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

Abstract

Provided are: a resin composition comprising a resin having a structure represented by formula (A-1); a cured product obtained by curing the composition and a method for producing the cured product; a laminate comprising the cured product and a method for producing the laminate; a semiconductor device and a method for producing the semiconductor device; and a novel polyimide.

Description

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

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

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

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

[0004] For example, Patent Document 1 describes a photosensitive resin composition comprising (A) at least one component selected from polyimide precursors and polyimides, (B) a photopolymerization initiator, (C) a solvent, and (D) an allyl group-containing compound of a specific structure.

[0005] Japanese Patent Publication No. 2024-091579

[0006] From the perspective of preventing dielectric breakdown in stress concentration on devices and the like, there is a demand for improving the elongation at break of the film formed in the resin composition.

[0007] An object of the present invention is to provide a resin composition from which a cured product having excellent elongation at break can be obtained, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device including the method for producing the cured product, and a semiconductor device including the cured product. Another object of the present invention is to provide a novel polyimide.

[0008] Examples of typical embodiments of the present invention are shown below. <1> A resin composition containing a resin which is a polyimide having a structure represented by the following formula (A-1). In formula (A-1), Z １ represents a group represented by the following formula (AA-1), and Q １ to Q ８ each independently represents a hydrogen atom or a monovalent organic group, n represents an integer of 0 to 2, m represents an integer of 0 to 2, n + m is 2, and when n is 2, two Qs １ to Q ４ may be the same or different from each other. When m is 2, two Qs ５ to Q ８ may be the same or different from each other. At least two of Q １ to Q ４ may combine to form a ring structure, and at least two of Q ５ to Q ８ may combine to form a ring structure. L １ each independently represents -O-, -C(=O)O- or -S-, L ２ each independently represents -O-, -C(=O)O- or -S-, and * each independently represents a bonding site with a nitrogen atom. In formula (AA-1), any two of G １ to G ８ represent a bonding site with L １ or L ２ in formula (A-1), and the other G １ to G８ Each of these independently represents a hydrogen atom or a monovalent organic group. <2> The resin composition according to <1>, wherein the resin has polymerizable groups. <3> The resin composition according to <2>, wherein the polymerizable value of the resin is 0.2 to 3.0 mmol / g. <4> The resin composition according to any one of <1> to <3>, wherein when a film with a thickness of 5 μm is formed using the resin composition, the transmittance of the film at a wavelength of 365 nm is 15% or more. <5> The resin composition according to any one of <1> to <4>, wherein the resin contains repeating units represented by the following formula (1-1). In formula (1-1), X １ represents an organic group with 4 or more carbon atoms, Y １ R represents an organic group with 4 or more carbon atoms. １ Each of these independently represents a structure expressed by the following formula (R-1), where a represents an integer from 0 to 4, b represents an integer greater than or equal to 0, and X １ and Y １ At least one of them includes a structure represented by formula (A-1). In formula (R-1), L １ represents a 1+1 valent linking group, A １ represents a polymerizable group, a1 represents an integer greater than or equal to 1, and * represents X in formula (1-1). １ or Y １ This represents the connection site with the above Y. １ The resin composition according to <5>, wherein the structure is represented by formula (A-1). <7> The sum of a and b in formula (1-1) is 1 or more, and there are a + b R １ In at least one of the equations, A in equation (R-1) １ The resin composition according to <5>, wherein at least one of is a vinylphenyl group, a maleimide group, a (meth)acrylokyyl group, a vinyl group, an allyl group, an epoxy group, or a group containing these. <8> The sum of a and b in formula (1-1) is 1 or more, and there are a + b R １ In at least one of the equations, A in equation (R-1) １ The resin composition according to <5>, wherein at least one of the members is a vinylphenyl group. <9> The resin composition according to <5>, wherein the resin further comprises repeating units represented by the following formula (1-2). In formula (1-2), X２ represents an organic group with 4 or more carbon atoms, Y ２ represents an organic group with 4 or more carbon atoms, X ２ and Y ２ None of them include the structure represented by formula (A-1), R ２ Each of these independently represents a structure expressed by equation (R-2), where m is an integer from 0 to 4, n is an integer greater than or equal to 0, and n+m is an integer greater than or equal to 1. In formula (R-2), L ２ represents a² + 1 valent linking group, A ２ represents a polymerizable group, a2 represents an integer greater than or equal to 1, and * represents X in formula (1-2). ２ or Y ２ This represents the bonding site with <10> m+n R in equation (1-2). ２ In at least one of the equations, A in equation (R-2) ２ The resin composition according to <9>, wherein at least one of is a vinylphenyl group, a maleimide group, a (meth)acryloyl group, a vinyl group, an allyl group, an epoxy group, or a group containing these. <11> m+n R in formula (1-2) ２ In at least one of the equations, A in equation (R-2) ２ The resin composition according to <9>, wherein at least one of is a vinylphenyl group. <12> X in formula (1-1) １ The resin composition according to <5>, wherein each of the structures is obtained by removing two or more hydrogen atoms from a structure represented by any of the following formulas (V-1) to (V-4). In formula (V-2), R Ｘ１ Each of these is independently a hydrogen atom, an alkyl group, or an alkyl halide. In formula (V-3), R Ｘ２ and R Ｘ３ Each of these independently represents a hydrogen atom or a substituent, R Ｘ２ and R Ｘ３ They may combine to form a ring structure. <13> X in formula (1-2) ２ The resin composition according to <9>, wherein each of the structures is obtained by removing two or more hydrogen atoms from a structure represented by any of the following formulas (V-1) to (V-4). In formula (V-2), R Ｘ１Each of these is independently a hydrogen atom, an alkyl group, or an alkyl halide. In formula (V-3), R Ｘ２ and R Ｘ３ Each of these independently represents a hydrogen atom or a substituent, R Ｘ２ and R Ｘ３ They may bond to form a ring structure. <14> Y in formula (1-2) ２ The resin composition according to <9>, wherein each of the structures is obtained by removing two or more hydrogen atoms from a structure represented by any of the following formulas (V-1) to (V-4). In formula (V-2), R Ｘ１ Each of these is independently a hydrogen atom, an alkyl group, or an alkyl halide. In formula (V-3), R Ｘ２ and R Ｘ３ Each of these independently represents a hydrogen atom or a substituent, R Ｘ２ and R Ｘ３The elements may bond to form a ring structure. <15> The resin composition according to any one of <1> to <14>, wherein the content of the structure represented by formula (A-1) relative to the mass of the polyimide is 0.1 to 2.0 mmol / g. <16> The resin composition according to any one of <1> to <15>, further comprising a photosensitive agent. <17> The resin composition according to any one of <1> to <16>, further comprising a polymerizable compound. <18> The resin composition according to any one of <1> to <17>, comprising a solvent having a boiling point of 100 to 260°C at 1 atmosphere. <19> The resin composition according to <18>, wherein the content of the solvent having a boiling point of 100 to 260°C is 40% by mass or more relative to the total mass of the composition. <20> The resin composition according to <18> or <19>, comprising two or more solvents having a boiling point of 100 to 260°C. <21> A resin composition according to any one of <1> to <20>, used for forming an interlayer insulating film for a redistribution layer. <22> A cured product obtained by curing the resin composition according to any one of <1> to <21>. <23> A laminate comprising two or more layers made of the cured product according to <22>, with a metal layer between any of the layers made of the cured product. <24> A method for manufacturing a cured product, comprising a film forming step of applying the resin composition according to any one of <1> to <21> onto a substrate to form a film. <25> A method for manufacturing a cured product according to <24>, comprising an exposure step of selectively exposing the film and a developing step of developing the film using a developer to form a pattern. <26> A method for manufacturing a cured product according to <24> or <25>, comprising a heating step of heating the film at 50 to 450°C. <27> A method for manufacturing a laminate, comprising the method for manufacturing a cured product according to <24>. <28> A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured product according to <24>. <29> A semiconductor device comprising the cured product described in <22>. <30> A polyimide having a structure represented by the following formula (A-1). In formula (A-1), Z １ Q represents the group shown in the following formula (AA-1), and １ ~Q ８ Each of these independently represents a hydrogen atom or a monovalent organic group, n represents an integer from 0 to 2, m represents an integer from 0 to 2, n + m is 2, and when n is 2, there are two Qs.１ to Q ４ may be the same or different from each other. When m is 2, there are two Qs present ５ to Q ８ may be the same or different from each other, Q １ to Q ４ at least two of which may combine to form a ring structure, Q ５ to Q ８ at least two of which may combine to form a ring structure, L １ each independently represents -O-, -C(=O)O- or -S-, L ２ each independently represents -O-, -C(=O)O- or -S-, and * each independently represents a bonding site with a nitrogen atom. In formula (AA-1), G １ to G ８ any two of which represent the bonding site with L １ or L ２ in formula (A-1), and the other G １ to G ８ each independently represents a hydrogen atom or a monovalent organic group. <31> The polyimide according to <30>, which contains a repeating unit represented by the following formula (1-1). In formula (1-1), X １ represents an organic group having 4 or more carbon atoms, Y １ represents an organic group having 4 or more carbon atoms, R １ each independently represents a structure represented by the following formula (R-1), a represents an integer of 0 to 4, b represents an integer of 0 or more, and at least one of X １ and Y １ contains a structure represented by formula (A-1). In formula (R-1), L １ represents an a1+1-valent linking group, A １ represents a polymerizable group, a1 represents an integer of 1 or more, and * represents the bonding site with X １ or Y １ in formula (1-1). <32> The polyimide according to <31>, wherein Y １ contains a structure represented by formula (A-1). <33> The sum of a and b in formula (1-1) is 1 or more, and a + b number of Rs １In at least one of them, A in formula (R-1) １ The polyimide according to <31>, wherein at least one of them is a vinylphenyl group. <34> The polyimide according to <31>, further comprising a repeating unit represented by the following formula (1-2). In formula (1-2), X ２ represents an organic group having 4 or more carbon atoms, and Y ２ represents an organic group having 4 or more carbon atoms, and X １ and Y １ both do not contain the structure represented by formula (A-1), and R ２ each independently represents the structure represented by formula (R-2), m represents an integer of 0 to 4, n represents an integer of 0 or more, and n + m is an integer of 1 or more. In formula (R-2), L ２ represents a linking group having a valence of a2 + 1, A ２ represents a polymerizable group, a2 represents an integer of 1 or more, and * represents the bonding site with X ２ or Y ２ in formula (1-2). <35> In at least one of the m + n R ２ in formula (1-2), A ２ in formula (R-2), at least one of them is a vinylphenyl group, The polyimide according to <34>.

