of the basic compound to be generated. By including a basic compound containing an acrylamide or a methacrylamide group or a base generator containing an acrylamide or a methacrylamide group in the treatment liquid, a chemical reaction such as polymerization may occur between the acrylamide or the methacrylamide group and the polymerizable group in the resin or polymerizable compound during the heating step, which may reduce the amount of outgassing from the treatment liquid.

[0025] Furthermore, from the viewpoint of the storage stability of the resin composition and the elongation at break of the resulting cured product, the basic compound is preferably an amine, and more preferably a secondary amine or a tertiary amine. From the viewpoint of the elongation at break of the resulting cured product, the base generator is preferably a compound that generates an amine, and more preferably a compound that generates a secondary amine or a tertiary amine. Here, the term "amine" refers to a compound in which the hydrogen atom of ammonia is substituted with a hydrocarbon group or an aromatic atomic group; if there is one substitution, it is called a primary amine, if there are two substitutions, it is called a secondary amine, and if there are three substitutions, it is called a tertiary amine.

[0026] When the basic compound is an amine, the number of amino groups in the basic compound is not particularly limited, but is preferably 1 to 10, more preferably 1 to 4, even more preferably 1 or 2, and particularly preferably 1. Furthermore, when the basic compound generated from the base generator is an amine, the number of amino groups in the basic compound is not particularly limited, but is preferably 1 to 10, more preferably 1 to 4, even more preferably 1 or 2, and particularly preferably 1.

[0027] -Basic Compound Having Amide Group- The basic compound having an amide group used in the present invention is preferably a compound having a structure represented by the following formula (1-1). In formula (1-1), R １ and R ２ each independently represents a hydrogen atom or a monovalent organic group; R １ and R ２ may bond to form a ring structure, and L １ represents a divalent linking group, L １ and R １ and R ２ may be bonded to at least one of the groups to form a ring structure, and R Ｎ represents a hydrogen atom or a monovalent organic group, R ３ represents a monovalent organic group.

[0028] In formula (1-1), R １ and R ２are each independently preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group. １ and R ２ The number of carbon atoms in the hydrocarbon group or alkyl group in formula (1-1) is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 4. In this specification, when simply referring to a hydrocarbon group, an alkyl group, an alkylene group, etc., it is intended to include any of a linear, branched, cyclic, or a structure represented by a bond thereof. １ and R ２ At least one of R is preferably a monovalent organic group, and it is more preferable that both of R are monovalent organic groups. １ and R ２ may be bonded to form a ring structure. The ring structure formed may be an aromatic ring structure or an aliphatic ring structure. The ring structure formed is preferably a 5-membered ring structure or a 6-membered ring structure. In addition, in formula (1-1), R １ and R ２ It is also possible to use an embodiment in which the groups are not bonded together and do not form a ring structure.

[0029] In formula (1-1), L １ represents a hydrocarbon group, or a hydrocarbon group and —O—, —C(═O)—, —S—, or —SO ２ A group represented by a bond to at least one structure selected from the group consisting of - and -NR- is preferred, and a hydrocarbon group is more preferred. R represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom. However, L １ The bonding sites between L and the two nitrogen atoms are preferably hydrocarbon groups. １ The hydrocarbon group in L is preferably an alkylene group. １ The number of carbon atoms in the hydrocarbon group in L is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 4. １ and R １ and R ２may be bonded to at least one of the following to form a ring structure. The ring structure formed may be an aromatic ring structure or an aliphatic ring structure. The ring structure formed is preferably a 5-membered ring structure or a 6-membered ring structure. In addition, in formula (1-1), L １ and R １ and R ２ An embodiment in which none of the above are bonded to form a ring structure can also be used.

[0030] In formula (1-1), 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.

[0031] In formula (1-1), R ３ represents a monovalent organic group, preferably a hydrocarbon group, more preferably an alkyl group or an alkenyl group. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 4 carbon atoms. The alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 2 to 4 carbon atoms. In particular, R ３ is a vinyl group or a 2-methylvinyl group is also one of the preferred embodiments of the present invention.

[0032] The basic compound having an amide group may also be a polymeric compound. Examples of polymeric compounds that are basic compounds having an amide group include polymeric compounds having a repeating unit having an amide group and an amino group. The amino group is preferably a secondary amino group or a tertiary amino group. Examples of polymeric compounds include polymeric compounds containing a repeating unit represented by the following formula (1-2): In formula (1-2), R １ and R ２ each independently represents a hydrogen atom or a monovalent organic group; R １ and R ２ may bond to form a ring structure, and L １ represents a divalent linking group, L １ and R １ and R ２may be bonded to at least one of the groups to form a ring structure, and R Ｎ represents a hydrogen atom or a monovalent organic group, R ４ represents a hydrogen atom or a monovalent organic group. １ , R ２ , R Ｎ and L １ are R in formula (1-1), respectively. １ , R ２ , R Ｎ and L １ In formula (1-2), R ４ is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group.

[0033] <<Physical Properties>> When the basic compound having an amide group is a low-molecular-weight compound, the molecular weight of the basic compound having an amide group is not particularly limited, but is preferably as small as possible. For example, it is preferably 500 or less, and more preferably 200 or less. Furthermore, when the basic compound having an amide group is a polymeric compound, it is preferably the weight-average molecular weight of the polymeric compound is as small as possible, for example, it is preferably 2,000 or less.

[0034] The boiling point of the basic compound having an amide group at 1 atmosphere is not particularly limited, but is preferably 200°C or lower, more preferably 180°C or lower, and even more preferably 160°C or lower. The melting point of the basic compound having an amide group at 1 atmosphere is not particularly limited, but is preferably a liquid at room temperature (23°C). Furthermore, when the treatment liquid contains a solvent, the boiling point of the basic compound having an amide group at 1 atmosphere is preferably higher than the boiling point of the solvent contained in the treatment liquid at 1 atmosphere minus 20°C, and more preferably higher than the boiling point of the solvent contained in the treatment liquid at 1 atmosphere. For example, when the boiling point of the solvent at 1 atmosphere is 100°C, the boiling point of the basic compound having an amide group at 1 atmosphere is preferably 80°C or higher, and more preferably 100°C or higher. The pKa of the conjugate acid of the basic compound having an amide group is not particularly limited, but is preferably 0 or higher, more preferably 3 or higher, and even more preferably 6 or higher. The upper limit of the pKa of the conjugate acid is not particularly limited, but is preferably 30 or lower. pKa is 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 is a value calculated using ACD / ChemSketch (registered trademark) unless otherwise specified. When the conjugate acid has multiple pKas, it is preferable that at least one of them is within the above range.

[0035] <<Specific Examples>> Examples of basic compounds having an amide group include, but are not limited to, the following compounds.

[0036] -Other Basic Compound- The treatment liquid may contain a basic compound without an amide group (also referred to as "other basic compound"). From the viewpoint of reliability when the other basic compound remains in the film after curing (adhesion to the substrate when the cured product is further heated), an organic base is preferred. Furthermore, as the other 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. From the viewpoint of the mechanical properties (elongation at break) of the cured product, the other basic compound is preferably one that is unlikely to remain in the cured film (the resulting cured product), and from the viewpoint of promoting imidization, it is preferred that the remaining amount is unlikely to decrease before heating due to vaporization, etc. Therefore, the boiling point of the other 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. Furthermore, the boiling point of the other basic compound is preferably higher than the boiling point of the organic solvent contained in the treatment liquid minus 20°C, and more preferably higher than the boiling point of the organic solvent contained in the treatment liquid. 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.

[0037] Specific examples of other basic compounds include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, butanediamine, 1,5-diamino Examples include pentane, N-methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, dimethylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, N,N,N,N-tetramethylethylenediamine, and N,N,N,N-tetramethyl-1,3-propanediamine.

[0038] <<Content>> The content of the basic compound is preferably 10% by mass or less, and more preferably 5% by mass or less, relative to the total mass of the treatment liquid. The lower limit of the content is not particularly limited, but is preferably 0.1% by mass or more. The content of the basic compound can also be 70 to 100% by mass, relative to the total mass of the treatment liquid. The treatment liquid may contain only one type of basic compound, or may contain two or more types. When two or more types of basic compounds are used, the total amount thereof is preferably within the above range.

[0039] -Base Generator Having an Amide Group- As the base generator having an amide group used in the present invention, any of the base generators having an amide group that can be used in the resin composition according to the present invention described below can be used without any particular limitation. Furthermore, the base generator having an amide group may be either a photobase generator or a thermal base generator, but is preferably a thermal base generator.

[0040] <<Physical Properties>> Preferred aspects of the physical properties such as molecular weight, boiling point, melting point, and pKa of the base generated from the base generator having an amide group are the same as the preferred aspects of each physical property of the base having an amide group described above.

[0041] <<Specific Examples>> Examples of the base generator having an amide group include, but are not limited to, the following compounds.

[0042] -Other base generator- The treatment liquid may contain, as the base generator, a base generator that does not have an amide group (also referred to as "other base generator"). As the other base generator, any of the base generators that do not have an amide group that are used in the resin composition according to the present invention, which will be described later, can be used without any particular restrictions. Furthermore, the other base generator may be either a photobase generator or a thermal base generator, but is preferably a thermal base generator.

[0043] <<Content>> The content of the base generator is preferably 10% by mass or less, and more preferably 5% by mass or less, relative to the total mass of the treatment liquid. Furthermore, the content is preferably 0.1% by mass or more. The treatment liquid may contain only one type of base generator, or two or more types. When two or more types of base generators are used, the total content thereof is preferably within the above range.

[0044] -Polymerization Inhibitor- The treatment liquid may further contain a polymerization inhibitor. A preferred embodiment of the present invention is one in which the treatment liquid of the present invention contains at least one compound selected from the group consisting of basic compounds having an acrylamide group or a methacrylamide group and base generators having an acrylamide group or a methacrylamide group, and also contains a polymerization inhibitor. Examples of polymerization inhibitors include, but are not limited to, phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

[0045] Specific compounds of the polymerization inhibitor include p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine cerium salt, N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso 1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenothiazine, phenoxazine, 1,1-diphenyl-2-picrylhydrazyl, dibutyldithiocarbonate copper(II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, and the like are preferably used. In addition, the polymerization inhibitors described in paragraph 0060 of JP 2015-127817 A and the compounds described in paragraphs 0031 to 0046 of WO 2015 / 125469 A can also be used, the contents of which are incorporated herein by reference.

[0046] When the treatment liquid 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 treatment liquid. Only one type of polymerization inhibitor may be used, or two or more types may be used. When two or more types of polymerization inhibitors are used, the total content thereof is preferably within the above range.

[0047] -Solvent- The treatment liquid may contain a solvent. Examples of the solvent include water or an organic solvent, and organic solvents are preferred. Examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate), ethyl ethoxyacetate, etc.), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate) pyruvates (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., and ethers such as diethylene 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 (PGME),Suitable examples of the solvent include propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone; cyclic hydrocarbons such as aromatic hydrocarbons, toluene, xylene, and anisole; and cyclic terpenes such as limonene; sulfoxides such as dimethyl sulfoxide; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol; and amides such as N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide. Furthermore, when the above-mentioned basic compound (e.g., organic base) is liquid in the environment in which the treatment liquid is used, the above-mentioned basic compound can be used as both a solvent and a basic compound.

[0048] Among these, the solvent contained in the treatment liquid preferably contains at least one selected from the group consisting of solvents having an amide group, propylene glycol monomethyl ether acetate, and γ-butyrolactone. Examples of solvents having an amide group include N-methyl-2-pyrrolidone, N-ethylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. The use of such a solvent facilitates the penetration of at least one compound selected from the group consisting of the basic compound and the base generator in the treatment liquid into the coating film, thereby improving the film properties.

[0049] When the treatment liquid contains a solvent, the content of the solvent relative to the total mass of the treatment liquid is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more. Furthermore, when the treatment liquid contains an organic solvent, the content of the organic solvent relative to the total mass of the treatment liquid is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more. The solvent may be one type only, or two or more types. When two or more types of solvents are used, the total content thereof is preferably within the above range.

[0050] Other Components The treatment liquid may further contain other components, such as known surfactants and known defoaming agents.

[0051] It is preferable that the method further includes, between the film-forming step and the treatment step, an exposure step of selectively exposing the film to light and a development step of developing the exposed film with a developer to form a patterned film. Hereinafter, the embodiment in which the film-forming step, exposure step, development step, and treatment step are performed will also be referred to as embodiment A. In embodiment A, the treatment step is a step in which the patterned film obtained by the development step is brought into contact with a treatment solution.

[0052] [Method of Supplying Treatment Liquid] The method of supplying the treatment liquid is not particularly limited as long as it can bring the treatment liquid into contact with the film. Examples include a method of supplying the treatment liquid onto the film obtained in the film-forming process, a method of supplying the treatment liquid onto the film exposed after the exposure process described below, and an embodiment of supplying the treatment liquid onto a patterned film. The supply method is not particularly limited, and includes a method of immersing the substrate in the treatment liquid, supplying the treatment liquid using a puddle (liquid puddle) on the substrate, supplying the treatment liquid onto the substrate by showering, and continuously supplying the treatment liquid onto the substrate using a straight nozzle or other means. From the viewpoints of the permeability of the treatment liquid into the image area, the removability of the non-image area, and manufacturing efficiency, methods of supplying the treatment liquid using a shower nozzle, straight nozzle, spray nozzle, etc. are available. Continuous supply using a nozzle is preferred, and from the viewpoint of the permeability of the treatment liquid into the image area, a method in which the treatment liquid supplied using a nozzle is maintained on the substrate is more preferred. The above-mentioned methods of supplying the treatment liquid (for example, a combination of puddle supply and shower supply, or puddle supply and straight nozzle supply) may be used in combination. For example, paddle supply has the effect of swelling the film, facilitating penetration of the subsequent treatment liquid, while shower supply or spray supply has the effect of improving the removability of non-image areas. Furthermore, the treatment liquid may be used in at least one of the combined methods. Here, in the present invention, a treatment step using a treatment liquid may be performed after supplying a liquid containing neither a basic compound having an amide group nor a base generator having an amide group onto a pattern (for example, after supplying a rinse liquid containing neither a basic compound having an amide group nor a base generator having an amide group onto a patterned film to wash the pattern). In the above embodiment, the method of supplying the treatment liquid containing neither a basic compound having an amide group nor a base generator having an amide group onto a pattern is not particularly limited, but includes supply using a paddle. In the above embodiment, the method of supplying the treatment liquid onto a pattern is not particularly limited, but preferred examples include shower supply and supply using a straight nozzle.By supplying a processing liquid that does not contain either a basic compound having an amide group or a base generator having an amide group using a paddle, the pattern swells, and at least one compound selected from the group consisting of a basic compound having an amide group and a base generator having an amide group in the processing liquid that is supplied later can easily penetrate into the pattern, thereby more easily achieving effects such as improved breaking elongation. Furthermore, supplying the processing liquid using a shower, a straight nozzle, or the like may also provide excellent removability (rinsing ability) of development residue and the like. The processing liquid can be supplied in the processing step using a method that continuously supplies the processing liquid to the substrate, a method that keeps the processing liquid substantially stationary on the substrate, a method that vibrates the processing liquid on the substrate using ultrasonic waves, or a combination thereof. Among these, the processing step is preferably a method in which the processing liquid is supplied to the developed pattern by a wide spray method such as a spray or shower, or a method in which the processing liquid is continuously supplied. It is also preferable that the development in the development step is performed by paddle development, and at least one of the supplying steps of the processing liquid in the processing step is performed by showering or continuous supply using a straight nozzle, or the like. According to the above-described aspect, it is considered that the swelling of the pattern by puddle development makes it easier for at least one compound selected from the group consisting of basic compounds and base generators in the processing solution to penetrate into the pattern, and thus makes it easier to obtain effects such as improved breaking elongation.