[0009] According to the present invention, there are provided a resin composition capable of obtaining a cured product excellent in elongation at break, a cured product obtained by curing the above resin composition, a laminate containing the above cured product, a method for producing the above cured product, a method for producing the above laminate, a method for producing a semiconductor device including the method for producing the above cured product, and a semiconductor device including the above cured product. Further, according to the present invention, a novel polyimide is provided.

[0010] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments explicitly stated. In this specification, numerical ranges represented by the symbol "~" mean a range that includes the numerical values ​​before and after "~" as the lower and upper limits, respectively. In this specification, the term "process" includes not only independent processes but also processes that are indistinguishable from other processes as long as the intended effect of the process is achieved. In the notation of groups (atomic groups) in this specification, notations that do not specify substituted or unsubstituted include both groups (atomic groups) with substituents and groups (atomic groups) without substituents. For example, "alkyl group" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of light used for exposure include the emission line spectrum of mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet (EUV) light, X-rays, electron beams, and other active light or radiation. In this specification, "(meth)acrylate" means both or either "acrylate" and "methacrylate," "(meth)acrylic" means both or either "acrylic" and "methacrylic," and "(meth)acryloyl" means both or either "acryloyl" and "methacryloyl." In this specification, Me in structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, total solids means the total mass of all components of the composition excluding the solvent. In this specification, solids concentration is the mass percentage of the components other than the solvent relative to the total mass of the composition. In this specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​measured using gel permeation chromatography (GPC) and are defined as polystyrene equivalent values, unless otherwise specified.In this specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, by using an HLC-8220GPC (manufactured by Tosoh Corporation) and connecting Guard Column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) in series as columns. Unless otherwise specified, these molecular weights shall be measured using NMP (N-methyl-2-pyrrolidone) as the eluent. However, if NMP is unsuitable as an eluent, such as in cases of low solubility, THF (tetrahydrofuran) may be used. Unless otherwise specified, detection in GPC measurements shall be performed using a UV (ultraviolet) wavelength 254 nm detector. In this specification, when the positional relationship of each layer constituting a laminate is described as "up" or "down," it is sufficient that there are other layers above or below the reference layer among the multiple layers of interest. That is, a third layer or element may be interposed between the reference layer and the other layers, and the reference layer and the other layers do not need to be in contact. Unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "up," or, if there is a resin composition layer, the direction from the substrate to the resin composition layer is referred to as "up," and the opposite direction is referred to as "down." Note that this setting of up and down directions is for convenience in this specification, and in actual embodiments, the "up" direction in this specification may differ from vertically upward. In this specification, unless otherwise specified, a composition may contain two or more compounds corresponding to each component contained in the composition. Also, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component. In this specification, unless otherwise specified, the temperature is 23°C, the atmospheric pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, preferred embodiments are more preferred embodiments.

[0011] (Resin Composition) The resin composition of the present invention (hereinafter also simply referred to as "resin composition") contains a polyimide having a structure represented by formula (A-1). Hereinafter, the polyimide having a structure represented by formula (A-1) is also simply referred to as "specific resin".

[0012] The resin composition of the present invention is preferably used to form a photosensitive film subjected to exposure and development, and more preferably used to form a photosensitive film subjected to exposure and development using a developer containing an organic solvent. The resin composition of the present invention can be used, for example, to form insulating films for semiconductor devices, interlayer insulating films for redistribution layers, stress buffer films, etc., and is preferably used to form interlayer insulating films for redistribution layers. Furthermore, the resin composition of the present invention is preferably used to form a photosensitive film subjected to negative-type development. In the present invention, negative-type development refers to development in which unexposed areas are removed by development during exposure and development, and positive-type development refers to development in which exposed areas are removed by development. As the exposure method, developer, and development method described above, for example, the exposure method, developer, and development method described in the exposure step, development step, etc., described later in the description of the method for manufacturing cured products may be used.

[0013] Conventionally, studies have been conducted to improve mechanical properties (elongation at break) by examining the structure of cyclized resins or their precursors. The cured product obtained from the resin composition of the present invention has a large elongation at break. The mechanism by which the above effect is obtained is unknown, but it is presumed to be as follows. The resin of the present invention has a structure represented by formula (A-1). Among the structures represented by formula (A-1), the structure represented by formula (AA-1) in particular has high cohesiveness, and L １ or L ２Because it contains -O-, -C(=O)O-, or -S-, it has a soft structure, which is thought to greatly increase the elongation at break of the resulting resin. Furthermore, because the structure represented by formula (AA-1) contains a rigid and highly planar polycyclic structure, interactions between resins, such as stacking of ring structures, are likely to occur, which is thought to increase the glass transition temperature. Thus, because the glass transition temperature is high and the elongation at break is excellent, the insulating properties are easily maintained over a long period of time, and it is thought to have excellent insulating reliability. In addition, the structure represented by formula (AA-1) has high compatibility with other components and high solubility in solvents added as needed. Therefore, when a resin composition containing a resin with such a specific structure is used, it is presumed that the surface flatness of the photosensitive film will be excellent. Furthermore, the structure represented by formula (A-1) is L １ and L ２ The conjugated system is cleaved by this. As a result, the absorption of exposure light by the resin is small (for example, increasing transmittance at 365 nm), and therefore, it is presumed that the resolution during exposure is also improved. Furthermore, the structure represented by formula (A-1) is a structure with a relatively large molecular weight, and by including this, the content of the imide ring structure in the cured resin becomes relatively small, which may result in a smaller dielectric loss tangent (Df).

[0014] However, Patent Document 1 does not describe a resin composition containing a resin that corresponds to a specific resin.

[0015] The components included in the resin composition of the present invention will be described in detail below.

[0016] <Specific Resin> The resin composition of the present invention includes a polyimide (specific resin) having a structure represented by formula (A-1).

[0017] In this specification, polyimide refers to a resin having repeating units containing imide structures within its molecular chain, and preferably a resin having repeating units containing imide ring structures within its molecular chain. Furthermore, if the polyimide is a linear resin, it is preferable that the polyimide is a resin having repeating units containing imide structures within its main chain, and more preferably a resin having repeating units containing imide ring structures within its main chain. In this specification, "main chain" refers to the relatively longest bonding chain in the resin molecule, and "side chains" refer to the other bonding chains. In this specification, imide structure refers to a structure represented by *-C(=O)N(-*)C(=O)-*, where * represents a bonding site with another structure, preferably a bonding site with a carbon atom, and more preferably a bonding site with a quaternary carbon atom. Furthermore, in this specification, "bonding site" refers to a site that directly bonds with the target without the intervening of a linking group. In this specification, imide ring structure refers to a ring structure that includes all of the two carbon atoms and nitrogen atoms in the above imide structure as ring members. The imide ring structure is preferably a five-membered ring. Polyimides may also be so-called polyamideimides, which have amide bonds in their molecular chains in addition to the imide structure. In this specification, an amide bond refers to a structure represented by *-C(=O)N(-#)-*, where * represents a bonding site with another structure, preferably a bonding site with a carbon atom, and more preferably a bonding site with a quaternary carbon atom. Also, # represents a bonding site with another structure, preferably a bonding site with a hydrogen atom or a carbon atom, and more preferably a bonding site with a hydrogen atom.

[0018] [Polymerizable Groups] It is preferable that the specific resin has polymerizable groups. Examples of polymerizable groups include groups having ethylenically unsaturated bonds, epoxy groups, oxetanyl groups, benzoxazolyl groups, etc., with groups having ethylenically unsaturated bonds being preferred. Examples of groups having ethylenically unsaturated bonds include vinyl groups, allyl groups, vinylphenyl groups, (meth)acryloyl groups, maleimide groups, etc. Among these, (meth)acryloyl groups, vinylphenyl groups, or maleimide groups are preferred, and from the viewpoint of reactivity, (meth)acryloyl groups are more preferred. Furthermore, from the viewpoint of reducing dielectric loss tangent, vinylphenyl groups or maleimide groups are preferred. Furthermore, from the viewpoint of adhesion, hydrophobic vinylphenyl groups are preferred.

[0019] The polymerizable value (polymerizability value) relative to the total mass of the specific resin is preferably 0.2 mmol / g or more, more preferably 0.3 mmol / g or more, and even more preferably 0.4 mmol / g or more. The polymerizability value is preferably 4.0 mmol / g or less, more preferably 3.5 mmol / g or less, and even more preferably 3.0 mmol / g or less. In particular, the radical polymerizable value (radical polymerizability value) relative to the total mass of the specific resin is preferably 0.2 mmol / g or more, more preferably 0.3 mmol / g or more, and even more preferably 0.4 mmol / g or more. The radical polymerizability value is preferably 3.0 mmol / g or less, more preferably 2.8 mmol / g or less, and even more preferably 2.6 mmol / g or less.

[0020] For example, the content of vinylphenyl groups in the resin of a composition can be calculated by the following method. The calculation method is the same for other polymerizable groups and radical polymerizable groups. Add 1 g of the composition to 50 g of methanol or water and crystallize to precipitate the specific resin, then filter. Collect the filtrate, dissolve it in 3.0 g of THF (tetrahydrofuran), add it to 50 g of methanol or water and crystallize, filter, and dry at 40°C for 20 hours. Dissolve 0.1 g of the dried specific resin in 0.9 g of didimethyl sulfoxide, １ The amount of vinylphenyl groups is calculated by measuring with 1H-NMR. １The number of 1H-NMR scans will be 640. For example, tetramethylsilane will be used as the reference substance. １ The molar amount of vinylphenyl groups in a specific resin can be calculated from the ratio of the integrated intensity of the peak around 5.0–7.0 ppm derived from vinylphenyl groups in the 1H-NMR chart to the integrated intensity of the peak derived from the reference substance, the amount of the reference substance, and the amount of the specific resin. The molar amounts of other structures can also be measured by calculating the integrated intensity of the peaks corresponding to each structure.

[0021] [Structure represented by formula (A-1)] The specified resin has the structure represented by the following formula (A-1). In formula (A-1), Z １ Q is a group represented by the following formula (AA-1), １ ~Q ８ Each of these independently represents a hydrogen atom or a monovalent organic group, n represents an integer from 0 to 2, m represents an integer from 0 to 2, n + m is 2, and when n is 2, there are two Qs. １ ~Q ４ These can be the same or different, and if m is 2, there are two Qs. ５ ~Q ８ Each of them may be the same or different, Q １ ~Q ４ At least two of them may bond together to form a ring structure, Q ５ ~Q ８ At least two of them may bond together to form a ring structure, L １ Each of these independently represents -O-, -C(=O)O-, or -S-, L ２ Each of the symbols independently represents -O-, -C(=O)O-, or -S-, and each of the symbols independently represents a bonding site with a nitrogen atom. In formula (AA-1), G １ ~G ８ Any two of these are L in equation (A-1) １ or L ２ This represents the bonding site with other G １ ~G ８ Each of these independently represents a hydrogen atom or a monovalent organic group.

[0022] - Q １ ~Q ８ - In formula (A-1), Q １ ~Q ８ Each of these independently represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom, an alkyl group which may be substituted with a hydrogen atom, an alkoxy group which may be substituted with a hydrogen atom, or a group having a polymerizable group. The alkyl group is preferably a C1-C10 alkyl group, more preferably a C1-C4 alkyl group, and even more preferably a methyl group or an ethyl group. Substituents for the alkyl group include halogen atoms. The alkoxy group is preferably a C1-C10 alkoxy group, more preferably a C1-C4 alkoxy group, and even more preferably a methoxy group or an ethoxy group. Substituents for the alkoxy group include halogen atoms (preferably fluorine atoms). The preferred embodiment of the polymerizable group in the group having the polymerizable group is the same as the preferred embodiment of the polymerizable group in the specific resin described above. The group having the polymerizable group is preferably the group represented by formula (R-1) described later.

[0023] -L １ , L ２ - In formula (A-1), L １ Each of them is preferably -O- independently. Also, L １ If is -C(=O)O-, then the carbon atoms of -C(=O)O- are Z １ It is preferable that this is the bonding site with. In formula (A-1), L ２ Each of them is preferably -O- independently. Also, L ２ If is -C(=O)O-, then the carbon atoms of -C(=O)O- are Z １ It is preferable that this is a bonding site with the

[0024] -Equation (AA-1)- <<G １ ~G ８ >> In formula (AA-1), G １ ~G ８ Any two of these are L in equation (A-1) １ and L ２ This represents the bonding site with one of the two, G １ and G５ G ３ and G ７ G １ and G ６ or G ３ It is preferable that either G8 or the above-mentioned bonding site is the bonding site.

[0025] Other G that do not fall under the above bonding sites １ ~G ８ Each of these independently represents a hydrogen atom or a monovalent organic group, and hydrogen atoms, optionally substituted alkyl groups, or optionally substituted alkoxy groups are preferred. The alkyl groups are preferably C1-C10 alkyl groups, more preferably C1-C4 alkyl groups, and even more preferably methyl or ethyl groups. Substituents for the alkyl groups include halogen atoms. The alkoxy groups are preferably C1-C10 alkoxy groups, more preferably C1-C4 alkoxy groups, and even more preferably methoxy or ethoxy groups. Substituents for the alkoxy groups include halogen atoms (preferably fluorine atoms). Also, the other G mentioned above... １ ~G ８ An embodiment in which all of these are hydrogen atoms is also one of the preferred embodiments of the present invention.

[0026] The following are specific examples of the group represented by formula (AA-1), but the present invention is not limited to these. In the following structure, * represents L in formula (A-1). １ or L ２ This represents the connection point.

[0027] -n, m- In formula (A-1), it is preferable that n = 2 or m = 2, and more preferably that n = 2.

[0028] Specific examples of the group represented by formula (A-1) are described below, but the present invention is not limited to these. In the structure below, * is equivalent to * in formula (A-1).

[0029] The molar content of the structure represented by formula (A-1) relative to the mass of the specific resin is preferably 0.1 to 3.0 mmol / g, more preferably 0.2 to 2.0 mmol / g, and even more preferably 0.4 to 1.5 mmol / g. The above content can be calculated by the following method. <Detection method> Add 1 g of the composition to 50 g of methanol or water and crystallize to precipitate the specific resin, then filter. Collect the filtrate, dissolve it in 3.0 g of THF (tetrahydrofuran), add it to 50 g of methanol or water and crystallize, filter, and dry at 40°C for 20 hours. Dissolve 0.1 g of the dried specific resin in 0.9 g of deuterated chloroform, １ The amount of the structure represented by formula (A-1) is calculated by measuring it using 1H-NMR. １ The number of 1H-NMR scans will be 640. For example, tetramethylsilane will be used as the reference substance. １ From the ratio of the integrated intensity of the peak originating from the naphthylene group to the integrated intensity of the peak originating from the reference substance in the H-NMR chart, the amount of the reference substance, and the amount of the specified resin, the molar amount of the structure represented by formula (A-1) in the specified resin can be calculated.

[0030] Furthermore, the mass content of the structure represented by formula (A-1) relative to the mass of the specific resin is preferably 20 to 80% by mass, more preferably 25 to 75% by mass, and even more preferably 28 to 70% by mass. The above content mass is calculated by the following formula: Mass content of A-1 structure (mass%) = Molecular weight of A-1 structure / Total molecular weight of each repeating unit × 100

[0031] [Repeating unit represented by formula (1-1)] The specific resin preferably has a repeating unit represented by formula (1-1). In formula (1-1), X １ represents an organic group with 4 or more carbon atoms, Y １ R represents an organic group with 4 or more carbon atoms. １ Each of these independently represents a structure expressed by the following formula (R-1), where a represents an integer from 0 to 4, b represents an integer greater than or equal to 0, and X １ and Y １At least one of them includes a structure represented by formula (A-1). In formula (R-1), L １ represents a 1+1 valent linking group, A １ represents a polymerizable group, a1 represents an integer greater than or equal to 1, and * represents X in formula (1-1). １ or Y １ This represents the connection point.