[0053] The treatment time in the treatment step (i.e., the time during which the treatment solution is in contact with the pattern) is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the treatment solution during the treatment step is not particularly limited, but is preferably 10 to 45°C, and more preferably 18 to 30°C.

[0054] <Exposure Step> The method for producing a cured product of the present invention may include an exposure step of selectively exposing the film formed in the film formation step. Selective exposure means exposing only a portion of the film. Furthermore, selective exposure forms exposed regions (exposed portions) and unexposed regions (unexposed portions) in the film. The exposure dose is not particularly limited as long as it can cure the resin composition of the present invention, but for example, it may be 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.

[0055] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

[0056] 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 include excimer laser (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron beam, and (7) YAG laser second harmonic 532 nm and third harmonic 355 nm. For the resin composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferred, and exposure with i-line is more preferred from the viewpoint of exposure sensitivity. The exposure method is not particularly limited as long as it is a method that exposes at least a portion of the film made of the resin composition of the present invention, and examples thereof include exposure using a photomask and exposure by laser direct imaging.

[0057] <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. can be used, with heating using a hot plate being preferred. 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.

[0058] <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.

[0059] [Developer] The developer used in the development step may be an aqueous alkaline solution or a developer containing an organic solvent.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] - Basic Compound, Base Generator - In Aspect A, the developer may contain at least one compound selected from the group consisting of a basic compound and a base generator. The treatment solution used in the above-described treatment step may be used as the developer. Another preferred aspect of the present invention is an aspect in which the developer contains neither a basic compound nor a base generator, in order to suppress swelling of the pattern due to the basic compound during development. According to this aspect, variation in pattern shape may be suppressed. Examples of preferred compounds as the at least one compound selected from the group consisting of a basic compound and a base generator include the preferred compounds of the basic compound and base generator contained in the above-described treatment solution.

[0065] The developer may further contain other components, such as known surfactants and known defoaming agents.

[0066] [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.

[0067] 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.

[0068] In the treatment step, the treatment liquid is also preferably a rinse liquid. A rinse liquid is a liquid used to wash a film, for example, a liquid used to wash a patterned film after exposure and development. The treatment step is preferably a rinse step in which the film is washed with the treatment liquid. The rinse step is preferably a rinse step in which the patterned film after the exposure step and development step is washed with the treatment liquid. In the rinse step, a method may be adopted in which the treatment liquid is supplied before the developer in contact with the pattern is completely dried. Specifically, by supplying the treatment liquid onto the patterned film after the development step using the above-mentioned treatment liquid supply method, the patterned film can be washed with the treatment liquid.

[0069] In the above-mentioned Aspect A, it is also preferable to carry out the treatment step after the patterned film obtained in the development step is washed by contacting it with a rinse liquid. That is, it is also preferable that the above-mentioned Aspect A further includes a rinsing step of contacting the patterned film with a rinse liquid between the development step and the treatment step. In the above-mentioned aspect, the rinse liquid may be a composition corresponding to the treatment liquid described above, or may be a rinse liquid that does not contain a base or a compound corresponding to a base generator. In the treatment step, a method may be adopted in which the treatment liquid is supplied before the rinse liquid in contact with the pattern is completely dried.

[0070] Examples of the rinse solution that does not contain a compound corresponding to a base or a base generator include a rinse solution containing an organic solvent. Examples of the organic solvent contained in the rinse solution 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 an organic solvent 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.

[0071] 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.

[0072] 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.

[0073] The rinse liquid may further contain other components, such as known surfactants and known defoaming agents.

[0074] The rinse liquid may be supplied by the same method as the treatment liquid supply method described above.

[0075] Furthermore, it is also preferable that the method for producing a cured product of the present invention includes an exposure step of selectively exposing the film between the film-forming step and the treatment step, and the treatment step is a step of developing the film using the treatment liquid as a developer to form a patterned film. Hereinafter, the mode in which the film-forming step, exposure step, and development step of developing the film using the treatment liquid as a developer to form a patterned film is also referred to as mode B. The exposure step in mode B is the same as the exposure step in mode A, and preferred modes are also the same. The development step in mode B is the same as the development step in mode A, except that a treatment liquid is used as the developer, and preferred modes are also the same. Furthermore, it is preferable that the development in the development step in mode B is negative development.

[0076] In the above-mentioned aspect B, it is also preferable that the method further includes a second treatment step of contacting the patterned film with a second treatment liquid after the treatment step (development step), and that the second treatment liquid contains at least one compound selected from the group consisting of a basic compound and a base generator.Preferred aspects of the second treatment liquid are the same as the preferred aspects of the treatment liquid described above.It is also preferable that the second treatment liquid is a rinse liquid.It is also preferable that the second treatment step is a rinse step of cleaning the patterned film with the treatment liquid.

[0077] <Heating / Cooling Step> After the above treatment step of the present invention, and before the heating step, it is preferable to include a heating / cooling step in which the film is heated to a temperature of 80 to 120°C and cooled. The heating / cooling step can, for example, dry the solvent in the treatment liquid. The heating temperature in the heating / cooling step is preferably 80 to 120°C, and more preferably 90 to 110°C. The heating time in the heating / cooling step is preferably 10 to 300 seconds, and more preferably 30 to 180 seconds. The heating means in the heating / cooling step is not particularly limited, and known hot plates, ovens, infrared heaters, etc. can be used, with heating using a hot plate being preferred. It is also preferable to perform heating in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.

[0078] The temperature of the film after cooling in the heating and cooling step is, for example, preferably 10 to 50°C, and more preferably 15 to 40°C. The cooling means is not particularly limited and any known cooling means can be used, including natural cooling (natural heat dissipation) and cooling using a known cooling device such as a device using a Peltier element. It is also preferable to perform cooling in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.

[0079] <Heating Step> The method for producing a cured product of the present invention includes a heating step in which the pattern obtained in the development step is heated. The method for producing a cured product of the present invention may also include a heating step in which a pattern obtained by another method without performing the development step, or a film obtained in the film formation step is heated. In the heating step, resins such as polyimide precursors are cyclized to form resins such as polyimides. Crosslinking of unreacted crosslinkable groups in the specific resin or in a crosslinking agent other than the specific resin also occurs. 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. In particular, an embodiment in which the heating temperature in the heating step is 180°C or less and the heating time is 3 hours or less is also preferred. In the above embodiment, the lower the heating temperature, the better from the viewpoint of suppressing deformation of the substrate, etc., but from the viewpoint of the imidization rate of the polyimide in the cured product, it is preferably, for example, 150° C. to 180° C., and more preferably 160° C. to 180° C. Furthermore, the shorter the heating time, the better from the viewpoint of suppressing deformation of the substrate, etc., but from the viewpoint of the imidization rate of the polyimide in the cured product, it is preferably 1 to 3 hours, and more preferably 2 to 3 hours.

[0080] 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.

[0081] 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.

[0082] The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the process of heating up to the maximum heating temperature. For example, when the resin composition of the present invention is applied to a substrate and then dried, the temperature is the temperature of the film (layer) after this drying, and it is preferable to raise the temperature from, for example, a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition.

[0083] 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.

[0084] 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.

[0085] 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 is preferably performed for a short period of time, such as 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps. For example, a first pretreatment step may be performed at a temperature in the range of 100 to 150°C, followed by a second pretreatment step at a temperature in the range of 150 to 200°C. Furthermore, cooling may be performed after heating. In this case, the cooling rate is preferably 1 to 5°C / min.

[0086] 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.

[0087] <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, 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 the exposure of a photobase generator, or a reaction in which elimination of an acid-decomposable group progresses due to the 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.

[0088] <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).

[0089] 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.

[0090] 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.

[0091] The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm, at the thickest part.

[0092] <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).

[0093] 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.

[0094] (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.

[0095] 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.

[0096] The laminate of the present invention preferably includes two or more layers made of a cured product and a metal layer between any of the layers made of the cured product. The metal layer is preferably formed by the metal layer-forming step. That is, the method for producing a laminate of the present invention preferably further includes a metal layer-forming step of forming a metal layer on a layer made of a cured product between multiple cured product production processes. A preferred embodiment of the metal layer-forming step is as described above. Examples of the laminate include a laminate having at least a layer structure in which three layers are stacked in this order: a layer made of a first cured product, a metal layer, and a layer made of a second cured product. It is preferred that both the layer made of the first cured product and the layer made of the second cured product are layers made of the cured product of the present invention. The resin composition of the present invention used to form the layer made of the first cured product and the resin composition of the present invention used to form the layer made of the second cured product may have the same composition or different compositions. The metal layer in the laminate of the present invention is preferably used as metal wiring, such as a rewiring layer.

[0097] <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.

[0098] 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.

[0099] 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.

[0100] In the present invention, a particularly preferred embodiment is one in which, after providing a metal layer, a cured product (resin layer) of the resin composition of the present invention is further formed so as to cover the metal layer.Specific examples include an embodiment in which the steps of (a) film formation step, (b) exposure step, (c) development step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step are repeated in this order, or an embodiment in which the steps of (a) film formation step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step are repeated in this order.By alternately performing the lamination step of laminating the resin composition layer (resin layer) of the present invention and the metal layer formation step, the resin composition layer (resin layer) of the present invention and the metal layer can be alternately laminated.

[0101] (Surface Activation Treatment Step) The method for producing a laminate of the present invention preferably includes a surface activation treatment step in which at least a portion of the metal layer and the resin composition layer are surface-activated. The surface activation treatment step is usually performed after the metal layer formation step, but after the development step (preferably after at least one of the heating step and the post-development exposure step), the resin composition layer may be surface-activated before the metal layer formation step. The surface activation treatment may be performed only on at least a portion of the metal layer, or only on at least a portion of the resin composition layer after exposure, or may be performed on at least a portion of both the metal layer and the resin composition layer after exposure. The surface activation treatment is preferably performed on at least a portion of the metal layer, and it is preferable to perform the surface activation treatment on part or all of the region of the metal layer on which the resin composition layer is to be formed. In this way, by performing the surface activation treatment on the surface of the metal layer, adhesion with the resin composition layer (film) provided on the surface can be improved. The surface activation treatment is also preferably performed on part or all of the resin composition layer (resin layer) after exposure. In this way, by performing the surface activation treatment on the surface of the resin composition layer, adhesion with the metal layer or resin layer provided on the surface that has been surface-activated can be improved. In particular, when negative development is performed, when the resin composition layer is cured, it is less susceptible to damage due to surface treatment and adhesion is likely to be improved. The surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of International Publication No. 2021 / 112189. The contents of this specification are incorporated herein by reference.

[0102] (Semiconductor device and manufacturing method thereof) The present invention also discloses a semiconductor device comprising the cured product or laminate of the present invention. The present invention also discloses a manufacturing method for a semiconductor device comprising the manufacturing method for the cured product or the manufacturing method for the laminate of the present invention. Specific examples of semiconductor devices using the resin composition of the present invention to form an interlayer insulating film for a rewiring layer can be found in paragraphs 0213 to 0218 and FIG. 1 of JP 2016-027357 A, the contents of which are incorporated herein by reference.

[0103] (Resin Composition) The resin composition is used in the method for producing a cured product of the present invention, the method for producing a laminate of the present invention, or the method for producing a semiconductor device of the present invention.

[0104] <Polyimide Precursor> The resin composition of the present invention contains a polyimide precursor (hereinafter also referred to as "specific resin") containing a repeating unit represented by formula (1). In formula (1), R １ and R ２ are each independently a hydrogen atom or a monovalent organic group, and R １ and R ２ At least one of X is a monovalent organic group having an ethylenically unsaturated bond. １ is a group containing a structure represented by the following formula (X-1), and Y １ is a divalent organic group represented by the following general formula (Y-1). In formula (X-1), Ar １ and Ar ２ each independently represents an aromatic ring structure, and X is -CR Ｘ１ ２ -, -C(=CR Ｘ２ ２ ) - or -S(=O) ２ represents -, and R Ｘ１ each independently represents a hydrogen atom, an aromatic hydrocarbon group which may have a substituent, or a hydrocarbon group which may be substituted with a halogen atom, and two R Ｘ１ may be bonded to form a ring structure, and R Ｘ２ represents a halogen atom, n represents an integer of 1 or more, m represents an integer of 1 or more, and * represents a bonding site to another structure. In formula (Y-1), R ３ ~R １０ are each independently a hydrogen atom or a monovalent group, and R ３ ~R １０ at least one of R is a fluorine atom, an alkyl group which may have a substituent, a substituent which has a fluorine atom, or an alkoxy group which may have a substituent, ５ and R ７ , R ６ and R ８may bond to form a ring structure, and * represents a bonding site with the nitrogen atom in formula (1).

[0105] [R １ and R ２ ] In formula (1), R １ and R ２ are each independently a hydrogen atom or a monovalent organic group, and R １ and R ２ At least one of R is a monovalent organic group having an ethylenically unsaturated bond. １ and R ２ and (III) are monovalent organic groups having an ethylenically unsaturated bond is also a preferred embodiment of the present invention. The monovalent organic group having an ethylenically unsaturated bond is preferably a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group), a (meth)acrylamide group, a group having a (meth)acryloyloxy group, or a group having a group represented by formula (III) below, and more preferably a group having a group represented by formula (III) below. Furthermore, an embodiment in which the monovalent organic group having an ethylenically unsaturated bond is a group represented by formula (III) below is also a preferred embodiment of the present invention.

[0106]

[0107] In formula (III), R ２００ represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, and is preferably a hydrogen atom or a methyl group. In formula (III), * represents a bonding site with another structure. In formula (III), R ２０１ represents an alkylene group having 2 to 12 carbon atoms, —CH ２ CH(OH)CH ２ -, a cycloalkylene group or a polyalkyleneoxy group. ２０１ Examples of the alkylene group include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, and a dodecamethylene group; a 1,2-butanediyl group, a 1,3-butanediyl group; a —CH ２ CH(OH)CH ２alkylene 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, 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.

[0108] In formula (1), R １is a hydrogen atom, or R ２ is a hydrogen atom, the specific resin 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.

[0109] In formula (1), R １ and R ２ The monovalent organic group having no ethylenically unsaturated bond may be a hydrocarbon group, a heterocyclic group, or a combination of at least one of a hydrocarbon group and a heterocyclic group and —O—, —C(═O)—, —S—, or —SO ２ -or-NR Ｎ A group represented by a combination of - and - is preferred, a hydrocarbon group or a group represented by a combination of a hydrocarbon group and -O- is more preferred, and an alkyl group, an aromatic hydrocarbon group, or a polyalkyleneoxy group is more preferred. In this specification, when simply referring to an alkyl group, the alkyl group includes any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group. The same applies to alkylene groups, aliphatic hydrocarbon groups, etc.

[0110] [X １ ] In formula (1), X １ is a group containing a structure represented by the following formula (X-1). In formula (X-1), Ar １ and Ar ２ each independently represents an aromatic ring structure, and X is -CR Ｘ１ ２ -, -C(=CR Ｘ２ ２ ) - or -S(=O) ２ represents -, and R Ｘ１ each independently represents a hydrogen atom, an aromatic hydrocarbon group which may have a substituent, or a hydrocarbon group which may be substituted with a halogen atom, and two R Ｘ１ may be bonded to form a ring structure, and R Ｘ２ represents a halogen atom, n represents an integer of 1 or more, m represents an integer of 1 or more, and * represents a bonding site to another structure.