[0032] -X １ - X １ The number of carbon atoms is 4 or more, preferably 4 to 50, and more preferably 4 to 40.

[0033] X １ If X includes a structure represented by formula (A-1), １ Preferably, the group is represented by the following formula (X-1). In formula (X-1), X ２ Each of these independently represents a trivalent linking group, L Ｘ１ represents a divalent linking group containing the structure represented by formula (A-1), and * represents the bonding site with the carbonyl group in formula (1-1).

[0034] In formula (X-1), X ２ Examples include linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups, or groups formed by linking two or more of these by single bonds or linking groups. Preferably, these are linear aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, aromatic groups having 6 to 20 carbon atoms, or groups formed by combining two or more of these by single bonds or linking groups. More preferably, these are aromatic groups having 6 to 20 carbon atoms, or groups formed by combining two or more aromatic groups having 6 to 20 carbon atoms by single bonds or linking groups. Examples of the linking groups include -O-, -S-, -C(=O)-, and -S(=O). ２-, alkylene groups, halogenated alkylene groups, arylene groups, or linking groups comprising two or more of these are preferred, and -O-, -S-, alkylene groups, halogenated alkylene groups, arylene groups, or linking groups comprising two or more of these are more preferred. As for the alkylene group, alkylene groups having 1 to 20 carbon atoms are preferred, alkylene groups having 1 to 10 carbon atoms are more preferred, and alkylene groups having 1 to 4 carbon atoms are even more preferred. As for the halogenated alkylene group, halogenated alkylene groups having 1 to 20 carbon atoms are preferred, halogenated alkylene groups having 1 to 10 carbon atoms are more preferred, and halogenated alkylene groups having 1 to 4 carbon atoms are even more preferred. In addition, examples of halogen atoms in the halogenated alkylene group include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being preferred. The above halogenated alkylene group may have hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferable that all of the hydrogen atoms are substituted with halogen atoms. Examples of preferred halogenated alkylene groups include the (ditrifluoromethyl)methylene group. The above arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and even more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0035] Also, X ２ It is preferable that the product is derived from a tricarboxylic acid compound in which at least one carboxyl group is halogenated. Chlorination is preferred as the halogenation. In the present invention, a compound having three carboxyl groups is referred to as a tricarboxylic acid compound. Two of the three carboxyl groups of the tricarboxylic acid compound may be acid anhydrides. Examples of tricarboxylic acid compounds that may be halogenated include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds. Only one of these tricarboxylic acid compounds may be used, or two or more may be used.

[0036] X ２ It is preferable that the structure does not contain an imide structure. Also, X ２It is preferable that the structure does not contain urethane bonds, urea bonds, and amide bonds. Furthermore, X ２ It is preferable that the structure does not contain ester bonds. Among these, X ２ It is preferable that the material does not contain imide structures, urethane bonds, urea bonds, and amide bonds, and more preferably that it does not contain imide structures, urethane bonds, urea bonds, amide bonds, and ester bonds.

[0037] Specifically, preferred tricarboxylic acid compounds include a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these groups by single bonds or linking groups. More preferred tricarboxylic acid compounds include an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms by single bonds or linking groups.

[0038] Furthermore, specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalentricarboxylic acid, and phthalic acid (or phthalic anhydride) and benzoic acid with a single bond, -O-, -CH ２ -, -C(CH ３ ) ２ -, -C (CF ３ ) ２ -, -SO ２ - Or, compounds linked by a phenylene group, etc. These compounds may be compounds in which two carboxyl groups have been converted to anhydrides (e.g., trimellitic anhydride), or compounds in which at least one carboxyl group has been halogenated (e.g., trimellitic anhydride chloride).

[0039] In formula (X-1), L Ｘ１ This includes a structure represented by formula (A-1). Preferred embodiments of the structure represented by formula (A-1) are as described above. In formula (X-1), L Ｘ１ The structure is represented by formula (A-1), and it is preferable that all of the * symbols in formula (A-1) are bonding sites with nitrogen atoms as described in formula (X-1).

[0040] Below, X １ A preferred embodiment in which the structure represented by formula (A-1) is not included will be described. In formula (1-1), X １ It is preferable that this represents an organic group containing a structure obtained by removing two or more hydrogen atoms from any of the following formulas (V-1) to (V-10), and more preferably that it represents an organic group containing a structure obtained by removing two or more hydrogen atoms from any of the following formulas (V-1) to (V-4). The structure obtained by removing two or more hydrogen atoms from any of the following formulas (V-1) to (V-10) does not include the structure represented by formula (A-1) mentioned above. １ The fact that the organic group contains a structure obtained by removing two or more hydrogen atoms from any of the structures represented by formulas (V-1) to (V-10) improves the chemical resistance and flatness of the cured product. Also, X １ By including an organic group containing a structure obtained by removing two or more hydrogen atoms from any of the structures represented by formulas (V-1) to (V-5), effects such as suppression of developing residue generation, lower dielectric constant of cured products, and reduction of thermal expansion coefficient can be obtained. By including an organic group containing a structure obtained by removing two or more hydrogen atoms from any of the structures represented by formulas (V-6) to (V-10), effects such as improved ultraviolet light transmittance, making it less likely for the cured product pattern to become tapered, and a wider tolerance for exposure amount can be obtained. In formula (V-2), R Ｘ１ Each of these is independently a hydrogen atom, an alkyl group, or an alkyl halide. In formula (V-3), R Ｘ２ and R Ｘ３ Each of these independently represents a hydrogen atom or a substituent, R Ｘ２ and R Ｘ３ They may bond to form a ring structure. In formula (V-8), R Ｘ５ Each of these is independently a hydrogen atom, an alkyl group, or an alkyl halogen.

[0041] In formula (V-2), R Ｘ１Each of these is preferably an alkyl group or a halogenated alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group or a trifluoromethyl group. A halogenated alkyl group is a group in which at least one hydrogen atom of the alkyl group is substituted with a halogen atom. The halogen atom is preferably F or Cl, and more preferably F. In formula (V-3), R Ｘ２ and R Ｘ３ Each of these is preferably a hydrogen atom. Ｘ２ and R Ｘ３ When R is bonded to form a ring structure, Ｘ２ and R Ｘ３ The structures formed by the bonding of these are single bonds, -O-, or -C(R) ２ It is preferable that it be -O- or -C(R) ２ It is more preferable that it be -, and even more preferable that it be -O-. R represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom. In formula (V-8), R Ｘ５ Each of these groups is preferably an alkyl group or a halogenated alkyl group, more preferably a C1-C4 alkyl group or a C1-C4 halogenated alkyl group, and even more preferably a methyl group or a trifluoromethyl group. A halogenated alkyl group is a group in which at least one hydrogen atom of the alkyl group is substituted with a halogen atom. The halogen atom is preferably F or Cl, and more preferably F.

[0042] X １ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-1), then X １ It is preferable that the group is represented by the following formula (V-1-1). In the following formula, * is X in formula (1-1). １ The four carbonyl groups to which it is bonded represent the bonding sites, and n1 represents an integer from 0 to 5, preferably an integer from 1 to 5. In addition, the hydrogen atom in the structure below is R in formula (1-1). １ Alternatively, it may be further substituted with known substituents such as hydrocarbon groups.

[0043] X １ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-2), then X １ It is preferable that the group is represented by the following formula (V-2-1) or formula (V-2-2), and from the viewpoint of lowering the amine value in the resin, it is preferable that the group is represented by formula (V-2-2). In this specification, a bond intersecting the edge of a ring structure means that one of the hydrogen atoms in that ring structure is substituted. In the following formula, L Ｘ１ represents a single bond or -O-, and * represents X in equation (1-1). １ This represents the bonding sites with the four carbonyl groups to which it is bonded. Also, R Ｘ１ The definition and preferred embodiment of are as described above. Furthermore, the hydrogen atom in these structures is R in formula (1-1). １ Alternatively, it may be further substituted with known substituents such as hydrocarbon groups.

[0044] X １ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-3), then X １ It is preferable that the group is represented by the following formula (V-3-1) or formula (V-3-2), and from the viewpoint of reducing the dielectric constant of the cured product, it is preferable that the group is represented by formula (V-3-2). In the following formula, * is X in formula (1-1). １ This represents the bonding sites with the four carbonyl groups to which it is bonded. Also, R Ｘ２ and R Ｘ３ The definition and preferred embodiment of are as described above. Furthermore, the hydrogen atom in these structures is R in formula (1-1). １ Alternatively, it may be further substituted with known substituents such as hydrocarbon groups.