[0111] In formula (X-1), Ar １ and Ar ２ may be an aromatic hydrocarbon ring structure or an aromatic heterocyclic structure, but is preferably an aromatic hydrocarbon ring structure. The aromatic hydrocarbon ring structure is preferably an aromatic hydrocarbon ring structure having 6 to 20 carbon atoms, more preferably a benzene ring structure or a naphthalene ring structure, and more preferably a naphthalene ring structure. Examples of heteroatoms in the aromatic heterocyclic structure include an oxygen atom, a nitrogen atom, and a sulfur atom, with a nitrogen atom being preferred. The aromatic heterocyclic structure may be a 5-membered ring structure, a 6-membered ring structure, or a ring structure represented by condensation of these, but is preferably a 6-membered ring structure.

[0112] In formula (X-1), X is -CR Ｘ１ ２ -, -C(=CR Ｘ２ ２ ) - or -S(=O) ２ represents -, -CR Ｘ１ ２ - is preferred. Ｘ１ are each independently a hydrogen atom, an aromatic hydrocarbon group which may have a substituent, or a hydrocarbon group which may be substituted with a halogen atom, and it is preferable that at least one of them is a hydrocarbon group which may be substituted with a halogen atom. A preferred example of the aromatic hydrocarbon group which may have a substituent is a phenyl group. Examples of the hydrocarbon group which may be substituted with a halogen atom include an alkyl group and a halogenated alkyl group, and a methyl group or a trifluoromethyl group is more preferable. Two R Ｘ１ may be bonded to form a ring structure, and the ring structure formed is preferably a six-membered ring structure. Ｘ２ represents a halogen atom, preferably a fluorine atom. n represents an integer of 1 or more, preferably 1 to 4, and more preferably 1 or 2. m represents an integer of 1 or more, preferably 1 to 4, and more preferably 1 or 2.

[0113] X in formula (1) １is also preferably a structure represented by the following formula (X-2). In formula (X-2), X is -CR Ｘ１ ２ -, -C(=CR Ｘ２ ２ ) - or -S(=O) ２ represents -, and R Ｘ１ each independently represents a hydrogen atom, an aromatic hydrocarbon group which may have a substituent, or a hydrocarbon group which may be substituted with a halogen atom, and two R Ｘ１ may be bonded to form a ring structure, and R Ｘ２ represents a halogen atom, and # represents a bonding site with the carbonyl group in formula (1). Ｘ１ , R Ｘ２ A preferred embodiment of the formula (X-1) is X, R Ｘ１ , R Ｘ２ This is the same as the preferred embodiment of the above.

[0114] Preferred embodiments of the structure represented by formula (X-2) include, but are not limited to, the following structures: In the following structures, * has the same meaning as # in formula (X-2).

[0115] In addition, from the viewpoint of breaking elongation, X in formula (1) １ Preferably, the compound has a bisphenol structure containing the structure represented by the formula (X-1). １ and Ar ２ is a benzene ring structure, n and m are 1 or more, and Ar １ and Ar ２ and a bisphenol structure formed by directly bonding with —O—.

[0116] In addition, from the viewpoint of breaking elongation, X in formula (1) １ is also preferably a structure represented by the following formula (X-3). In formula (X-3), X is -CR Ｘ１ ２ -, -C(=CR Ｘ２ ２ ) - or -S(=O) ２ represents -, and RＸ１ each independently represents a hydrogen atom, an aromatic hydrocarbon group which may have a substituent, or a hydrocarbon group which may be substituted with a halogen atom, and two R Ｘ１ may be bonded to form a ring structure, and R Ｘ２ represents a halogen atom, and # represents a bonding site with the carbonyl group in formula (1). Ｘ１ , R Ｘ２ A preferred embodiment of the formula (X-1) is X, R Ｘ１ , R Ｘ２ This is the same as the preferred embodiment of the above.

[0117] Specific examples of the structure represented by formula (X-3) are shown below, but the present invention is not limited thereto. In the following structures, * has the same meaning as # in formula (X-3).

[0118] [Y １ 〕 Y １ is a divalent organic group represented by formula (Y-1). From the viewpoint of moisture and heat resistance, R ３ ~R １０ At least one of the groups is preferably an alkyl group, a fluorine atom, or a perfluoroalkyl group, and more preferably a fluorine atom or a trifluoromethyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group. The perfluoroalkyl group is preferably a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a trifluoromethyl group. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and more preferably a methoxy group. In addition, the groups of formula (Y-1)R ５ and R ７ , R ６ and R ８ may be bonded to form a ring structure. The ring structure formed is not particularly limited, but a hydrocarbon ring is preferred. The ring structure formed is preferably a 5-membered ring structure or a 6-membered ring structure, and more preferably a 5-membered ring structure. Y １ is also preferably a divalent organic group represented by formula (Y-2). In formula (Y-2), R ５ and R ８are each independently an alkyl group, a fluorine atom, or a trifluoromethyl group, and * represents a bonding site with the nitrogen atom in formula (1). ５ and R ８ are each preferably independently a fluorine atom or a trifluoromethyl group. ５ and R ８ The alkyl group in is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.

[0119] Specific examples of the divalent organic group represented by formula (Y-1) include structures represented by the following formulae, but the present invention is not limited to these. In the following formulae, * has the same meaning as * in formula (Y-1).

[0120] Also, Y １ is also preferably a group represented by formula (Y-3). １ A repeating unit represented by formula (Y-1) and Y １ and a repeating unit represented by formula (Y-2). In formula (Y-3), R １２ ~R １５ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group, and * represents a bonding site with the nitrogen atom in formula (1). １２ ~R １５ In one preferred embodiment of the present invention, all of R are hydrogen atoms. １２ ~R １５ The halogen atom in formula (Y-3) is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a fluorine atom or a chlorine atom, and even more preferably a fluorine atom. １２ ~R １５Examples of the monovalent organic group in the formula (I) include a hydrocarbon group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylcarbonyloxy group, an arylcarbonyloxy group, a poly(alkyleneoxy) group, a poly(aryleneoxy) group, a poly(alkyleneoxycarbonyl) group, a poly(aryleneoxycarbonyl) group, a hydroxy group, and a cyano group.

[0121] Others, Y １ is R in formula (2) described later. １１１ It may have a similar structure.

[0122] From the viewpoint of breaking elongation, it is preferable that the specific resin further contains a repeating unit represented by the following formula (3). In formula (3), Z ２ is a tetravalent organic group represented by any one of the following formulas (2a) to (2d), and Y ２ is a divalent organic group, and A １ and A ２ are each independently an oxygen atom or —NR Ｚ - and R Ｚ is a hydrogen atom or a monovalent organic group, and R １ and R ２ are each independently a hydrogen atom or a monovalent organic group, and R １ and R ２ At least one of the groups is a monovalent organic group having an ethylenically unsaturated bond. ２ is preferably a tetravalent organic group represented by formula (2a) or formula (2d), and more preferably a tetravalent organic group represented by formula (2a). In formulas (2a) to (2d), L １ and L ２ are each independently a divalent group that is not conjugated with the benzene ring to which it is bonded, or a single bond, and *1 to *4 each represent a bonding site with the carbonyl group in formula (3).

[0123] In formula (2c), L １ and L ２ are each independently -C(R Ｃ ) ２ -, -Si(R Ｓ) ２ -, -O-, or a single bond is preferred, and -C(R Ｃ ) ２ -, -Si(R Ｓ ) ２ It is more preferable that L is - or -O-. １ and L ２ At least one of the groups is -C(R Ｃ ) ２ - or -Si(R Ｓ ) ２ - is preferred. Ｃ are each independently a hydrogen atom or a hydrocarbon group, preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group. Ｃ may be bonded to form a ring structure. Ｓ are each independently a hydrocarbon group, preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group. Ｓ In formulas (2a) to (2d), either *1 or *2 may be bonded to A in formula (3). １ and the other bonded to a carbonyl group bonded to a structure outside the repeating unit represented by formula (3), and one of *3 or *4 is A in formula (3). ２ and the other bonded to a carbonyl group bonded to NH described in formula (3). In addition, the hydrogen atoms in the ring structures described in formulas (2a) to (2d) may be substituted with known substituents. Examples of the substituent include alkyl groups, halogen atoms, and alkyl groups in which hydrogen atoms are substituted with halogen atoms.

[0124] Specific examples of the groups represented by formulae (2a) to (2d) include the following structures, but the present invention is not limited to these. In the structures below, *1 to *4 have the same meanings as *1 to *4 in formulae (2a) to (2d), respectively.

[0125] In formula (3), Y ２ , A１ , A ２ , R １ and R ２ A preferred embodiment of the formula is Y １ , A １ , A ２ , R １ and R ２ This is the same as the preferred embodiment of the above.

[0126] The specific resin may further contain a repeating unit represented by the following formula (2) as a repeating unit different from both the repeating unit represented by the above formula (1) and the repeating unit represented by the formula (3). In other words, neither the repeating unit represented by the formula (1) nor the repeating unit represented by the formula (3) corresponds to the 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.

[0127] 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.

[0128] R １１１ is preferably derived from a diamine. Examples of diamines used in the production of the specific resin 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.

[0129] 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.

[0130] 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- or 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.

[0131] Also preferred are the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of WO 2017 / 038598.

[0132] 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.

[0133] 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.

[0134] 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.

[0135] R in formula (2) １１５ represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is more preferred. In formula (5) or formula (6), * each independently represents a bonding site to another structure. In formula (5), R １１２ represents a single bond or a divalent linking group, and is a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ２-, -NHCO-, and a group selected from a combination thereof are preferred, and a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, and -SO ２ - is more preferably a group selected from -CH ２ -, -C(CF ３ ) ２ -, -C(CH ３ ) ２ -, -O-, -CO-, -S- and -SO ２ It is more preferably a divalent group selected from the group consisting of -.

[0136] R １１５ Specifically, R may be a tetracarboxylic acid residue remaining after removal of the anhydride group from a tetracarboxylic dianhydride. １１５ The tetracarboxylic acid dianhydride may contain only one kind or two or more kinds of tetracarboxylic acid dianhydride residues as a structure corresponding to the formula (I). The tetracarboxylic acid dianhydride is preferably represented by the following formula (O). In formula (O), R １１５ represents a tetravalent organic group. １１５ The preferred range of R in formula (2) is １１５ The same applies to the preferred range.

[0137] 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.

[0138] Further, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017 / 038598 are also preferred examples.

[0139] 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.

[0140] 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 contained in the specific resin 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 above formula (III), with the group represented by the above formula (III) being preferred.

[0141] In formula (2), R １１３ is a hydrogen atom, or R １１４ is a hydrogen atom, the specific resin 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.

[0142] In formula (2), R １１３ and R １１４At 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.

[0143] The specific resin preferably has a fluorine atom in its structure. The fluorine atom content in the specific resin is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and even more preferably 5 to 20% by mass.

[0144] Furthermore, for the purpose of improving adhesion to the substrate, the specific resin 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.

[0145] 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 specific resins used in the present invention is a precursor having a repeating unit represented by formula (2-A). When the specific resin contains a repeating unit represented by formula (2-A), it becomes possible to further widen the range of 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 １１４each 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.

[0146] 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.

[0147] The specific resin 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 specific resin may also contain other types of repeating units in addition to the repeating unit of formula (2).

[0148] The specific resin may further contain other repeating units different from the repeating units represented by formulas (1) to (3). Examples of other repeating units include the repeating unit represented by formula (PAI-2) below. In formula (PAI-2), R １１７ represents a trivalent organic group, R １１１ represents a divalent organic group, A ２ represents an oxygen atom or —NH—, R １１３ represents a hydrogen atom or a monovalent organic group.

[0149] In formula (PAI-2), R １１７is exemplified by a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group in which two or more of these are linked by a single bond or a linking group, and is preferably a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined by a single bond or a linking group, and more preferably an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group. Examples of the linking group include -O-, -S-, -C(=O)-, -S(=O) ２ Preferred are -, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these, and more preferred are -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these. The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. The halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 4 carbon atoms. Furthermore, examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. The halogenated alkylene group may contain hydrogen atoms or may have all of the hydrogen atoms substituted with halogen atoms, but it is preferable that all of the hydrogen atoms be substituted with halogen atoms. Examples of preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group. The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and even more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0150] Also, R １１７is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated. The halogenation is preferably chlorination. In the present invention, a compound having three carboxy groups is referred to as a tricarboxylic acid compound. Two of the three carboxy groups in the tricarboxylic acid compound may be converted to acid anhydrides. Examples of tricarboxylic acid compounds that may be halogenated and are used in the production of polyamide-imide precursors include branched aliphatic, cyclic aliphatic, and aromatic tricarboxylic acid compounds. These tricarboxylic acid compounds may be used alone or in combination of two or more.

[0151] Specifically, the tricarboxylic acid compound is preferably a tricarboxylic acid compound containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined via a single bond or a linking group, and more preferably a tricarboxylic acid compound containing an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined via a single bond or a linking group.

[0152] Specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and compounds in which phthalic acid (or phthalic anhydride) and benzoic acid are bonded with a single bond, —O—, —CH ２ -, -C(CH ３ ) ２ -, -C(CF ３ ) ２ -, -SO ２ These compounds may be compounds in which two carboxy groups are anhydride (e.g., trimellitic anhydride), or compounds in which at least one carboxy group is halogenated (e.g., trimellitic anhydride chloride).

[0153] In formula (PAI-2), R １１１ , A ２ , R １１３are R in the above formula (2), １１１ , A ２ , R １１３ The same applies to the preferred embodiments.

[0154] In one embodiment of the specific resin, the content of the repeating units represented by formula (1) and the repeating units represented by formula (3) 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 specific resin except for the terminal repeating units may be repeating units represented by formula (1), or may be repeating units represented by formula (1) and repeating units represented by formula (3). When the specific resin contains repeating units represented by formula (1) and repeating units represented by formula (3), the content of the repeating units represented by formula (1) is preferably 5 to 70 mol%, more preferably 20 to 50 mol%, relative to the total molar content of the repeating units represented by formula (1) and the repeating units represented by formula (3).

[0155] The weight average molecular weight (Mw) of the specific resin is preferably 5,000 to 200,000, more preferably 10,000 to 100,000, and even more preferably 40,000 to 85,000. The number average molecular weight (Mn) of the specific resin is preferably 1,000 to 100,000, more preferably 3,000 to 50,000, and even more preferably 10,000 to 40,000. The molecular weight dispersity of the specific resin is preferably 4.0 or less, more preferably 3.0 or less, and even more preferably 2.0 or less. In this specification, the molecular weight dispersity is a value calculated by weight average molecular weight / number average molecular weight. When the resin composition contains multiple types of specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one specific resin be within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity, calculated by treating the plurality of specific resins as one resin, are each within the above ranges.

[0156] [Method for Producing Specific Resin] The specific resin can be synthesized, for example, by the method described in the Examples below, but is not limited thereto. Specifically, the specific resin can be obtained by, for example, reacting a tetracarboxylic dianhydride with a diamine at low temperature; reacting a tetracarboxylic dianhydride with a diamine at low temperature to obtain a polyamic acid, and then esterifying the polyamic acid using a condensing agent or an alkylating agent; obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then reacting the diamine with a condensing agent; or obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting the diamine. Among the above-mentioned production methods, the method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting the diamine, is more preferred. Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride. Examples of the alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate. Examples of the halogenating agent include thionyl chloride, oxalyl chloride, and phosphorus oxychloride. In the method for producing the specific resin, it is preferable to use an organic solvent during the reaction. One type of organic solvent may be used, or two or more types may be used. The organic solvent can be appropriately selected depending on the raw materials, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone. In the method for producing the specific resin, it is preferable to add a basic compound during the reaction. The basic compound may be one type or two or more types.The basic compound can be appropriately selected depending on the raw material, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and N,N-dimethyl-4-aminopyridine.

[0157] -End-capping agent- In order to further improve storage stability during the production method of the specific resin, it is preferable to cap the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the resin terminal of the specific resin. When capping the carboxylic acid anhydride or acid anhydride derivative remaining at the resin terminal, examples of the end-capping agent include monoalcohols, phenols, thiols, thiophenols, and monoamines. In terms of reactivity and film stability, it is more preferable to use monoalcohols, phenols, or monoamines. Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecynol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol; secondary alcohols such as isopropanol, 2-butanol, cyclohexyl alcohol, cyclopentanol, and 1-methoxy-2-propanol; and tertiary alcohols such as t-butyl alcohol and adamantane alcohol. Preferred phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene.Preferred examples of the monoamine compound include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, Examples of suitable end-capping agents include 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may be used, and multiple end-capping agents may be reacted to introduce multiple different end groups. Furthermore, when capping the amino groups at the resin ends, they can be capped with a compound having a functional group capable of reacting with the amino group. Preferred examples of the capping agent for the amino group include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, sulfonic acid carboxylic acid anhydrides, etc., and more preferred are carboxylic acid anhydrides and carboxylic acid chlorides. Preferred carboxylic acid anhydride compounds include acetic anhydride, propionic acid anhydride, oxalic acid anhydride, succinic acid anhydride, maleic acid anhydride, phthalic acid anhydride, benzoic acid anhydride, and 5-norbornene-2,3-dicarboxylic acid anhydride.Preferred examples of carboxylic acid chloride compounds include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearic acid chloride, and benzoyl chloride.

[0158] -Solid Precipitation- The method for producing the specific resin may include a step of precipitating a solid. Specifically, after filtering out water-absorbing by-products of the dehydration condensation agent coexisting in the reaction solution as needed, the resulting polymer component is added to a poor solvent such as water, a lower aliphatic alcohol, or a mixture thereof to precipitate the polymer component as a solid, which is then dried to obtain the specific resin. To improve the degree of purification, the specific resin may be repeatedly subjected to operations such as redissolving, reprecipitation, and drying. Furthermore, the method may include a step of removing ionic impurities using an ion exchange resin.

[0159] [Content] The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the resin composition. Furthermore, the content of the specific resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition. The resin composition of the present invention may contain only one type of specific resin, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0160] <Specific Metal Complex> The resin composition of the present invention preferably contains a metal complex having a π-conjugated moiety containing a nitrogen atom (also referred to as a "specific metal complex").

[0161] [Metal Atoms] The type of metal atom contained in the specific metal complex is not particularly limited, but is preferably a Group 4 metal atom, more preferably a titanium atom, zirconium atom, or hafnium atom, and even more preferably a titanium atom from the viewpoint of storage stability. This is presumably because the titanium atom has a small atomic radius, which improves the stability of the compound. The number of metal atoms contained in the specific metal complex is not particularly limited, but may be 1 or more, more preferably 1 to 4, even more preferably 1 or 2, and particularly preferably 1. Furthermore, when the specific metal complex contains two or more of the above metal atoms, the types of the metal atoms may be the same or different. For example, when the specific metal complex contains two of the above metal atoms, it may contain two titanium atoms, or it may contain a titanium atom and a zirconium atom.

[0162] [π-conjugated moiety containing a nitrogen atom] The specific metal complex has a π-conjugated moiety containing a nitrogen atom. 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 them is directly bonded to a metal atom in the specific metal complex. Here, the specific metal complex may have only one or two π-conjugated moieties containing a nitrogen atom, but it is preferable that it has one to two.

[0163] The π-conjugated moiety containing a nitrogen atom preferably has a structure represented by the following formula (T1-1). In formula (T1-1), 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.

[0164] In formula (T1-1), 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(-*)=.

[0165] In formula (T1-1), at least two structures bonded to * may be bonded to form a ring structure.

[0166] The specific metal complex is preferably a compound having a π-conjugated moiety containing a nitrogen atom and at least one group selected from the group consisting of a hydroxy group, a mercapto group, and a carboxy group on the same ligand, wherein the hydroxy group, the mercapto group, and the carboxy group are preferably bonded to the metal atom as -O-, -S-, or -C(=O)-.

[0167] The specific metal complex may further have another structure different from the π-conjugated moiety containing a nitrogen atom. The other structure is not particularly limited, and a structure consisting of a known ligand can be used. Examples of the ligand include a monodentate alkoxide ligand, a monodentate aryloxide ligand, a multidentate aryloxide ligand, and a cyclopentadienyl ligand, and these ligands may further have a substituent. From the viewpoint of the stability of the specific metal complex, a substituted or unsubstituted cyclopentadienyl ligand is preferred.

[0168] The specific metal complex is preferably a compound represented by the following formula (2-1). In formula (2-1), M is titanium, zirconium, or hafnium, l1 is an integer of 0 to 2, l2 is 0 or 1, l1 + l2 × 2 is an integer of 0 to 2, m is an integer of 0 to 4, n is an integer of 0 to 2, l1 + l2 + m + n × 2 = 4, and R １１ are each independently a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenoxy group; R １２ is a substituted or unsubstituted hydrocarbon group, R ２ are each independently a group containing a structure represented by the following formula (2-2), and R ３ are each independently a group containing a structure represented by the following formula (2-2), Ａ are each independently an oxygen atom or a sulfur atom. In formula (2-2), X １ ~X ３each independently represents -C(-*)= or -N=, * represents a bonding site to another structure, and # represents a bonding site to a metal atom.

[0169] In formula (2-1), from the viewpoint of storage stability of the composition, M is preferably titanium. In formula (2-1), an embodiment in which l1 and l2 are 0 is also one of the preferred embodiments of the present invention. In formula (2-1), m is preferably 2 or 4, and more preferably 2. In formula (2-1), n ​​is preferably 1 or 2, and more preferably 1. Here, it is also preferable that in formula (2-1), l1 and l2 are 0, and m is 0, 2, or 4.

[0170] In the formula (2-1), from the viewpoint of the stability of the specific metal complex, R １１ is preferably a substituted or unsubstituted cyclopentadienyl ligand. １１ The cyclopentadienyl group, alkoxy group and phenoxy group in the formula (I) may be substituted, but an embodiment in which they are unsubstituted is also one of the preferred embodiments of the present invention.

[0171] In formula (2-1), 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. １２The phenylene group in is preferably a 1,2-phenylene group.

[0172] In formula (2-1), R ２ and R ３ A preferred embodiment of the structure represented by formula (2-2) included in the formula (2-1) is the same as the preferred embodiment of formula (T1-1) above. In formula (2-1), m is 2 or more, and R ２ If two or more are included, ２ In formula (2-1), n ​​is 2 or more, and R ３ If two or more are included, ３ The structures may be the same or different.

[0173] R in formula (2-1) ２ Specific examples of the compound are shown below, but are not limited to these. In the following structures, * represents X in formula (2-1). Ａ represents the bonding site with M in formula (2-1).

[0174] R in formula (2-1) ３ Specific examples of the formula (2-1) are shown below, but the formula is not limited thereto. Ａ represents the bonding site with M in formula (2-1).

[0175] From the viewpoint of the stability of the specific metal complex, one of the preferred embodiments of the present invention is one in which the specific metal complex does not have any monodentate ligand other than cyclopentadienyl.

[0176] The specific metal complex preferably generates an amine when heated to 250°C. The temperature is preferably 230°C, more preferably 200°C, and even more preferably 180°C. In the present invention, a specific metal complex is defined as generating an amine at X°C if a solution of the specific metal complex at the same concentration as the resin composition of the present invention dissolved in the same solvent as the resin composition of the present invention is prepared and heated at X°C, and an amine is generated in an amount of 10 mol% or more relative to the total molar amount of the specific metal complex. Furthermore, from the viewpoint of the elongation at break of the resulting cured product, the pKa of the conjugate acid of the amine is preferably 3 or more, more preferably 6 or more. The upper limit of the pKa of the conjugate acid is not particularly limited, but is preferably 30 or less. Furthermore, from the viewpoint of storage stability, the pKa of the conjugate acid of the specific metal complex itself is preferably less than 3, preferably -5 or less, and more preferably -10 or less. pKa refers to the equilibrium constant Ka of a dissociation reaction in which hydrogen ions are released from an acid, expressed as its negative common logarithm, pKa. In this specification, unless otherwise specified, pKa is a value calculated by ACD / ChemSketch (registered trademark). When the conjugate acid has multiple pKa values, it is preferable that at least one of them is within the above range.

[0177] The solubility parameter of the specific metal complex is preferably an SP (solubility parameter) value of 9 or more, more preferably 10 or more. There is no particular upper limit to the SP value, and it may be, for example, 30 or less. In this specification, the SP value is determined by the Hoy method (H.L. Hoy, Journal of Painting, 1970, Vol. 42, 76-118), unless otherwise specified. In addition, although the unit of the SP value is omitted, the unit is cal １／２ cm －３／２ is.

[0178] [Molecular Weight] The molecular weight of the specific metal complex is preferably 200 to 2,000, more preferably 250 to 1,500, and even more preferably 300 to 1,000.

[0179] [Synthesis Method] The specific metal complex can be synthesized, for example, by reacting a titanium alkoxide with a compound having an alkoxy group or a carboxyl group. Alternatively, other known synthesis methods may be used for synthesis, and the synthesis method is not particularly limited.

[0180] Specific examples of the specific metal complex include, but are not limited to, J-1 to J-4 used in the examples.

[0181] The content of the specific metal complex relative to the total solid content of the resin composition of the present invention is preferably 0.05 to 20% by mass. The lower limit is more preferably 0.10% by mass or more, even more preferably 0.2% by mass or more, particularly preferably 0.5% by mass or more, and most preferably 1% by mass or more. The upper limit is more preferably 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 8% by mass or less. One type of specific metal complex 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 is preferably within the above range.

[0182] <Other Resins> The resin composition of the present invention may contain the above-described specific resin and another resin (hereinafter simply referred to as "other resin") different from the specific resin. Examples of other resins include polyimide precursors that do not fall under the category of specific resins (for example, polyimide precursors that do not contain a repeating unit represented by formula (1) and contain a repeating unit represented by formula (2)), polybenzoxazole precursors, polyamideimide precursors, polyimides, polybenzoxazoles, polyamideimides, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins. For example, by further adding a (meth)acrylic resin, a resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained. For example, instead of or in addition to the polymerizable compound described below, a 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. －３By adding a (meth)acrylic resin (having a molecular weight of 1000 to 1000 mol / g or more) to the resin composition, it is possible to improve the coatability of the resin composition and the solvent resistance of the pattern (cured product).

[0183] When the 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 resin composition. The content of the other resin in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on the total solid content of the resin composition. A preferred embodiment of the resin composition of the present invention may also be an embodiment in which the content of the other resin is low. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the resin composition. The lower limit of the content is not particularly limited, as long as it is 0% by mass or more. The resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0184] <Polymerizable Compound> The 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.

[0185] [Radical Crosslinking Agent] The resin composition of the present invention preferably contains a radical crosslinking agent. The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group containing an ethylenically unsaturated bond. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group. Among these, a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferred, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferred.

[0186] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds. The radical crosslinking agent may have three or more ethylenically unsaturated bonds. The compound having two or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and even more preferably a compound having 2 to 6 ethylenically unsaturated bonds. From the viewpoint of the film strength of the obtained pattern (cured product), it is also preferable that the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and the compound having three or more ethylenically unsaturated bonds.

[0187] 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.

[0188] 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.

[0189] 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.

[0190] 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.

[0191] 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.

[0192] 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).

[0193] 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.

[0194] 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.

[0195] 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.

[0196] The radical crosslinking agent is preferably a radical crosslinking agent having at least one structure selected from the group consisting of a urea bond, a urethane bond, and an amide bond (hereinafter also referred to as "crosslinking agent U"). In the present invention, the urea bond is defined as *-NR Ｎ —C(═O)—NRＮ - 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, preferably a bonding site with a hydrocarbon group. 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, preferably a bonding site with a hydrocarbon group. In the present invention, the amide bond is *-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, preferably a bonding site with a hydrocarbon group. The inclusion of crosslinking agent U in a resin composition may improve chemical resistance, resolution, and the like. The mechanism by which this effect is achieved is unclear; however, it is thought that, for example, during curing by heating, a portion of crosslinking agent U thermally decomposes, generating amines and the like, which then promote cyclization of the polyimide precursor. Crosslinking agent U may have only one urea bond, urethane bond, or amide bond, or may have two or more structures selected from the group consisting of urea bonds, urethane bonds, and amide bonds. The total number of urea bonds, urethane bonds, and amide bonds in crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0197] 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.

[0198] 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 a single bond, —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 represents a single bond or an (n+1)-valent organic group, X represents a radical polymerizable group, n represents an integer of 1 or more, and m represents an integer of 1 or more.

[0199] 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 preferable. Ｕ１ The bonding site with A in R is preferably a hydrocarbon group. 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 bond between these groups. 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.

[0200] It is also preferable that the crosslinking agent U has at least one of a hydroxy group, an alkyleneoxy 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 is preferably an alcoholic hydroxy group. 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, still more preferably an ethylene group or a propylene 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 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, the structure is a polyalkyleneoxy 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, and cyano group may be present at any position in the crosslinking agent U, but from the viewpoint of chemical resistance, it is also preferred that the crosslinking agent U has at least one selected from the group consisting of the hydroxy group, alkyleneoxy group, and cyano group linked to at least one radically polymerizable group contained in the crosslinking agent U via a linking group containing a urea bond, a urethane bond, or an amide bond (hereinafter also referred to as "linking group L2-1"). In particular, when the crosslinking agent U contains only one radically polymerizable group, it is preferable that the radically polymerizable group contained in the crosslinking agent U and at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, and a cyano group are linked via a linking group containing a urea bond, a urethane bond, or an amide 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 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. 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 thereof. Furthermore, preferred embodiments of the radically polymerizable group are the same as those of the radically polymerizable group in crosslinking agent U described above. Among these, from the viewpoints of adhesion to the substrate, chemical resistance, and suppression of Cu voids, it is preferable that crosslinking agent U has a hydroxy group.

[0201] 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, a urethane bond, or an amide bond contained in the crosslinking agent U. When the crosslinking agent U contains two or more urea bonds, urethane bonds, or amide bonds, it is preferable that one of the urea bonds, urethane bonds, or amide 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 heterocyclic ring 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, as in indole and 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, a urethane bond, or an amide bond, or a linking group that links at least one selected from the group consisting of the above-mentioned hydroxy group, alkyleneoxy group, and cyano group to at least one radical polymerizable group contained in the crosslinking agent U.

[0202] The number of atoms (linking chain length) between the urea bond, urethane bond, or amide 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, urethane bonds, or amide bonds, when it contains two or more radical polymerizable groups, or when it contains two or more urea bonds, urethane bonds, or amide bonds and two or more radical polymerizable groups, the minimum number of atoms (linking chain length) between the urea bond, urethane bond, or amide 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, urethane bond, or amide 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 linked 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.

[0203] [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 agents U within the composition film.

[0204] [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.

[0205] The method for producing the crosslinking agent U is not particularly limited, but it can be obtained, for example, by reacting a radically polymerizable compound and a compound having an isocyanate group with a compound having at least one of a hydroxy group and an amino group.

[0206] Specific examples of the crosslinking agent U include the following compounds and M-8 to M-13 in the examples described below, but the crosslinking agent U is not limited to these.

[0207] From the viewpoints of pattern resolution and film stretchability, the 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, 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 diacrylate of bisphenol A, propylene oxide (PO) adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, EO-modified isocyanuric acid 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 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.

[0208] When a radical crosslinking agent is contained, the content of the radical crosslinking agent is preferably more than 0% by mass and not more than 60% by mass, based on the total solid content of the resin composition. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0209] 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.