[0045] X １ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-4), then X １ It is preferable that the group is represented by the following formula (V-4-1). In the following formula (V-4-1), * is X in formula (1-1). １The four carbonyl groups to which it is bonded are represented by n1, which is an integer from 0 to 5. Also, the hydrogen atom in formula (V-4-1) is R in formula (1-1). １ Alternatively, it may be further substituted with known substituents such as hydrocarbon groups. Examples of known substituents include alkyl groups, alkyl halides, and halogen atoms. However, it is also preferable that none of the hydrogen atoms in the structure represented by (V-4-1) are substituted.

[0046] X １ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-5), then X １ It is preferable that the group is represented by the following formula (V-5-1). In the following formula, * is X in formula (1-1). １ This represents the bonding sites with the four carbonyl groups to which it is bonded. Also, the hydrogen atom in formula (V-5-1) is R in formula (1-1). １ Alternatively, it may be further substituted with known substituents such as hydrocarbon groups. Examples of known substituents include alkyl groups, alkyl halides, and halogen atoms. However, it is also preferable that none of the hydrogen atoms in the structure represented by (V-5-1) are substituted.

[0047] X １ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-6), then X １ It is preferable that the group is represented by the following formula (V-6-1). In the following formula, * is X in formula (1-1). １ This represents the bonding sites with the four carbonyl groups to which it is bonded. Also, the hydrogen atom in the structure below is R in formula (1-1). １ Alternatively, it may be further substituted with known substituents such as hydrocarbon groups.

[0048] X １ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-7), then X １ It is preferable that the group is represented by the following formula (V-7-1). In the following formula, * is X in formula (1-1). １This represents the bonding sites with the four carbonyl groups to which it is bonded. Also, the hydrogen atom in the structure below is R in formula (1-1). １ Alternatively, it may be further substituted with known substituents such as hydrocarbon groups.

[0049] X １ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-8), then X １ It is preferable that the group is represented by the following formula (V-8-1). In the following formula, * is X in formula (1-1). １ This represents the bonding sites with the four carbonyl groups to which it is attached. Ｘ５ The definition and preferred embodiment are as described above. Furthermore, the hydrogen atom in the structure below is R in formula (1-1). １ Alternatively, it may be further substituted with known substituents such as hydrocarbon groups.

[0050] X １ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-9), then X １ It is preferable that the group is represented by the following formula (V-9-1). In the following formula, * is X in formula (1-1). １ This represents the bonding sites with the four carbonyl groups to which it is bonded. Also, the hydrogen atom in the structure below is R in formula (1-1). １ Alternatively, it may be further substituted with known substituents such as hydrocarbon groups.

[0051] X １ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-10), then X １ It is preferable that the group is represented by the following formula (V-10-1). In the following formula, * is X in formula (1-1). １ This represents the bonding sites with the four carbonyl groups to which it is bonded. Also, the hydrogen atom in the structure below is R in formula (1-1). １ They may be further substituted with known substituents such as hydrocarbon groups.

[0052] Other, X １This may be a tetracarboxylic acid residue remaining after the removal of the anhydride group from the tetracarboxylic dianhydride described in paragraphs 0055 to 0057 of Japanese Patent Application Publication No. 2023-003421.

[0053] Also, X １ It is preferable that the structure does not contain an imide structure. Also, X １ Preferably, the structure does not contain urethane bonds, urea bonds, or amide bonds. In the present invention, urethane bonds are defined as *-O-C(=O)-NR Ｎ -* is a combination represented by R Ｎ R represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom. Ｎ The hydrogen atom or hydrocarbon group is preferred, the hydrogen atom or alkyl group is more preferred, and the hydrogen atom is even more preferred. In the present invention, the urea bond is *-NR Ｎ -C(=O)-NR Ｎ -* is a combination represented by R Ｎ Each of the symbols independently represents a hydrogen atom or a monovalent organic group, and each of the symbols * represents a bonding site with a carbon atom. Ｎ The preferred embodiment is as described above. Furthermore, X １ Preferably, the structure does not contain ester bonds. In the present invention, an ester bond is a bond represented by *-O-C(=O)-*. Among these, X １ It is preferable that the material does not contain imide structures, urethane bonds, urea bonds, and amide bonds, and more preferably that it does not contain imide structures, urethane bonds, urea bonds, amide bonds, and ester bonds.

[0054] Also, X １ This is the structure represented by the following formula (X-2), or X in the structure represented by formula (X-2). ２ A hydrogen atom or L of the group represented by ３ The hydrogen atom of the group represented by is R in formula (1-1) １ The structure may be substituted with a group represented by . In formula (X-2), X ２ Each of these independently represents a trivalent linking group, L ３represents a divalent linking group, and * represents a bonding site with other structures. However, L ３ The structure does not contain the structure represented by formula (A-1), and the structure corresponding to formula (X-1) does not correspond to the structure represented by formula (X-2).

[0055] In formula (X-2), X ２ A preferred embodiment is X in the above formula (X-1). ２ This is similar to the preferred embodiment.

[0056] In formula (X-2), L ３ Examples of these groups include linear or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, or groups formed by linking two or more of these groups by single bonds or linking groups. Preferably, these groups include linear aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, aromatic groups having 6 to 20 carbon atoms, or groups formed by combining two or more of these groups by single bonds or linking groups. More preferably, these groups include aromatic groups having 6 to 20 carbon atoms, or groups formed by combining two or more aromatic groups having 6 to 20 carbon atoms by single bonds or linking groups. Examples of the linking groups include -O-, -S-, -C(=O)-, and -S(=O). ２-, alkylene groups, halogenated alkylene groups, arylene groups, or linking groups comprising two or more of these are preferred, and -O-, -S-, alkylene groups, halogenated alkylene groups, arylene groups, or linking groups comprising two or more of these are more preferred. As for the alkylene group, alkylene groups having 1 to 20 carbon atoms are preferred, alkylene groups having 1 to 10 carbon atoms are more preferred, and alkylene groups having 1 to 4 carbon atoms are even more preferred. As for the halogenated alkylene group, halogenated alkylene groups having 1 to 20 carbon atoms are preferred, halogenated alkylene groups having 1 to 10 carbon atoms are more preferred, and halogenated alkylene groups having 1 to 4 carbon atoms are even more preferred. In addition, examples of halogen atoms in the halogenated alkylene group include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being preferred. The above halogenated alkylene group may have hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferable that all of the hydrogen atoms are substituted with halogen atoms. Examples of preferred halogenated alkylene groups include the (ditrifluoromethyl)methylene group. The above arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and even more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0057] Also, X １ This is the structure represented by the following formula (X-3), or X in the structure represented by formula (X-3). ２ A hydrogen atom or L of the group represented by ３ The hydrogen atom of the group represented by is R in formula (1-1) １ The structure may be substituted with a group represented by . In formula (X-3), X ２ Each of these independently represents a trivalent linking group, L ３ represents a divalent linking group, and * represents a bonding site with other structures. In formula (X-3), X ２ and L ３ A preferred embodiment is X in formula (X-2) ２ and L ３ This is similar to the preferred embodiment.

[0058] -Y １ - Y１ The number of carbon atoms is 4 or more, preferably 4 to 50, and more preferably 4 to 40. In formula (1-1), Y １ It is preferable that it includes a structure represented by formula (A-1), where all of the * in formula (A-1) are Y as described in formula (1-1). １ It is preferable that this is the bonding site with the nitrogen atom to which it is bonded.

[0059] Below, Y １ A preferred embodiment in which the structure represented by formula (A-1) is not included will be described. In formula (1-1), Y １ If it does not include the structure represented by formula (A-1) (i.e., X １ If only Y contains the structure represented by formula (A-1), １ The group may include a structure obtained by removing two or more hydrogen atoms from the structure represented by any of the above formulas (V-1) to (V-10). By including an organic group with a structure obtained by removing two or more hydrogen atoms from the structure represented by any of the above formulas (V-1) to (V-10), the chemical resistance and flatness of the cured product are improved.

[0060] Y １ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-1), then Y １ It is preferable that the group is represented by the following formula (V-1-2). In the following formula, * is Y in formula (1-1). １ The symbol represents the bonding site with the two nitrogen atoms to which it is bonded, and n1 represents an integer from 1 to 5. Also, the hydrogen atom in the structure below is represented by R in formula (1-1). １ Alternatively, it may be further substituted with known substituents such as hydrocarbon groups.