[0210] [Other Crosslinking Agents] The resin composition of the present invention preferably contains another crosslinking agent different from the radical crosslinking agent described above. The other crosslinking agent refers to a crosslinking agent other than the radical crosslinking agent described above. 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, and 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 under the action of an acid or a base. The acid or base is preferably an acid or base generated from a photoacid generator or photobase generator in the exposure step. The other crosslinking agent is preferably a compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group, and an alkoxymethyl group, and more preferably a compound having a structure in which at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group, and an alkoxymethyl group is directly bonded to a nitrogen atom. Other crosslinking agents include compounds having a structure in which an amino group-containing compound such as melamine, glycoluril, urea, alkyleneurea, or benzoguanamine is reacted with formaldehyde or formaldehyde and an alcohol, and the hydrogen atom of the amino group is substituted with an acyloxymethyl group, a methylol group, an ethylol group, or an alkoxymethyl group. The method for producing these compounds is not particularly limited, and any compound having a structure similar to that of the compound produced by the above method may be used. Oligomers formed by self-condensation of the methylol groups of these compounds may also be used. As for the amino group-containing compounds, crosslinking agents using melamine are referred to as melamine-based crosslinking agents, crosslinking agents using glycoluril, urea, or alkyleneurea are referred to as urea-based crosslinking agents, crosslinking agents using alkyleneurea are referred to as alkyleneurea-based crosslinking agents, and crosslinking agents using benzoguanamine are referred to as benzoguanamine-based crosslinking agents. Among these, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from the group consisting of glycoluril-based crosslinking agents and melamine-based crosslinking agents, which will be described later.

[0211] Examples of compounds containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention include compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group or a nitrogen atom of the urea structure described below, or on a triazine. The alkoxymethyl group or acyloxymethyl group contained in the above compound preferably has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms. The total number of alkoxymethyl groups and acyloxymethyl groups contained in the above compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6. The molecular weight of the above compound is preferably 1,500 or less, more preferably 180 to 1,200.

[0212]

[0213] R １００ represents an alkyl group or an acyl group. １０１ and R １０２ each independently represents a monovalent organic group, and may be bonded to each other to form a ring.

[0214] Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group include compounds represented by the following general formula:

[0215]

[0216] In the formula, X represents a single bond or a divalent organic group, and each R １０４ each independently represents an alkyl group or an acyl group, R １０３ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a group that decomposes under the action of an acid to generate an alkali-soluble group (for example, a group that is eliminated under the action of an acid, -C(R ４ ) ２ COOR ５ A group represented by R ４ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ５ represents a group that is eliminated by the action of an acid. １０５each independently represents an alkyl group or an alkenyl group, a, b, and c each independently represent 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less. A group that decomposes under the action of an acid to produce an alkali-soluble group, a group that is eliminated under the action of an acid, -C(R ４ ) ２ COOR ５ R in the group represented by ５ For example, -C(R ３６ ) (R ３７ ) (R ３８ ), -C(R ３６ ) (R ３７ ) (OR ３９ ), -C(R ０１ ) (R ０２ ) (OR ３９ In the formula, R ３６ ~R ３９ R each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. ３６ and R ３７ may be bonded to each other to form a ring. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms. The alkyl group may be either linear or branched. The cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, more preferably a cycloalkyl group having 3 to 8 carbon atoms. The cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring. The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably a phenyl group. The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, more preferably an aralkyl group having 7 to 16 carbon atoms. The aralkyl group refers to an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as those of the alkyl and aryl groups described above. The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, more preferably an alkenyl group having 3 to 16 carbon atoms. These groups may further have a known substituent.

[0217] R ０１ and R ０２ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

[0218] The group that decomposes under the action of an acid to generate an alkali-soluble group or the group that is eliminated under the action of an acid is preferably a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, etc., more preferably a tertiary alkyl ester group or an acetal group.

[0219] Furthermore, as the compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group, and an alkoxymethyl group, a compound having at least one group selected from the group consisting of a urea bond and a urethane bond is also preferred. The preferred embodiments of the above compound are the same as the preferred embodiments of the above crosslinking agent U, except that the polymerizable group is not a radical polymerizable group but at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group, and an alkoxymethyl group.

[0220] Specific examples of compounds having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, and an ethylol group include the following structures: Compounds having an acyloxymethyl group include compounds in which the alkoxymethyl group in the following compound is replaced with an acyloxymethyl group: Compounds having an alkoxymethyl group or acyloxymethyl in the molecule include, but are not limited to, the following compounds:

[0221]

[0222]

[0223]

[0224] The compound containing at least one of an alkoxymethyl group and an acyloxymethyl group may be a commercially available compound or may be synthesized by a known method. From the viewpoint of heat resistance, a compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring is preferred.

[0225] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.

[0226] Specific examples of the urea-based crosslinking agent include glycoluril-based crosslinking agents such as monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, diethoxymethylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, and tetrabutoxymethylated glycoluril; urea-based crosslinking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea; Ethylene urea-based crosslinking agents such as monohydroxymethylated ethylene urea or dihydroxymethylated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethylated ethylene urea, monobutoxymethylated ethylene urea, or dibutoxymethylated ethylene urea; propylene urea-based crosslinking agents such as monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea; Examples thereof include 1,3-di(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone and 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone.

[0227] Specific examples of benzoguanamine-based crosslinking agents include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

[0228] In addition, as the compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group, a compound in which at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is directly bonded to an aromatic ring (preferably a benzene ring) is also preferably used. Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylidenetris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1,3-benzenedimethanol], and 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol.

[0229] As other crosslinking agents, commercially available products may be used, and suitable commercially available products include 46DMOC, 46DMOEP (all manufactured by Asahi Organic Chemicals Co., Ltd.), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, and TriML-35XL. , TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac (registered trademark, the same applies hereinafter) MX-290, Nikalac MX-280, Nikalac MX-270, Nikalac MX-279, Nikalac MW-100LM, Nikalac MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.), and the like.

[0230] The resin composition of the present invention also preferably contains, as another crosslinking agent, at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds.

[0231] - Epoxy Compound (Compound Having Epoxy Group) - The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. Epoxy groups undergo a crosslinking reaction at 200°C or less, and since dehydration reactions resulting from crosslinking do not occur, film shrinkage is unlikely to occur. Therefore, the inclusion of an epoxy compound is effective in low-temperature curing of the resin composition and suppressing warpage.

[0232] The epoxy compound preferably contains a polyethylene oxide group, which further reduces the modulus of elasticity and suppresses warpage. The polyethylene oxide group refers to a group having two or more repeating ethylene oxide units, and preferably has 2 to 15 repeating units.

[0233] Examples of epoxy compounds include, but are not limited to, bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and epoxy group-containing silicones such as polymethyl(glycidyloxypropyl)siloxane. Specifically, Epicron (registered trademark, the same applies hereinafter) 850-S, Epicron HP-4032, Epicron HP-7200, Epicron HP-820, Epicron HP-4700, Epicron HP-4770, Epicron EXA-830LVP, Epicron EXA-8183, Epicron EXA-8169, Epicron N-660, Epicron N-665-EXP-S, Epicron N-740 (all trade names, manufactured by DIC Corporation), Rikaresin (registered trademark, the same applies below) BEO-20E, Rikaresin BEO-60E, Rikaresin HBE-100, Rikaresin DME-100, Rikaresin L-200 (all trade names, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (all trade names, manufactured by ADEKA Corporation), Ceroxa Epolead (registered trademark, the same applies hereinafter) 2021P, Celloxide 2081, Celloxide 2000, EHPE3150, Epolead (registered trademark, the same applies hereinafter) GT401, Epolead PB4700, Epolead PB3600 (all trade names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-30 00-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (all trade names, manufactured by Nippon Kayaku Co., Ltd.), and the like.The following compounds are also preferably used:

[0234]

[0235] In the formula, n is an integer of 1 to 5, and m is an integer of 1 to 20.

[0236] Among the above structures, it is preferable that n is 1 to 2 and m is 3 to 7 in order to achieve both improved heat resistance and improved elongation.

[0237] -Oxetane Compound (Compound Having an Oxetanyl Group)- Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, such as 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester. Specific examples include the Aron Oxetane series (e.g., OXT-121, OXT-221) manufactured by Toagosei Co., Ltd., which may be used alone or in combination of two or more.

[0238] - Benzoxazine Compound (Compound Having a Benzoxazolyl Group) - Benzoxazine compounds are preferred because they undergo a crosslinking reaction derived from a ring-opening addition reaction, so that degassing does not occur during curing, and further, they reduce thermal shrinkage and suppress the occurrence of warping.

[0239] Preferred examples of the benzoxazine compound include Pd-type benzoxazine, Fa-type benzoxazine (all trade names, manufactured by Shikoku Chemical Industry Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resins, and phenol novolac-type dihydrobenzoxazine compounds. These may be used alone or in combination of two or more.

[0240] The content of the other crosslinking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass, based on the total solid content of the resin composition. Only one type of other crosslinking agent may be contained, or two or more types may be contained. When two or more types of other crosslinking agents are contained, the total amount thereof is preferably within the above range.

[0241] [Polymerization initiator] The resin composition of the present invention preferably contains a polymerization initiator. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable to contain a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular restrictions on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible range is preferred. Alternatively, it may be an activator that reacts with a photoexcited sensitizer to generate active radicals.

[0242] 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.

[0243] 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.

[0244] 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.

[0245] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used as the photoradical polymerization initiator. More specifically, for example, the aminoacetophenone initiators described in JP-A-10-291969 and the acylphosphine oxide initiators described in Japanese Patent No. 4225898 can be used, the contents of which are incorporated herein by reference. Furthermore, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like can also be suitably used as the acylphosphine oxide. Furthermore, examples of commercially available acylphosphine oxide initiators include Omnirad TPO H.

[0246] 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).

[0247] 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).

[0248] 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.

[0249] As the photoradical polymerization initiator, an oxime compound is more preferably used. By using an oxime compound, it is possible to more effectively improve the exposure latitude. An oxime compound is particularly preferred because it has a wide exposure latitude (exposure margin) and also functions as a photocuring accelerator.

[0250] 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.

[0251] 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, 5-(4-isopropylphenylthio)-1,2-indanedione, 2-(O-acetyl)oxime, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one. In the resin composition, it is particularly preferable to use an oxime compound as a photoradical polymerization initiator. The oxime compound serving as a photoradical polymerization initiator has a linking group >C=N--O--C(=O)-- in the molecule.

[0252]

[0253] Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF), Omnirad 1312 (manufactured by IGM Resins), and B.V.), 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.), SpeedCure PDO (manufactured by SARTOMER ARKEMA). In addition, oxime compounds having the following structure can also be used.

[0254] 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.

[0255] As the photopolymerization initiator, an aromatic ring group Ar in which an electron-withdrawing group is introduced into the aromatic ring can be used. ＯＸ１ It is also possible to use an oxime compound having the aromatic ring group Ar ＯＸ１ Examples of the electron-withdrawing group include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group. Acyl and nitro groups are preferred, and an acyl group is more preferred because it is easier to form a film with excellent light resistance, and a benzoyl group is even more preferred. The benzoyl group may have a substituent. The substituent is preferably a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group, an arylsulfanyl group, an acyl group, or an amino group. An alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, or an amino group is more preferred, and an alkoxy group, an alkylsulfanyl group, or an amino group is even more preferred.

[0256] The oxime compound OX is preferably at least one selected from the compounds represented by formula (OX1) and the compounds represented by formula (OX2), and more preferably the compound represented by formula (OX2). In the formula, RＸ１ represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group or a sulfamoyl group; R Ｘ２ represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, or an amino group; R Ｘ３ ~R Ｘ１４ each independently represents a hydrogen atom or a substituent. Ｘ１０ ~R Ｘ１４ At least one of the groups is an electron-withdrawing group.

[0257] In the above formula, R Ｘ１２ is an electron-withdrawing group, and R Ｘ１０ , R Ｘ１１ , R Ｘ１３ , R Ｘ１４ is preferably a hydrogen atom.

[0258] Specific examples of the oxime compound OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein by reference.

[0259] Particularly preferred oxime compounds include oxime compounds having specific substituents as disclosed in JP-A-2007-269779 and oxime compounds having a thioaryl group as disclosed in JP-A-2009-191061, the contents of which are incorporated herein by reference.

[0260] From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds.

[0261] The photoradical polymerization initiator is a trihalomethyltriazine compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, a benzophenone compound, or an acetophenone compound, more preferably at least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, or a benzophenone compound, and even more preferably a metallocene compound or an oxime compound.

[0262] As the photoradical polymerization initiator, the compounds described in paragraphs 0175 to 0179 of WO 2021 / 020359 and the compounds described in paragraphs 0048 to 0055 of WO 2015 / 125469 can also be used, the contents of which are incorporated herein by reference.

[0263] As the photoradical polymerization initiator, a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, thereby obtaining good sensitivity. Furthermore, when a compound with an asymmetric structure is used, crystallinity is reduced and solubility in solvents is improved, making it less likely to precipitate over time, and improving the stability of the resin composition over time. Specific examples of the bifunctional or trifunctional or higher functional photoradical polymerization initiator include dimers of oxime compounds described in JP-T-2010-527339, JP-T-2011-524436, WO 2015 / 004565, WO 2016-532675, paragraphs 0407 to 0412, and WO 2017 / 033680, paragraphs 0039 to 0055; compounds (E) and (G) described in JP-T-2013-522445; oxime ester photoinitiators described in paragraph 0007 of JP-T-2017-523465, photoinitiators described in paragraphs 0020 to 0033 of JP-A-2017-167399, photopolymerization initiator (A) described in paragraphs 0017 to 0026 of JP-A-2017-151342, and oxime ester photoinitiators described in Japanese Patent No. 6469669, the contents of which are incorporated herein by reference.

[0264] When the resin composition contains a photopolymerization initiator, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass, based on the total solid content of the resin composition. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more types of photopolymerization initiators are contained, the total amount is preferably within the above range. Note that the photopolymerization initiator may also function as a thermal polymerization initiator, and therefore crosslinking by the photopolymerization initiator may be further promoted by heating in an oven, hot plate, or the like.

[0265] [Sensitizer] The resin composition may contain a sensitizer. The sensitizer absorbs specific actinic radiation and becomes electronically excited. The electronically excited sensitizer comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and undergoes electron transfer, energy transfer, heat generation, and other actions. This causes the thermal radical polymerization initiator or the photoradical polymerization initiator to undergo a chemical change and decompose, generating a radical, acid, or base. Usable sensitizers include benzophenone-based, Michler's ketone-based, coumarin-based, pyrazole azo-based, anilino azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, and indigo-based compounds.Examples of the sensitizer include 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.

[0266] When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20 mass %, more preferably 0.1 to 15 mass %, and still more preferably 0.5 to 10 mass %, based on the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more types.

[0267] [Chain Transfer Agent] The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pages 683-684. Examples of chain transfer agents include those having -S-S-, -SO ２ Examples of compounds that can be used include compounds having -S-, -N-O-, SH, PH, SiH, and GeH, and dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthate compounds having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These compounds can donate hydrogen to low-activity radicals to generate radicals, or can be oxidized and then deprotonated to generate radicals. Thiol compounds are particularly preferred.

[0268] 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.

[0269] When the resin composition contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the total solid content of the resin composition. Only one type of chain transfer agent may be used, or two or more types may be used. When two or more types of chain transfer agents are used, the total content thereof is preferably within the above range.

[0270] <Base Generator> The resin composition of the present invention may contain a base generator. Here, a base generator is a compound capable of generating a base through physical or chemical action. Preferred base generators include thermal base generators and photobase generators. By including a thermal base generator in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, resulting in improved mechanical properties and chemical resistance of the cured product, and improved performance as an interlayer insulating film for a rewiring layer included in a semiconductor package. Another preferred embodiment of the present invention is one in which the resin composition does not contain a compound that generates a base. Specifically, the content of the base generator is preferably 0.1% by mass or less, more preferably 0.01% by mass or less, relative to the total mass of the resin composition. The content may even be 0% by mass. The base generator may be an ionic base generator or a nonionic base generator. Examples of bases generated by 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, acyloxyimino compounds, etc. Specific examples of non-ionic base generators include compounds represented by formula (B1), formula (B2), or formula (B3).