[0061] Y １ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-2), then Y １ It is preferable that the group is represented by the following formula (V-2-3) or formula (V-2-4), and from the viewpoint of reducing the dielectric constant of the cured product, it is preferable that the group is represented by formula (V-2-4). In the following formula, L Ｘ１ represents a single bond or -O-, and * represents Y in equation (1-1). １This represents the bonding site with the two nitrogen atoms to which it is bonded. Also, R Ｘ１ The preferred embodiments are as described above. Furthermore, the hydrogen atoms in these structures are R in formula (1-1). 1 Alternatively, it may be further substituted with known substituents such as hydrocarbon groups.

[0062] Y １ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-3), then Y １ It is preferable that the group is represented by the following formula (V-3-3) or formula (V-3-4), and from the viewpoint of reducing the dielectric constant of the cured product, it is preferable that the group is represented by formula (V-3-3). In the following formula, * is Y in formula (1-1). １ This represents the bonding site with the two nitrogen atoms to which it is bonded. Also, R Ｘ２ and R Ｘ３ The preferred embodiments are as described above. Furthermore, the hydrogen atoms in these structures are R in formula (1-1). １ Alternatively, it may be further substituted with known substituents such as hydrocarbon groups.

[0063] Y １ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-4), then Y １ It is preferable that the group is represented by the following formula (V-4-2) or formula (V-4-3). In the following formula, * is Y in formula (1-1). １ The ∫ represents the bonding site with the two nitrogen atoms to which it is bonded, and n1 represents an integer from 0 to 5. The embodiment in which n1 is 0 is also one of the preferred embodiments of the present invention. Furthermore, the hydrogen atom in the following structure is R in formula (1-1). １ Alternatively, it may be further substituted with known substituents such as hydrocarbon groups. Known substituents include alkyl groups, alkyl halides, halogen atoms, and the like.

[0064] Y １ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-5), then Y １It is preferable that the group is represented by the following formula (V-5-2). In the following formula, * is Y in formula (1-1). １ This represents the bonding site with the two nitrogen atoms to which it is bonded. Also, the hydrogen atom in formula (V-5-2) is R in formula (1-1). １ Alternatively, it may be further substituted with known substituents such as hydrocarbon groups. Examples of known substituents include alkyl groups, alkyl halides, and halogen atoms. However, it is also preferable that none of the hydrogen atoms in the structure represented by (V-5-2) are substituted.

[0065] Y １ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-6), then Y １ It is preferable that the group is represented by the following formula (V-6-2). In the following formula, * is Y in formula (1-1). １ This represents the bonding site with the two nitrogen atoms to which it is bonded. Also, the hydrogen atom in the structure below is R in formula (1-1). １ Alternatively, it may be further substituted with known substituents such as hydrocarbon groups.

[0066] Y １ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-7), then Y １ It is preferable that the group is represented by the following formula (V-7-2). In the following formula, * is Y in formula (1-1). １ This represents the bonding site with the two nitrogen atoms to which it is bonded. Also, the hydrogen atom in the structure below is R in formula (1-1). １ Alternatively, it may be further substituted with known substituents such as hydrocarbon groups.

[0067] Y １ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-8), then Y １ It is preferable that the group is represented by the following formula (V-8-2). In the following formula, * is Y in formula (1-1). １ R represents the bonding site with the two nitrogen atoms to which it is bonded. Ｘ５The definition and preferred embodiment are as described above. Furthermore, the hydrogen atom in the structure below is R in formula (1-1). １ Alternatively, it may be further substituted with known substituents such as hydrocarbon groups.

[0068] Y １ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-9), then Y １ It is preferable that the group is represented by the following formula (V-9-2). In the following formula, * is Y in formula (1-1). １ This represents the bonding site with the two nitrogen atoms to which it is bonded. Also, the hydrogen atom in the structure below is R in formula (1-1). １ Alternatively, it may be further substituted with known substituents such as hydrocarbon groups.

[0069] Y １ However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-10), then Y １ It is preferable that the group is represented by the following formula (V-10-2). In the following formula, * is Y in formula (1-1). １ This represents the bonding site with the two nitrogen atoms to which it is bonded. Also, the hydrogen atom in the structure below is R in formula (1-1). １ Alternatively, it may be further substituted with known substituents such as hydrocarbon groups.

[0070] Other, Y １ This may be the basis described in paragraphs 0042 to 0053 of Japanese Patent Publication No. 2023-003421. Also, Y １ It is preferable that the structure does not contain an imide structure. Also, Y １ It is preferable that the structure does not contain urethane bonds, urea bonds, and amide bonds. Furthermore, Y １ It is preferable that the structure does not contain ester bonds. Among these, Y １ It is preferable that the material does not contain imide structures, urethane bonds, urea bonds, and amide bonds, and more preferably that it does not contain imide structures, urethane bonds, urea bonds, amide bonds, and ester bonds.

[0071] -R１ - In formula (1-1), R １ This is a group represented by formula (R-1). In formula (R-1), L １ represents a 1+1 valent linking group, A １ represents a polymerizable group, a1 represents an integer greater than or equal to 1, and * represents X in formula (1-1). １ or Y １ This represents the connection point.

[0072] In formula (R-1), L １ Preferably, the group is represented by the following formula (L-2). In formula (L-2), Z ２ -O-, -NR Ｎ -, -C(=O)O- or -C(=O)NR Ｎ - represents R Ｎ represents a hydrogen atom or a monovalent organic group, and when a1 is 1, L ｘ represents a single bond or a divalent linking group, and when a1 is 2 or more, L ｘ represents a1+1 valent linking group, a1 represents an integer greater than or equal to 1, and * represents X in equation (1-1). １ or Y １ This indicates a bonding site with other structures inside, and # represents A in equation (R-1). １ This represents the connection point.

[0073] In formula (L-2), Z ２ It is preferable that is -O- or -C(=O)O-. Also, Z ２ ga-NR Ｎ - or -C(=O)NR Ｎ - If R Ｎ A hydrogen atom or a hydrocarbon group is preferred, a hydrogen atom, an alkyl group or a phenyl group is more preferred, and a hydrogen atom is even more preferred. In formula (L-2), when a1 is 1, L ｘ It is preferably an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, even more preferably an alkylene group having 1 to 4 carbon atoms, and particularly preferably a methylene group. In formula (L-2), when a1 is 2 or more, L ｘIt is preferably a hydrocarbon group, a heterocyclic group, or a group represented by a combination thereof, more preferably a saturated aliphatic hydrocarbon group having 2 to 20 carbon atoms, and even more preferably a saturated aliphatic hydrocarbon group having 3 to 15 carbon atoms. In formula (L-2), a1 is the same as a1 in formula (R-1).

[0074] In formula (R-1), A １ represents a polymerizable group. The preferred embodiment of the polymerizable group is as described above for the preferred embodiment of the polymerizable group possessed by the specific resin.

[0075] Among these, A １ The group is preferably a vinylphenyl group, a maleimide group, a (meth)acryloyl group, a vinyl group, an allyl group, an epoxy group, or a group containing these, and more preferably a maleimide group, a (meth)acryloyl group, or a vinylphenyl group. In particular, from the viewpoint of reactivity, the (meth)acryloyl group is preferred. Also, from the viewpoint of reducing the dielectric loss tangent of the cured product, the maleimide group or a vinylphenyl group is preferred, and the vinylphenyl group is more preferred. In particular, the sum of a and b in formula (1-1) is 1 or more, and there are a + b R １ In at least one of the equations, A in equation (R-1) １ At least one of the groups is preferably a vinylphenyl group, a maleimide group, a (meth)acryloyl group, a vinyl group, an allyl group, an epoxy group, or a group containing these; more preferably a maleimide group, a (meth)acryloyl group, or a vinylphenyl group; and even more preferably a vinylphenyl group. In the above embodiment, it is preferable that b is an integer of 1 or more.

[0076] Among these, A in equation (R-1) １ is a vinylphenyl group, L １ It is preferable that the group is represented by formula (L-2-1) or -C(=O)O-. １ If is -C(=O)O-, then the carbon atoms in -C(=O)O- are A １ It is preferable that the site is a bonding site with a vinylphenyl group. In formula (L-2-1), L Ｘ２represents a hydrocarbon group, and a1 represents an integer greater than or equal to 1. In formula (L-2-1), L Ｘ２ A more preferable is an aliphatic saturated hydrocarbon group. When a1 is 1, L Ｘ２ An alkylene group is preferred, an alkylene group having 1 to 10 carbon atoms is more preferred, an alkylene group having 1 to 4 carbon atoms is even more preferred, and a methylene group is particularly preferred. In formula (L-2-1), a1 is the same as a1 in formula (R-1).