[0271] In formula (B1) and formula (B2), Rb １ , Rb ２ and Rb ３ each independently represents an organic group not having a tertiary amine structure, a halogen atom, or a hydrogen atom, provided that Rb １ and Rb ２cannot be hydrogen atoms at the same time. １ , Rb ２ and Rb ３ None of the above has a carboxy group. In this specification, the term "tertiary amine structure" refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to carbon atoms of a hydrocarbon group. Therefore, if the carbon atom bonded to the trivalent nitrogen atom is a carbon atom constituting a carbonyl group, i.e., if it forms an amide group together with the nitrogen atom, it is not a tertiary amine structure.

[0272] In formula (B1) and formula (B2), Rb １ , Rb ２ and Rb ３ Preferably, at least one of these contains a cyclic structure, and more preferably, at least two contain a cyclic structure. The cyclic structure may be either a monocyclic ring or a fused ring, and a monocyclic ring or a fused ring in which two monocyclic rings are fused is preferred. The monocyclic ring is preferably a 5-membered or 6-membered ring, and more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring or a benzene ring, and more preferably a cyclohexane ring.

[0273] More specifically, Rb １ and Rb ２ is preferably a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 25 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms). These groups may have a substituent. Rb １ and Rb ２ may be bonded to each other to form a ring. The ring formed is preferably a 4- to 7-membered nitrogen-containing heterocyclic ring. １ and Rb ２is preferably a linear, branched, or cyclic alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms) which may have a substituent, more preferably a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably having 3 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms) which may have a substituent, and even more preferably a cyclohexyl group which may have a substituent.

[0274] Rb ３ Examples of the alkyl group include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 12 carbon atoms, and even more preferably having 2 to 6 carbon atoms), an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), an arylalkenyl group (preferably having 8 to 24 carbon atoms, more preferably having 8 to 20 carbon atoms, and even more preferably having 8 to 16 carbon atoms), an alkoxyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryloxy group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), and an arylalkyloxy group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms). Among these, a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably having 3 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferred. ３ may further have a substituent.

[0275] The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or (B1-2):

[0276] In the formula, Rb １１ and Rb １２ , and Rb ３１ and Rb ３２ respectively represent Rb in formula (B1). １ and Rb ２ is the same as Rb １３is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), which may have a substituent. １３ is preferably an arylalkyl group.

[0277] Rb ３３ and Rb ３４ are each independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 8 carbon atoms, and still more preferably having 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 8 carbon atoms, and still more preferably having 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and still more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and still more preferably having 7 to 11 carbon atoms), and a hydrogen atom is preferred.

[0278] Rb ３５ represents an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 10 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), with an aryl group being preferred.

[0279] The compound represented by formula (B1-1) is preferably a compound represented by formula (B1-1a).

[0280] Rb １１ and Rb １２ represents Rb in formula (B1-1). １１ and Rb １２ Rb １５ and Rb １６is a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and even more preferably having 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 6 carbon atoms, and even more preferably having 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 11 carbon atoms), and preferably a hydrogen atom or a methyl group. １７ represents an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 10 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), and among these, an aryl group is preferred.

[0281]

[0282] In formula (B3), L represents a divalent hydrocarbon group having a saturated hydrocarbon group on the path of a linking chain connecting adjacent oxygen atoms and carbon atoms, and the number of atoms on the path of the linking chain is 3 or more. Ｎ１ and R Ｎ２ each independently represents a monovalent organic group.

[0283] In this specification, the term "linking chain" refers to the chain of atoms on the path connecting two atoms or groups of atoms to be linked, which links these atoms or groups of atoms in the shortest possible manner (with the smallest number of atoms). For example, in the compound represented by the following formula, L is composed of a phenyleneethylene group and has an ethylene group as the saturated hydrocarbon group, the linking chain is composed of four carbon atoms, and the number of atoms on the path of the linking chain (i.e., the number of atoms constituting the linking chain, hereinafter also referred to as the "linking chain length" or "length of the linking chain") is 4.

[0284] The number of carbon atoms in L in formula (B3) (including carbon atoms other than those in the connecting chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, even more preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of rapidly progressing the intramolecular cyclization reaction, the upper limit of the connecting chain length of L is preferably 12 or less, more preferably 8 or less, even more preferably 6 or less, and particularly preferably 5 or less. In particular, the connecting chain length of L is preferably 4 or 5, and most preferably 4. Specific preferred compounds for the base generator include, for example, the compounds described in paragraphs 0102 to 0168 of WO 2020 / 066416 and the compounds described in paragraphs 0143 to 0177 of WO 2018 / 038002.

[0285] The base generator also preferably contains a compound represented by the following formula (N1).

[0286] In formula (N1), R Ｎ１ and R Ｎ２ each independently represents a monovalent organic group, R Ｃ１ represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

[0287] L is a divalent linking group, and is preferably a divalent organic group. The linking chain length of the linking group is preferably 1 or more, more preferably 2 or more. The upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The linking chain length is the number of atoms present in the atomic sequence that forms the shortest path between the two carbonyl groups in the formula.

[0288] In formula (N1), R Ｎ１ and R Ｎ２R each independently represents a monovalent organic group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), and is preferably a hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 1 to 10 carbon atoms). Specific examples include an aliphatic hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 1 to 10 carbon atoms) or an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), and an aliphatic hydrocarbon group is preferred. Ｎ１ and R Ｎ２ When an aliphatic hydrocarbon group is used as the base, the basicity of the generated base is high, and this is preferable. The aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in the aliphatic hydrocarbon chain, in the aromatic ring, or in the substituent. In particular, an embodiment in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain is exemplified.

[0289] R Ｎ１ and R Ｎ２Examples of the aliphatic hydrocarbon group constituting the alkyl group include linear or branched chain alkyl groups, cyclic alkyl groups, groups containing a combination of a linear alkyl group and a cyclic alkyl group, and alkyl groups having an oxygen atom in the chain. The linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms. Examples of the linear or branched chain alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, isobutyl, secondary butyl, tertiary butyl, isopentyl, neopentyl, tertiary pentyl, and isohexyl groups. The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. Examples of the cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups. The group containing a combination of a chain alkyl group and a cyclic alkyl group preferably has 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, and even more preferably 4 to 12 carbon atoms. Examples of the group containing a combination of a chain alkyl group and a cyclic alkyl group include a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, and an ethylcyclohexylethyl group. The alkyl group having an oxygen atom in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The alkyl group having an oxygen atom in the chain may be chain or cyclic, and may be linear or branched. In particular, from the viewpoint of increasing the boiling point of the decomposition product base described below, R Ｎ１ and R Ｎ２ is preferably an alkyl group having 5 to 12 carbon atoms. However, in a formulation where importance is placed on adhesion when laminating with a metal (e.g., copper) layer, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferred.

[0290] R Ｎ１ and R Ｎ２ may be linked to each other to form a cyclic structure. The cyclic structure may have an oxygen atom or the like in the chain. Ｎ１ and R Ｎ２The cyclic structure formed by may be a monocyclic ring or a fused ring, but is preferably a monocyclic ring. The cyclic structure formed is preferably a 5- or 6-membered ring containing a nitrogen atom in formula (N1), for example, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolidine ring, a pyrazolidine ring, a piperidine ring, a piperazine ring, a morpholine ring, etc., and preferred examples include a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring.

[0291] R Ｃ１ represents a hydrogen atom or a protecting group, preferably a hydrogen atom. The protecting group is preferably a protecting group that decomposes under the action of an acid or a base, and preferably a protecting group that decomposes with an acid. Specific examples of the protecting group include linear or cyclic alkyl groups and linear or cyclic alkyl groups having an oxygen atom in the chain. Examples of linear or cyclic alkyl groups include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, and a cyclohexyl group. Examples of linear alkyl groups having an oxygen atom in the chain include alkyloxyalkyl groups, and preferred are a methyloxymethyl (MOM) group and an ethyloxyethyl (EE) group. Examples of cyclic alkyl groups having an oxygen atom in the chain include an epoxy group, a glycidyl group, an oxetanyl group, a tetrahydrofuranyl group, and a tetrahydropyranyl (THP) group.

[0292] In formula (N1), the divalent linking group constituting L is not particularly limited, but is preferably a hydrocarbon group, and more preferably an aliphatic hydrocarbon group. The hydrocarbon group may have a substituent and may have atoms other than carbon atoms in the hydrocarbon chain. The divalent linking group is more preferably a divalent hydrocarbon linking group that may have an oxygen atom in the chain, more preferably a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain, a divalent aromatic hydrocarbon group, or a group containing a combination of a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group, and even more preferably a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain. These groups may not have an oxygen atom. The divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. The group containing a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (for example, an arylene alkyl group) preferably has 7 to 22 carbon atoms, more preferably 7 to 18, and even more preferably 7 to 10 carbon atoms.

[0293] Specific examples of the linking group L include linear or branched chain alkylene groups, cyclic alkylene groups, groups containing a combination of linear alkylene groups and cyclic alkylene groups, alkylene groups having an oxygen atom in the chain, linear or branched chain alkenylene groups, cyclic alkenylene groups, arylene groups, and arylene alkylene groups. The linear or branched chain alkylene groups preferably have 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The cyclic alkylene groups preferably have 3 to 12 carbon atoms, more preferably 3 to 6. The groups containing a combination of linear alkylene groups and cyclic alkylene groups preferably have 4 to 24 carbon atoms, more preferably 4 to 12, and even more preferably 4 to 6. The alkylene groups having an oxygen atom in the chain may be linear or cyclic, linear or branched. The alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.

[0294] The linear or branched chain alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3. The linear or branched chain alkenylene group preferably has 1 to 10 C═C bonds, more preferably 1 to 6, and even more preferably 1 to 3. The cyclic alkenylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6. The cyclic alkenylene group preferably has 1 to 6 C═C bonds, more preferably 1 to 4, and even more preferably 1 to 2. The arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. The arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11. Among these, a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkenylene group, an arylene group, and an arylene alkylene group are preferred, and a 1,2-ethylene group, a propanediyl group (particularly a 1,3-propanediyl group), a cyclohexanediyl group (particularly a 1,2-cyclohexanediyl group), a vinylene group (particularly a cis-vinylene group), a phenylene group (1,2-phenylene group), a phenylenemethylene group (particularly a 1,2-phenylenemethylene group), and an ethyleneoxyethylene group (particularly a 1,2-ethyleneoxy-1,2-ethylene group) are more preferred.

[0295] Examples of the base generator include, but are not limited to, the following compounds:

[0296]

[0297] 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.

[0298] Specific preferred compounds for the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of WO 2018 / 038002.

[0299] Specific examples of ammonium salts include, but are not limited to, the following compounds:

[0300] Specific examples of iminium salts include, but are not limited to, the following compounds:

[0301] 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.

[0302] <Solvent> The resin composition of the present invention preferably contains a solvent. Any known solvent can be used as the solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0303] 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, alkyl alkyloxyacetates (for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkyloxypropionates (for example, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionates, Preferred examples of the alkyl cypropionate include alkyl cypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, and propyl 2-alkyloxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, and ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, and diethyl malonate.

[0304] 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.

[0305] Suitable examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0306] Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0307] A preferred example of the sulfoxides is dimethyl sulfoxide.

[0308] 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.

[0309] Preferred examples of ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0310] 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.

[0311] From the viewpoint of improving the properties of the coated surface, it is also preferable to mix two or more kinds of solvents.

[0312] 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, 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. A combination of dimethyl sulfoxide and γ-butyrolactone, or a combination of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred.

[0313] From the viewpoint of coatability, the content of the solvent is preferably an amount such that the total solids concentration of the resin composition of the present invention is 5 to 80 mass%, more preferably an amount such that the total solids concentration is 5 to 75 mass%, even more preferably an amount such that the total solids concentration is 10 to 70 mass%, and even more preferably an amount such that the total solids concentration is 20 to 70 mass%. The solvent content may be adjusted depending on the desired thickness of the coating film and the coating method. When two or more solvents are contained, the total amount of the solvents is preferably within the above range.

[0314] <Metal Adhesion Improver> The resin composition of the present invention preferably contains a metal adhesion improver from the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc. Examples of the metal adhesion improver include a silane coupling agent having an alkoxysilyl group, an aluminum-based adhesion aid, a titanium-based adhesion aid, a compound having a sulfonamide structure, a compound having a thiourea structure, a phosphoric acid derivative compound, a β-ketoester compound, and an amino compound.

[0315] [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.).

[0316]

[0317] 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.).

[0318] [Aluminum-Based Adhesion Aid] Examples of aluminum-based adhesion aids include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0319] 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.

[0320] 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.

[0321] <Migration Inhibitor> The resin composition of the present invention preferably further contains a migration inhibitor. By including a migration inhibitor, for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, migration of metal ions derived from the metal layer (or metal wiring) into the film can be effectively inhibited.

[0322] 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.

[0323] As the migration inhibitor, an ion trapping agent that traps anions such as halogen ions can also be used.

[0324] Other migration inhibitors, for example, other migration inhibitors, 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, the compounds described in paragraph 0166 of WO 2015 / 199219, and the like can be used, the contents of which are incorporated herein by reference.

[0325] Specific examples of the migration inhibitor include the following compounds.

[0326]

[0327] When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass%, more preferably 0.05 to 2.0 mass%, and even more preferably 0.1 to 1.0 mass%, based on the total solid content of the resin composition.

[0328] 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.

[0329] <Polymerization Inhibitor> The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

[0330] 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, tris(2,6-dimethyl-3-hydroxy-4-tert-butyl-benzyl)isocyanurate, and the like, the contents of which are incorporated herein by reference.

[0331] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20 mass%, more preferably 0.02 to 15 mass%, and even more preferably 0.05 to 10 mass%, based on the total solid content of the resin composition.

[0332] 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.

[0333] <Acid Scavenger> The resin composition of the present invention preferably contains an acid scavenger to reduce performance changes over time from exposure to heating. Here, the acid scavenger refers to a compound capable of capturing generated acid by its presence in the system, and is preferably a compound with low acidity and high pKa. The acid scavenger is preferably a compound having an amino group, and is preferably a primary amine, a secondary amine, a tertiary amine, an ammonium salt, or a tertiary amide. Primary amines, secondary amines, tertiary amines, or ammonium salts are preferred, with secondary amines, tertiary amines, or ammonium salts being more preferred. Preferred examples of the acid scavenger include compounds having an imidazole structure, a diazabicyclo structure, an onium structure, a trialkylamine structure, an aniline structure, or a pyridine structure, alkylamine derivatives having a hydroxyl group and / or an ether bond, and aniline derivatives having a hydroxyl group and / or an ether bond. When the acid scavenger has an onium structure, it is preferably a salt having a cation selected from ammonium, diazonium, iodonium, sulfonium, phosphonium, pyridinium, or the like, and an anion of an acid less acidic than the acid generated by the acid generator.

[0334] Examples of acid scavengers having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole. Examples of acid scavengers having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene, and 1,8-diazabicyclo[5,4,0]undec-7-ene. Examples of acid scavengers having an onium structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, and sulfonium hydroxides having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, tris(t-butylphenyl)sulfonium hydroxide, bis(t-butylphenyl)iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. Examples of acid scavengers having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Examples of acid scavengers having an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Examples of acid scavengers having a pyridine structure include pyridine and 4-methylpyridine. Examples of alkylamine derivatives having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris(methoxyethoxyethyl)amine. Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N,N-bis(hydroxyethyl)aniline.