[0077] Also, A in equation (R-1) １ The maleimide group is L １ is a group represented by formula (L-2), where L in formula (L-2) Ｘ It is preferable that the group is an aromatic group or an aliphatic saturated hydrocarbon group having four or more carbon atoms. The aromatic group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, but an aromatic hydrocarbon group is preferred. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having six to ten carbon atoms, and more preferably an aromatic hydrocarbon group having six carbon atoms. Examples of heteroatoms in the aromatic heterocyclic group include oxygen atoms, nitrogen atoms, sulfur atoms, etc. The number of heteroatoms in the aromatic heterocyclic group is preferably one or two. Furthermore, the aromatic heterocyclic group is preferably a five-membered ring or a six-membered ring containing the above heteroatoms. In addition, other aromatic heterocyclic groups or other aromatic hydrocarbon ring groups may be fused to the aromatic heterocyclic group. The aliphatic saturated hydrocarbon group having four or more carbon atoms may have a linear, branched, cyclic, or combination thereof structure. The number of carbon atoms in the aliphatic saturated hydrocarbon group having four or more carbon atoms is preferably four to 20, and more preferably five to 10.

[0078] In formula (R-1), a1 is preferably an integer between 1 and 4, and more preferably an integer between 1 and 2. Furthermore, the embodiment in which a1 is 1 is also one of the preferred embodiments of the present invention.

[0079] Furthermore, it is preferable that the number of ester bonds in formula (R-1) is 1 or 0.

[0080] -a and b- In formula (1-1), a is preferably an integer between 0 and 2, and more preferably 0 or 1. The embodiment in which a is 0 is also one of the preferred embodiments of the present invention. In formula (1-1), the embodiment in which b is 0 is also one of the preferred embodiments of the present invention. In formula (1-1), when b is 1 or more, it is more preferably 1 or 2, and even more preferably 2.

[0081] [Repeating units represented by formula (1-2)] A specific resin may have repeating units represented by formula (1-2). The repeating units represented by formula (1-1) described above are not considered to be the repeating units represented by formula (1-2). In formula (1-2), X ２ represents an organic group with 4 or more carbon atoms, Y ２ represents an organic group with 4 or more carbon atoms, X ２ and Y ２ None of them include the structure represented by formula (A-1), R ２ Each of these independently represents a structure expressed by equation (R-2), where m is an integer from 0 to 4, n is an integer greater than or equal to 0, and n+m is an integer greater than or equal to 1. In formula (R-2), L ２ represents a² + 1 valent linking group, A ２ represents a polymerizable group, a2 represents an integer greater than or equal to 1, and * represents X in formula (1-2). ２ or Y ２ This represents the connection point.

[0082] -X ２ - In formula (1-2), X ２ A preferred embodiment is X in formula (1-1) described above. １ This is similar to the preferred embodiment when the structure represented by formula (A-1) is not included. However, the reference to "formula (1-1)" in the description of these preferred embodiments shall be read as "formula (1-2)". Among these, X in formula (1-2) ２ However, it is preferable that each of these structures includes a structure obtained by removing two or more hydrogen atoms from the structure represented by any of the above formulas (V-1) to (V-4). Preferred embodiments of formulas (V-1) to (V-4) are as described above.

[0083] -Y２ - In formula (1-2), Y ２ A preferred embodiment is Y in formula (1-1) described above. １ This is similar to the preferred embodiment when the structure represented by formula (A-1) is not included. However, the reference to "formula (1-1)" in the description of these preferred embodiments shall be read as "formula (1-2)". Among these, Y in formula (1-2) ２ However, it is preferable that each of these structures includes a structure obtained by removing two or more hydrogen atoms from the structure represented by any of the above formulas (V-1) to (V-4). Preferred embodiments of formulas (V-1) to (V-4) are as described above.

[0084] -Formula (R-2)- In formula (R-2), L ２ A ２ A preferred embodiment of a2 is L in the above formula (R-1). １ A １ The same as the preferred embodiment of a1. However, in the descriptions of these preferred embodiments, the term "formula (1-1)" shall be read as "formula (1-2)" and the term "formula (R-1)" shall be read as "formula (R-2)".

[0085] In formula (1-2), m is preferably an integer between 0 and 2, and more preferably 0 or 1. The embodiment in which m is 0 is also one of the preferred embodiments of the present invention. In formula (1-2), n is preferably 1 or more, more preferably 1 or 2, and even more preferably 2.

[0086] Here, the m+n Rs in equation (1-2) ２ In at least one of the equations, A in equation (R-2) ２ At least one of these is preferably a vinylphenyl group, a maleimide group, a (meth)acryloyl group, a vinyl group, an allyl group, an epoxy group, or a group containing these, and more preferably a vinylphenyl group. In the above embodiment, it is preferable that n is an integer of 1 or more.

[0087] [Repeating units represented by formula (1-3)] The specified resin may contain repeating units represented by formula (1-3). Repeating units corresponding to the repeating units represented by formula (1-1) or formula (1-2) shall not be considered to be repeating units represented by formula (1-3). In formula (1-3), X ３ represents an organic group with 4 or more carbon atoms, Y ３ represents an organic group with 4 or more carbon atoms, X ３ and Y ３ None of them contain the structure or polymerizable group represented by formula (A-1).

[0088] -X ３ - In formula (1-3), X ３ A preferred embodiment is X in formula (1-1) described above. １ This is similar to the preferred embodiment when the structure represented by formula (A-1) is not included. However, the reference to "formula (1-1)" in the description of these preferred embodiments shall be read as "formula (1-3)".

[0089] -Y ３ - In formula (1-3), Y ３ A preferred embodiment is Y in formula (1-1) described above. １ This is similar to the preferred embodiment when the structure represented by formula (A-1) is not included. However, the reference to "formula (1-1)" in the description of these preferred embodiments shall be read as "formula (1-3)".

[0090] [Repeating unit represented by formula (2-1)] The specific resin may also preferably contain a repeating unit represented by formula (2-1). In formula (2-1), A ２１ and A ２２ Each is independently an oxygen atom or -NR ｚ - represents R ｚ represents a hydrogen atom or a monovalent organic group, X ２１ represents an organic group with 4 or more carbon atoms, Y ２１ R represents an organic group with 4 or more carbon atoms. ２３ Each of these independently represents a structure expressed by the above formula (R-1), and R ２１ and R ２２Each of these independently represents a hydrogen atom or a monovalent organic group, a represents an integer from 0 to 4, b represents an integer of 0 or more, and X ２１ and Y ２１ At least one of them includes a structure represented by formula (A-1).

[0091] -A ２１ and A ２２ - In formula (2-1), A ２１ It is preferably an oxygen atom. ２１ ga-NR Ｎ R in the case of - Ｎ It is preferable that represents a monovalent organic group, and more preferably an alkyl group. In formula (2-1), A ２２ A preferred embodiment is A ２１ This is similar to the preferred embodiment of the above. Among these, A in formula (2-1) ２１ and A ２２ Preferably, all of them are oxygen atoms.

[0092] -R ２１ and R ２２ - In formula (2-1), R ２１ and R ２２ It is preferable that the polymerizable group is an organic group containing a polymerizable group. Preferred embodiments of the polymerizable group are as described above.

[0093] Also, in equation (2-1), R ２１ and R ２２ It is preferable that the group contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkylene oxy group.

[0094] Also, in equation (2-1), R ２１ and R ２２At least one of the groups may be a polarity-converting group such as an acid-degradable group. The acid-degradable group is not particularly limited as long as it decomposes under the action of acid to produce alkali-soluble groups such as phenolic hydroxyl groups and carboxyl groups, but acetal groups, ketal groups, silyl groups, silyl ether groups, and tertiary alkyl ester groups are preferred, and from the viewpoint of exposure sensitivity, acetal groups or ketal groups are more preferred. Specific examples of acid-degradable groups include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group, tert-butoxycarbonylmethyl group, and trimethylsilyl ether group. From the viewpoint of exposure sensitivity, ethoxyethyl groups or tetrahydrofuranyl groups are preferred.

[0095] Among these, in equation (2-1), R ２１ and R ２２ It is preferable that at least one of them is a group represented by the following formula (R2-1), and more preferably that both are groups represented by the following formula (R2-1). In formula (R2-1), n ​​represents an integer greater than or equal to 1, L represents an n+1 valent linking group, and A is independently -O-, -S-, or -NR Ｎ - and R Ｎ R is a hydrogen atom or an organic group, R is independently a hydrogen atom, a fluorine atom or an optionally substituted alkyl group, and * is A in formula (2-1). ２１ Or A ２２ This represents the connection point.

[0096] In formula (R2-1), n ​​is preferably an integer between 1 and 5, more preferably 1 or 2, and even more preferably 1.