[0335] Specific examples of preferred acid scavengers 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, ethylenediamine, 1,5-diaminopentane ... diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, ethylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, aminomorpholine, aminoalkylmorpholine, and the like.

[0336] The acid scavenger may be used alone or in combination of two or more. The composition according to the present invention may or may not contain an acid scavenger, but when it contains an acid scavenger, the content of the acid scavenger is preferably 0.001 to 10 mass %, more preferably 0.01 to 5 mass %, based on the total solid content of the composition.

[0337] The ratio of the acid generator to the acid scavenger used is preferably acid generator / acid scavenger (molar ratio) = 2.5 to 300. That is, from the viewpoints of sensitivity and resolution, the molar ratio is preferably 2.5 or more, and from the viewpoint of suppressing a decrease in resolution due to thickening of the relief pattern over time after exposure until heat treatment, it is preferably 300 or less. The acid generator / acid scavenger (molar ratio) is preferably 5.0 to 200, more preferably 7.0 to 150.

[0338] <Other Additives> The resin composition of the present invention may contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, UV absorbers, organic titanium compounds, antioxidants, anti-aggregation agents, phenolic compounds, other polymeric compounds, plasticizers, and other auxiliary agents (e.g., antifoaming agents, flame retardants, etc.), as needed, within the scope of obtaining 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, paragraphs 0183 and after of JP 2012-003225 A (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812), and paragraphs 0101 to 0104, 0107 to 0109, etc. of JP 2008-250074 A, the contents of which are incorporated herein by reference. When these additives are incorporated, the total content is preferably 3% by mass or less of the solid content of the resin composition of the present invention.

[0339] [Surfactant] Various surfactants can be used as the surfactant, such as a fluorine-based surfactant, a silicone-based surfactant, a hydrocarbon-based surfactant, etc. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0340] By adding a surfactant to the resin composition of the present invention, the liquid properties (particularly fluidity) of the coating liquid composition when prepared are further improved, and the uniformity of the coating thickness and the liquid saving can be further improved. That is, when a film is formed using a coating liquid containing a surfactant, the interfacial tension between the surface to be coated and the coating liquid is reduced, improving the wettability of the surface to be coated and the coatability of the surface to be coated. Therefore, it is possible to more suitably form a uniform film with small thickness unevenness.

[0341] Examples of fluorine-based surfactants include the compounds described in paragraph 0328 of WO 2021 / 112189, the contents of which are incorporated herein by reference. As the fluorine-based surfactant, fluorine-containing polymer compounds containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups) can also be preferably used, and examples thereof include the following compounds.

[0342] The weight-average molecular weight of the above compound is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. As the fluorosurfactant, a fluorine-containing polymer having an ethylenically unsaturated bond in the side chain can also be used. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP 2010-164965 A, the contents of which are incorporated herein by reference. Commercially available products include Megafac RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

[0343] The fluorine content in the fluorine-containing surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-containing surfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and liquid saving, and also has good solubility in the composition.

[0344] Examples of silicone surfactants, hydrocarbon surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants include the compounds described in paragraphs 0329 to 0334 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0345] The surfactant may be used alone or in combination of two or more. The content of the surfactant is preferably 0.001 to 2.0 mass %, more preferably 0.005 to 1.0 mass %, based on the total solid content of the composition.

[0346] [Higher Fatty Acid Derivative] In order to prevent polymerization inhibition caused by oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to the resin composition of the present invention, and the higher fatty acid derivative may be unevenly distributed on the surface of the resin composition of the present invention during drying after application.

[0347] In addition, the higher fatty acid derivative may be a compound described in paragraph 0155 of WO 2015 / 199219, the contents of which are incorporated herein by reference.

[0348] When the resin composition contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10 mass% based on the total solid content of the resin composition. Only one type of higher fatty acid derivative may be used, or two or more types may be used. When two or more types of higher fatty acid derivatives are used, the total content thereof is preferably within the above range.

[0349] [Thermal Polymerization Initiator] Examples of thermal polymerization initiators include thermal radical polymerization initiators. Thermal radical polymerization initiators are compounds that generate radicals by thermal energy and initiate or promote 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. In addition, photopolymerization initiators may also have the function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.

[0350] 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.

[0351] When a thermal polymerization initiator is contained, the content thereof is preferably 0.1 to 30 mass% relative to the total solid content of the resin composition, more preferably 0.1 to 20 mass%, and even more preferably 0.5 to 15 mass%. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more types of thermal polymerization initiators are contained, it is preferable that the total amount is in the above range.

[0352] [Inorganic Particles] Specific examples of inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.

[0353] The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, even more preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. The above average particle size of the inorganic particles is the primary particle size and also the volume average particle size. The volume average particle size can be measured, for example, by dynamic light scattering using a Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurement is difficult, it can also be measured by centrifugal sedimentation light transmission method, X-ray transmission method, or laser diffraction / scattering method.

[0354] [Ultraviolet absorber] Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, triazine-based, etc. Specific examples of the ultraviolet absorber include the compounds described in paragraphs 0341 to 0342 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0355] The ultraviolet absorbers may be used singly or in combination of two or more. When the resin composition contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.001% by mass or more and 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less, based on the total solid mass of the resin composition.

[0356] [Organotitanium Compound] When the resin composition contains an organotitanium compound, a resin layer having excellent chemical resistance can be formed even when cured at low temperatures.

[0357] Usable organic titanium compounds include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of organic titanium compounds are shown below in I) to VII): I) Titanium chelate compounds: Titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability to the resin composition and a good curing pattern. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), and titanium diisopropoxide bis(ethylacetoacetate). II) Tetraalkoxytitanium compounds: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], etc. III) Titanocene compounds: for example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc. IV) Monoalkoxytitanium compounds: for example, titanium tris(dioctylphosphate)isopropoxide, titanium tris(dodecylbenzenesulfonate)isopropoxide, etc. V) Titanium oxide compounds: for example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc.VI) Titanium tetraacetylacetonate compounds: for example, titanium tetraacetylacetonate, etc. VII) Titanate coupling agents: for example, isopropyl tridodecylbenzenesulfonyl titanate, etc.

[0358] Among these, from the viewpoint of better chemical resistance, the organic titanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

[0359] When an organotitanium compound is contained, its content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the specific resin. When the content is 0.05 part by mass or more, the heat resistance and chemical resistance of the obtained cured pattern are improved, and when it is 10 parts by mass or less, the storage stability of the composition is superior.

[0360] [Antioxidant] By including an antioxidant as an additive, the elongation properties of the cured film and adhesion to metal materials can be improved. Examples of antioxidants include phenol compounds, phosphite ester compounds, and thioether compounds. Specific examples of antioxidants include the compounds described in paragraphs 0348 to 0357 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0361] The content of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. By adding an amount of 0.1 part by mass or more, it is easy to obtain the effect of improving elongation properties and adhesion to metal materials even in high-temperature, high-humidity environments, and by adding an amount of 10 parts by mass or less, the sensitivity of the resin composition is improved, for example, through interaction with the photosensitizer. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof be within the above range.

[0362] [Anti-aggregating Agent] Examples of the anti-aggregating agent include sodium polyacrylate.

[0363] The anti-aggregating agent may be used singly or in combination of two or more. When the resin composition contains an anti-aggregating agent, the content of the anti-aggregating agent is preferably 0.01 mass % or more and 10 mass % or less, and more preferably 0.02 mass % or more and 5 mass % or less, relative to the total mass of the solid content of the resin composition.

[0364] [Phenol-based compounds] Examples of phenol-based compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetrith-FR-CR, and BisRS-26X (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, and BIR-BIPC-F (all trade names, manufactured by Asahi Organic Chemicals Co., Ltd.).

[0365] The phenolic compound may be used alone or in combination of two or more. When the resin composition contains a phenolic compound, the content of the phenolic compound is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less, based on the total solid mass of the resin composition.

[0366] [Other Polymer Compounds] Examples of other polymer compounds include siloxane resins, (meth)acrylic polymers copolymerized with (meth)acrylic acid, novolac resins, resol resins, polyhydroxystyrene resins, and copolymers thereof. The other polymer compounds may be modified compounds into which crosslinking groups such as methylol groups, alkoxymethyl groups, and epoxy groups have been introduced.

[0367] The other polymer compounds may be used singly or in combination of two or more. When the resin composition contains the other polymer compounds, the content of the other polymer compounds is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less, based on the total solid mass of the resin composition.

[0368] <Characteristics of Resin Composition> The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. ２ / s~12,000mm ２ / s is preferred, and 2,000 mm ２ / s~10,000mm ２ / s is more preferable, and 2,500 mm ２ / s~8,000mm ２ Within the above range, it is easy to obtain a highly uniform coating film. ２ If the thickness is more than 12,000 mm / s, it is easy to apply the coating to a thickness required for an insulating film for rewiring, for example. ２ / s or less, a coating film with excellent surface condition can be obtained. The absolute value of the viscosity change rate, expressed by the following formula, of the viscosity of the resin composition after storage at 23°C for 14 days after preparation, relative to the viscosity of the resin composition on the day of preparation, is preferably 10% or less, more preferably 8% or less, and even more preferably 5% or less. Viscosity change rate (%) = {(viscosity of resin composition on the day of preparation) - (viscosity of resin composition after storage)} / (viscosity of resin composition on the day of preparation) × 100 The viscosity of the composition can be measured, for example, using a viscometer (such as Toki Sangyo RE85R) at a temperature adjusted to 25°C.

[0369] <Restrictions on substances contained in the resin composition> The water content of the resin composition of the present invention is preferably less than 0.5% by mass, more preferably less than 0.3% by mass, and even more preferably less than 0.1% by mass. If it is less than 0.5% by mass, the storage stability of the resin composition is improved. Methods for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.

[0370] From the viewpoint of insulating properties, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. 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.

[0371] Furthermore, examples of methods for reducing metal impurities unintentionally contained in the resin composition of the present invention include selecting raw materials with a low metal content as raw materials for constituting the resin composition of the present invention, filtering the raw materials for constituting the resin composition of the present invention, and lining the inside of the apparatus with polytetrafluoroethylene or the like to perform distillation under conditions that minimize contamination as much as possible.

[0372] Considering the use of the resin composition of the present invention as a semiconductor material, the content of halogen atoms is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass, from the viewpoint of wiring corrosion. In particular, those present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferable that the total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above-mentioned range. Preferred methods for adjusting the content of halogen atoms include ion exchange treatment.

[0373] A conventionally known container can be used as a container for storing the resin composition of the present invention. For the purpose of preventing impurities from being mixed into the raw materials or the resin composition of the present invention, it is also preferable to use a multi-layer bottle whose inner wall is made of six types of six resin layers, or a bottle with a seven-layer structure made of six types of resin. Examples of such containers include the container described in JP 2015-123351 A.

[0374] <Cured Product of Resin Composition> A cured product of the resin composition can be obtained by curing the resin composition of the present invention. The cured product of the present invention is a cured product obtained by the method for producing a cured product of the present invention. The shape of the cured product of the resin composition is not particularly limited, and can be selected depending on the application, such as a film, a rod, a sphere, or a pellet. In the present invention, the cured product is preferably in the form of a film. By patterning the resin composition, the shape of the cured product can be selected depending on the application, such as forming a protective film on a wall surface, forming via holes for electrical conductivity, adjusting impedance, capacitance, or internal stress, or imparting heat dissipation functionality. The film thickness of the cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less. The shrinkage rate upon curing of the resin composition of the present invention is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage rate refers to the percentage change in volume of the resin composition before and after curing, and can be calculated using the following formula: Shrinkage rate [%] = 100 - (volume after curing / volume before curing) x 100

[0375] <Characteristics of cured product of resin composition> The imidization reaction rate of the cured product obtained by the method for producing a cured product 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 obtained by the method for producing a cured product 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 obtained by the method for producing a cured product of the present invention is preferably 180°C or more, more preferably 210°C or more, and even more preferably 230°C or more. The linear thermal expansion coefficient of the cured product obtained by the method for producing a cured product of the present invention is preferably 55 ppm / K or less, more preferably 50 ppm / K or less, and even more preferably 45 ppm / K or less.

[0376] <Preparation of Resin Composition> The resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and can be carried out by a conventionally known method. Examples of the mixing method include mixing with a stirring blade, mixing with a ball mill, and mixing by rotating a tank. The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.

[0377] Filtration using a filter is preferably performed to remove foreign matter such as dust and fine particles from the resin composition of the present invention. The filter pore size is, for example, preferably 5 μm or less, more preferably 1 μm or less, even more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. When the filter material is polyethylene, HDPE (high-density polyethylene) is more preferable. The filter may be pre-washed with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or parallel. When multiple types of filters are used, filters with different pore sizes or materials may be combined. An example of a connection mode is a mode in which an HDPE filter with a pore size of 1 μm is connected in series as the first stage and an HDPE filter with a pore size of 0.2 μm is connected in series as the second stage. Various materials may also be filtered multiple times. When filtration is performed multiple times, circulating filtration may be used. Filtration may also be performed under pressure. When filtering under pressure, the pressure to be applied is preferably 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, even more preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less. In addition to filtering using a filter, a process of removing impurities using an adsorbent may be performed. Filter filtration and a process of removing impurities using an adsorbent may be combined. Known adsorbents can be used as the adsorbent. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. After filtering using a filter, the resin composition filled in a bottle may be subjected to a degassing process by placing it under reduced pressure.

[0378] 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.

[0379] Synthesis of Polyimide Precursor [Synthesis Example P-1C: Synthesis of Polyimide Precursor (P-1C)] 21.2 g of 4,4'-oxydiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, and 250 mL of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at 60°C for 4 hours to synthesize a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to -10°C, and 17.0 g of thionyl chloride was added over 60 minutes while maintaining the temperature at -10±5°C. After dilution with 50 mL of N-methylpyrrolidone, a solution of 12.6 g of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture over 60 minutes at -10±5°C, and the mixture was stirred at room temperature for 2 hours. Thereafter, 10.0 g of ethanol was added and the mixture was stirred at room temperature for 1 hour. Next, 6,000 g of water was added to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The precipitate (solid polyimide precursor) after stirring was collected by filtration and dissolved in 500 g of tetrahydrofuran. 6,000 g of water (poor solvent) was added to the resulting solution to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The precipitate (solid polyimide precursor) after stirring was again filtered and dried at 45°C under reduced pressure for 3 days. 46.6 g of the dried powder was dissolved in 419.6 g of tetrahydrofuran, and then 2.3 g of triethylamine was added and the mixture was stirred at room temperature for 35 minutes. Then, 3,000 g of ethanol was added, and the precipitate was collected by filtration. The resulting precipitate was dissolved in 281.8 g of tetrahydrofuran. To this was added 17.1 g of water and 46.6 g of ion exchange resin UP6040 (manufactured by AmberTec), followed by stirring for 4 hours. Thereafter, the ion exchange resin was removed by filtration, and the resulting polymer solution was added to 5,600 g of water to obtain a precipitate. The precipitate was collected by filtration and dried under reduced pressure at 45°C for 24 hours to obtain 45.1 g of polyimide precursor (P-1C). The structure of polyimide precursor (P-1C) is represented by the following formula (P-1C). The structure of each repeating unit is: １The molecular weight of the polyimide precursor (P-1) was determined from a H-NMR spectrum. The weight average molecular weight (Mw) of the polyimide precursor (P-1) was measured by gel permeation chromatography (standard polystyrene equivalent) and was found to be 20,000.

[0380] Synthesis Example P-2: Synthesis of Polyimide Precursor (P-2) 10.4 g (47.6 mmol) of pyromellitic anhydride, 10.6 g (20.4 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride), 17.8 g (137 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 22.8 g (289 mmol) of pyridine, and 75 g of diglyme were mixed and stirred at a temperature of 60°C for 5 hours to produce a diester of pyromellitic anhydride and 4,4'-(4,4''-isopropylidenediphenoxy)bis(phthalic anhydride) with 2-hydroxyethyl methacrylate. The mixture was then cooled to -20°C, and 17.70 g (141 mmol) of thionyl chloride was added dropwise over 90 minutes. The mixture was stirred for 2 hours, resulting in a white precipitate of pyridinium hydrochloride. Next, 21.1 g (66.0 mmol) of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl dissolved in 100 mL of NMP (N-methyl-2-pyrrolidone) was added dropwise over 2 hours. 10.0 g (217 mmol) of ethanol was then added, and the mixture was stirred for 2 hours. The polyimide precursor was then precipitated in 4 liters of water, and the water-polyimide precursor mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor was collected by filtration, stirred again in 4 liters of water for 30 minutes, and filtered again. The resulting polyimide precursor was then dried under reduced pressure at 45°C for 2 days to obtain polyimide precursor (P-2). The resulting polyimide precursor (P-2) had a weight average molecular weight of 60,500 and a number average molecular weight of 24,400. The polyimide precursor (P-2) is a resin having two repeating units represented by the following formula (P-2). The structure of each repeating unit is: １ Determined from H-NMR spectrum.

[0381] [Synthesis Example P-16: Synthesis of Polyimide Precursor (P-16)] Polyimide precursor (P-16) was synthesized in the same manner as polyimide precursor (P-2), except that the diamine used was changed appropriately. Polyimide precursor (P-16) is a resin having two repeating units represented by the following formula (P-16). The structure of each repeating unit is: １ Determined from H-NMR spectrum. The composition ratio, weight average molecular weight, and number average molecular weight were as follows: Here, with regard to the composition ratio (mol %), for example, "A / B=50 / 50" means that 50 mol % of repeating units represented by "A" and 50 mol % of repeating units represented by "B" are included.

[0382]

[0383] [Synthesis Examples P-3 to P-15: Synthesis of Polyimide Precursors (P-3) to (P-15)] Polyimide precursors (P-3) to (P-15) were synthesized in the same manner as for polyimide precursor (P-2), except that the carboxylic acid dianhydride used was changed appropriately. Polyimide precursors (P-3) to (P-15) were synthesized in the same manner as for polyimide precursor (P-2), respectively, Ｘ The structure of each repeating unit is represented by the formulas (RX-3) to (RX-15). １ The molecular weights were determined from H-NMR spectra. The composition ratios (mol % of repeating units), weight average molecular weights, and number average molecular weights of the polyimide precursors (P-2) to (P-15) are shown in the table below. Here, for example, a description of the composition ratio (mol %), "A / B=70 / 30," means that the polyimide precursor contains 70 mol % of repeating units designated "A" and 30 mol % of repeating units designated "B."

[0384]

[0385] Synthesis Example P-16C: Synthesis of Polyimide Precursor (P-16C) 77.5 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 73.5 g of 4,4'-biphthalic dianhydride were placed in a separable flask, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added. 79.1 g of pyridine was added with stirring at room temperature to obtain a reaction mixture. After the heat generated by the reaction had ceased, the mixture was allowed to cool to room temperature and allowed to stand for an additional 16 hours. Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Subsequently, a suspension of 93.0 g of 4,4'-diaminodiphenyl ether suspended in 350 ml of γ-butyrolactone was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and the mixture was stirred for 1 hour. Thereafter, 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was collected by filtration to obtain a reaction solution. The resulting reaction solution was added to 3 liters of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer, and the resulting precipitate was collected by filtration and vacuum dried to obtain a powdered polyimide precursor (P-16C). The weight average molecular weight (Mw) of this polyimide precursor (P-16C) was measured and found to be 22,600. The polyimide precursor (P-16C) contains repeating units having the following structure. The structure of each repeating unit is as follows: １ Determined from H-NMR spectrum.

[0386] <Synthesis of Polymerizable Compound> [Synthesis of M-8] In a flask equipped with a stirrer and a condenser, 27.44 g (200 mmol) of 2-(4-aminophenyl)ethyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.03 g of p-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 250 mL of tetrahydrofuran and cooled to 0°C. Next, 29.48 g (190 mmol) of Karenz MOI (manufactured by Showa Denko K.K.) was added dropwise over 1 hour, and the mixture was stirred at 0°C to 10°C for 1 hour, then heated to 25°C and stirred for 2 hours. Subsequently, this was crystallized in a solution of 800 mL of ethyl acetate / 200 mL of hexane and filtered. The residue was then stirred in 500 mL of ethyl acetate for 1 hour and filtered. This was dried at 45°C for 24 hours to obtain 45 g of M-8. It was confirmed that this was M-8. １ The structure of M-8 was confirmed by H-NMR spectrum. The structure of M-8 is shown in the following formula (M-8).

[0387] [Synthesis of M-9 to M-13] M-9 to M-13 were synthesized in the same manner as in the synthesis of M-8, except that the raw materials were appropriately changed. The structures of M-9 to M-13 are shown in the following formulas (M-9) to (M-13).

[0388] Examples and Comparative Examples In each example, the components listed in the table below were mixed to obtain a resin composition. In each comparative example, the components listed in the table below were mixed to obtain a comparative composition. Specifically, the content of each component listed in the table was the amount (parts by mass) listed in the "Parts by Mass" column of each column in the table. The obtained resin composition and comparative composition were pressure-filtered using a polytetrafluoroethylene filter with a pore width of 0.5 μm. In the table, a "-" indicates that the composition did not contain the corresponding component. In each example or comparative example, the viscosity change rate (%) of the resin composition or comparative composition after storage at 23°C for 14 days after formulation, relative to the viscosity of the composition on the day of formulation, was measured, as expressed by the following formula. The measurement results are listed in the "Storage Stability" column of the table. The numerical values ​​in the table are in %. It is preferable that the absolute value of the viscosity change rate is 10% or less. Viscosity change rate (%) = {(viscosity of resin composition on the day of blending) - (viscosity of resin composition after the above storage)} / (viscosity of resin composition on the day of blending) x 100 Viscosity can be measured, for example, using a viscometer RE85R (rotor: 1°34' x R24) manufactured by Toki Sangyo Co., Ltd., with the temperature adjusted to 25°C.

[0389]

[0390]

[0391]

[0392]

[0393]

[0394]

[0395]

[0396] Details of each component listed in the table are as follows:

[0397] [Polyimide precursors] P-1C, P-2 to P-15, P-16C: Synthetic products of the above. P-1C and P-16C are compounds that do not fall under the category of the above-mentioned specific resins. P-2 to P-15 are compounds that fall under the category of the above-mentioned specific resins.

[0398] [Monomers (polymerizable compounds)] M-1: tetraethylene glycol dimethacrylate M-2: tetraethylene glycol diacrylate M-3: ethylene glycol dimethacrylate M-4: diethylene glycol dimethacrylate M-5: triethylene glycol dimethacrylate M-6: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) M-7: NK Ester A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.) M-8 to M-13: synthetic products as above M-14: the following compound

[0399] [Polymerization initiator] I-1: Irgacure OXE-01 ...

Claims

1. a film-forming step of applying a resin composition containing a polyimide precursor having a repeating unit represented by formula (1) and a solvent onto a substrate to form a film; a treatment step of contacting the membrane with a treatment solution; and a heating step of heating the film after the treating step; The treatment liquid contains at least one compound selected from the group consisting of a basic compound and a base generator. A method for producing a cured product. 【Chemistry 1】 In formula (1), R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group; R 1 and R 2 At least one of X is a monovalent organic group having an ethylenically unsaturated bond. 1 is a group containing a structure represented by the following formula (X-1), 1 is a divalent organic group represented by the following general formula (Y-1). 【Chemistry 2】 In formula (X-1), Ar 1 and Ar 2 each independently represents an aromatic ring structure; X is -CR X1 2 -, -C(=CR X2 2 ) - or -S(=O) 2 - represents R X1 each independently represents a hydrogen atom, an aromatic hydrocarbon group which may have a substituent, or a hydrocarbon group which may be substituted with a halogen atom; X1 may be bonded to form a ring structure, R X2 represents a halogen atom, n represents an integer of 1 or more, m represents an integer of 1 or more, and * represents a bonding site with another structure. 【Chemistry 3】 In formula (Y-1), R 3 ~R 10 are each independently a hydrogen atom or a monovalent group; R 3 ~R 10 at least one of R is a fluorine atom, an alkyl group which may have a substituent, a substituent having a fluorine atom, or an alkoxy group which may have a substituent; 5 and R 7 , R 6 and R 8 may be bonded to form a ring structure, and each * represents a bonding site with the nitrogen atom in formula (1).

2. X in formula (1) 1 The method for producing a cured product according to claim 1, wherein the compound (A) is a structure represented by the following formula (X-2): 【Chemistry 4】 In formula (X-2), X is -CR X1 2 -, -C(=CR X2 2 ) - or -S(=O) 2 - represents R X1 each independently represents a hydrogen atom, an aromatic hydrocarbon group which may have a substituent, or a hydrocarbon group which may be substituted with a halogen atom; X1 may be bonded to form a ring structure, R X2 represents a halogen atom, and # represents a bonding site with the carbonyl group in formula (1).

3. X in formula (1) 1 The method for producing a cured product according to claim 1, wherein the compound (I) has a bisphenol structure including a structure represented by formula (X-1).

4. X in formula (1) 1 The method for producing a cured product according to claim 1 or 3, wherein the compound (A) is a structure represented by the following formula (X-3): 【Chemistry 5】 In formula (X-3), X is -CR X1 2 -, -C(=CR X2 2 ) - or -S(=O) 2 - represents R X1 each independently represents a hydrogen atom, an aromatic hydrocarbon group which may have a substituent, or a hydrocarbon group which may be substituted with a halogen atom; X1 may be bonded to form a ring structure, R X2 represents a halogen atom, and # represents a bonding site with the carbonyl group in formula (1).

5. The method for producing a cured product according to any one of claims 1 to 3, wherein the base contained in the treatment liquid is a secondary amine or a tertiary amine, and the base generator is a compound that generates a secondary amine or a tertiary amine.

6. The method for producing a cured product according to any one of claims 1 to 3, wherein the base and the base generator contained in the treatment liquid are compounds having an amide group.

7. The method for producing a cured product according to any one of claims 1 to 3, wherein the base or base generator contained in the treatment liquid is a compound having an acrylamide group or a methacrylamide group.

8. The method for producing a cured product according to any one of claims 1 to 3, wherein the heating temperature in the heating step is 180°C or lower and the heating time is 3 hours or less.

9. The method for producing a cured product according to any one of claims 1 to 3, further comprising, between the film-forming step and the treatment step, an exposure step of selectively exposing the film to light, and a development step of developing the exposed film with a developer to form a patterned film.

10. The method for producing a cured product according to claim 9 , wherein the treatment step is a rinsing step of washing the patterned film with the treatment liquid.

11. The method for producing a cured product according to claim 9 , further comprising the step of: cleaning the patterned film by contacting it with a rinse liquid, and then carrying out a treatment step.

12. The method for producing a cured product according to any one of claims 1 to 3, further comprising an exposure step of selectively exposing the film to light between the film-forming step and the treatment step, the treatment step being a step of developing the film using the treatment liquid as a developer to form a patterned film.

13. The method for producing a cured product according to claim 9 , wherein the development is a negative development.

14. The method for producing a cured product according to any one of claims 1 to 3, further comprising, after the treatment step and before the heating step, a heating and cooling step of heating the film at a temperature of 80 to 120°C and cooling it.

15. The method for producing a cured product according to any one of claims 1 to 3, wherein the resin composition contains a photopolymerization initiator.

16. The method for producing a cured product according to any one of claims 1 to 3, wherein the obtained cured product has a linear thermal expansion coefficient of 50 ppm / K or less in the range of 25°C to 125°C.

17. The method for producing a cured product according to any one of claims 1 to 3, wherein the resulting cured product has a breaking elongation of 50% or more.

18. The method for producing a cured product according to any one of claims 1 to 3, wherein an absolute value of a viscosity change rate of the resin composition after storage at 23°C for 14 days after preparation relative to a viscosity of the resin composition on a day of preparation, the viscosity change rate being represented by the following formula, is 10% or less. Viscosity change rate (%)={(viscosity of the resin composition on the day of preparation)−(viscosity of the resin composition after the storage)} / (viscosity of the resin composition on the day of preparation)×100

19. A method for producing a semiconductor device, comprising the method for producing a cured product according to any one of claims 1 to 3.

20. A treatment liquid used in a method for producing a cured product, the method including a film-forming step of applying a resin composition containing a polyimide precursor having a repeating unit represented by formula (1) and a solvent onto a substrate to form a film, a treatment step of contacting the film with a treatment liquid, and a heating step of heating the film after the treatment step, At least one compound selected from the group consisting of a basic compound and a base generator. Processing liquid. 【Chemistry 6】 In formula (1), R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group; R 1 and R 2 At least one of X is a monovalent organic group having an ethylenically unsaturated bond. 1 is a group containing a structure represented by the following formula (X-1), 1 is a divalent organic group represented by the following general formula (Y-1). 【Chemistry 7】 In formula (X-1), Ar 1 and Ar 2 each independently represents an aromatic ring structure; X is -CR X1 2 -, -C(=CR X2 2 ) - or -S(=O) 2 - represents R X1 each independently represents a hydrogen atom, an aromatic hydrocarbon group which may have a substituent, or a hydrocarbon group which may be substituted with a halogen atom; X1 may be bonded to form a ring structure, R X2 represents a halogen atom, n represents an integer of 1 or more, m represents an integer of 1 or more, and * represents a bonding site with another structure. 【Chemistry 8】 In formula (Y-1), R 3 ~R 10 are each independently a hydrogen atom or a monovalent group; R 3 ~R 10 at least one of R is a fluorine atom, an alkyl group which may have a substituent, a substituent having a fluorine atom, or an alkoxy group which may have a substituent; 5 and R 7 , R 6 and R 8 may be bonded to form a ring structure, and each * represents a bonding site with the nitrogen atom in formula (1).

21. A resin composition comprising a polyimide precursor having a repeating unit represented by formula (1), the resin composition is applied to a substrate to form a film, a treatment step is a treatment step of contacting the film with a treatment liquid, and a heating step is a heating step of heating the film after the treatment step, the treatment liquid containing at least one compound selected from the group consisting of a basic compound and a base generator; Resin composition. 【Chemistry 9】 In formula (1), R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group; R 1 and R 2 At least one of X is a monovalent organic group having an ethylenically unsaturated bond. 1 is a group containing a structure represented by the following formula (X-1), 1 is a divalent organic group represented by the following general formula (Y-1). 【Chemistry 10】 In formula (X-1), Ar 1 and Ar 2 each independently represents an aromatic ring structure; X is -CR X1 2 -, -C(=CR X2 2 ) - or -S(=O) 2 - represents R X1 each independently represents a hydrogen atom, an aromatic hydrocarbon group which may have a substituent, or a hydrocarbon group which may be substituted with a halogen atom; X1 may be bonded to form a ring structure, R X2 represents a halogen atom, n represents an integer of 1 or more, m represents an integer of 1 or more, and * represents a bonding site with another structure. 【Chemistry 11】 In formula (Y-1), R 3 ~R 10 are each independently a hydrogen atom or a monovalent group; R 3 ~R 10 at least one of R is a fluorine atom, an alkyl group which may have a substituent, a substituent having a fluorine atom, or an alkoxy group which may have a substituent; 5 and R 7 , R 6 and R 8 may be bonded to form a ring structure, and each * represents a bonding site with the nitrogen atom in formula (1).

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