[0097] In formula (R2-1), L is a hydrocarbon group, or a hydrocarbon group and -O-, -C(=O)-, -S-, -S(=O) ２ -, and -NR ＮA group bonded with at least one group selected from the group consisting of - is more preferable, and a hydrocarbon group is more preferable. The hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a bond between these, but it is preferably an aliphatic hydrocarbon group, and more preferably a saturated aliphatic hydrocarbon group. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 2 to 20 carbon atoms, more preferably an aliphatic hydrocarbon group having 2 to 10 carbon atoms, and even more preferably an aliphatic hydrocarbon group having 2 to 6 carbon atoms. 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 an aromatic hydrocarbon group having 6 carbon atoms. The hydrogen atoms in the hydrocarbon group may be substituted with halogen atoms, hydroxyl groups, etc. Specific examples of L are shown below, but the present invention is not limited to these. In the structure below, * is A in formula (2-1). ２１ Or A ２２ The symbols and represent the bonding sites, and # represents the bonding site with A in equation (R2-1).

[0098] In formula (R-1), A is preferably -O- or -S-, and more preferably -O-.

[0099] In formula (R-1), R independently represents a hydrogen atom, a fluorine atom, or an optionally substituted alkyl group, preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

[0100] -X ２１ , Y ２１ , R ２３ a and b - In equation (2-1), X ２１ , Y ２１ , R ２３ Preferred embodiments of a and b are X in formula (1-1). １ , Y １ , R １ , similar to the preferred embodiments of a and b. In these descriptions, the term "formula (1-1)" shall be read as "formula (2-1)".

[0101] [Repeating units represented by formula (2-2)] The specific resin may also preferably contain repeating units represented by formula (2-2). The repeating units represented by formula (2-1) described above shall not be considered to be the repeating units represented by formula (2-2). In formula (2-2), A ２３ and A ２４ Each is independently an oxygen atom or -NR ｚ - represents R ｚ represents a hydrogen atom or a monovalent organic group, X ２２ represents an organic group with 4 or more carbon atoms, Y ２２ R represents an organic group with 4 or more carbon atoms. ２６ Each of these independently represents a structure expressed by the above formula (R-1), and R ２４ and R ２５ Each of these independently represents a hydrogen atom or a monovalent organic group, n represents an integer from 0 to 4, m represents an integer of 0 or more, and n+m is an integer of 1 or more, X ２２ and Y ２２ None of them contain the structure represented by formula (A-1).

[0102] -A ２３ A ２４ , R ２４ and R ２５ - In formula (2-2), A ２３ A ２４ , R ２４ and R ２５ Preferred embodiments are, respectively, A in formula (2-1). ２１ A ２２ , R ２１ and R ２２ This is similar to the preferred embodiment. In these explanations, the term "Formula (2-1)" shall be read as "Formula (2-2)".

[0103] -X ２２ , Y ２２ , R ２６ , m and n- In equation (2-2), X ２２ , Y ２２ , R ２６ Preferred embodiments of m and n are, respectively, X in formula (1-2). ２ , Y ２ , R ２, similar to preferred embodiments of m and n. In these descriptions, the term "Formula (1-2)" shall be read as "Formula (2-2)".

[0104] [Repeating units represented by formula (2-3)] The specified resin may contain repeating units represented by formula (2-3). The repeating units represented by formula (2-1) and formula (2-2) described above shall not be considered to be the repeating units represented by formula (2-3). In formula (2-3), A ２５ and A ２６ Each is independently an oxygen atom or -NR ｚ - represents R ｚ represents a hydrogen atom or a monovalent organic group, X ２３ represents an organic group with 4 or more carbon atoms, Y ２３ R represents an organic group with 4 or more carbon atoms. ２７ and R ２８ Each of these independently represents a hydrogen atom or a monovalent organic group, X ２３ and Y ２３ None of them contain the structure or polymerizable group represented by formula (A-1).

[0105] -A ２５ A ２６ , R ２７ and R ２８ - In formula (2-3), A ２５ A ２６ , R ２７ and R ２８ Preferred embodiments are, respectively, A in formula (2-1). ２１ A ２２ , R ２１ and R ２２ This is similar to the preferred embodiment. In these explanations, the term "Formula (2-1)" shall be read as "Formula (2-3)".

[0106] -X ２３ and Y ２３ - In formula (2-3), X ２３ and Y ２３ Preferred embodiments are, respectively, X in formula (1-3). ３ and Y ３This is similar to the preferred embodiment. In these explanations, the notation "Formula (1-3)" shall be read as "Formula (2-3)".

[0107] The content of the repeating unit represented by formula (1-1) relative to the total mass of the specified resin is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and particularly preferably 50% by mass or more. The upper limit of the above content is not particularly limited and may be 100% by mass. The total content of the repeating unit represented by formula (1-1), the repeating unit represented by formula (1-2), and the repeating unit represented by formula (1-3) relative to the total mass of the specified resin 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. The upper limit of the above content is not particularly limited and may be 100% by mass. The specified resin may further contain any of the repeating units represented by formula (2-1), formula (2-2), or formula (2-3). Furthermore, the specific resin may contain two or more repeating units that correspond to the same formula but have different structures, with respect to the repeating units represented by formulas (1-1), (1-2), (1-3), (2-1), (2-2), or (2-3). In this case, it is preferable that the total amount of the two or more repeating units is within the above range. For example, if two or more repeating units represented by formula (1-1) are included, it is preferable that their total amount falls within the preferred range of content for the repeating unit represented by formula (1-1) described above.

[0108] The weight-average molecular weight (Mw) of the specific resin is preferably 3,000 to 100,000. The lower limit of Mw is preferably 5,000 or more, more preferably 8,000 or more, and even more preferably 10,000 or more. The upper limit of Mw is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less. By setting the weight-average molecular weight to 3,000 or more, the bending resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties (e.g., elongation at break), the weight-average molecular weight is particularly preferably 5,000 or more. The number-average molecular weight (Mn) of the specific resin is preferably 1,000 to 40,000, more preferably 2,000 to 30,000, and even more preferably 5,000 to 20,000. The degree of molecular weight dispersion of a specific resin is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no upper limit for the degree of molecular weight dispersion of polyimide, but for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, even more preferably 6.0 or lower, even more preferably 4.5 or lower, and particularly preferably 3.0 or lower. In this specification, the degree of molecular weight dispersion is a value calculated by weight-average molecular weight / number-average molecular weight. When a resin composition contains multiple types of polyimide as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the resins are within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated when the multiple types of resins are treated as a single resin are each within the above ranges.

[0109] The imidization rate (also called the "ring closure rate") of the specific resin is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, from the viewpoint of the film strength and insulating properties of the resulting organic film. The upper limit of the above imidization rate is not particularly limited, and it is acceptable as long as it is 100% or less. Furthermore, the content of the imide structure in the specific resin is preferably 3 mmol / g or less, and more preferably 2.5 mmol / g or less. The lower limit of the above content is not particularly limited, but for example, it can be 0.5 mmol / g or more. The above imidization rate is measured, for example, by the following method: the infrared absorption spectrum of the specific resin is measured, and the absorption peak derived from the imide structure is 1377 cm⁻¹. －１ The peak intensity P1 in the vicinity is determined. Next, the specific resin is heat-treated at 350°C for 1 hour, and then the infrared absorption spectrum is measured again, at 1377 cm⁻¹. －１ Determine the nearby peak intensity P2. Using the obtained peak intensities P1 and P2, the imidization rate of the specific resin can be determined based on the following formula: Imidization rate (%) = (Peak intensity P1 / Peak intensity P2) × 100

[0110] [Terminal] From the viewpoint of adhesion and other factors, the resin preferably has an alkyl group having 4 or more carbon atoms at its terminal, and more preferably has an alkyl group having 4 or more carbon atoms at the end of the main chain. The number of carbon atoms in the alkyl group is preferably 4 to 30, and more preferably 4 to 20. The alkyl group may be linear, branched, cyclic, or have a structure formed by the bonding of these. The substituent of the alkyl group may be a known substituent such as a halogen atom, but an unsubstituted form is also one of the preferred embodiments of the present invention.

[0111] [Method for producing the specific resin] The specific resin can be synthesized, for example, by the method described in paragraphs 0134-0136 of International Publication No. 2022 / 145355, or by reference to that method. The above description is incorporated herein by reference. It may also be synthesized by reference to other known methods.

[0112] [Content] The content of the specific resin in the resin composition of the present invention is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, yet more preferably 30% by mass or more, and particularly preferably 50% by mass or more based on the total solid content of the resin composition. Also, the content of the resin in the resin composition of the present invention is preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less, yet 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. The resin composition of the present invention may contain only one kind of the specific resin or two or more kinds. When two or more kinds are contained, the total amount preferably falls within the above range.

[0113] <Other Resins> The resin composition of the present invention may contain another resin different from the above-described specific resin (hereinafter also simply referred to as "other resin"). Examples of the other resin include resins different from the specific resin, such as polyimide precursors, polyimides, polybenzoxazole precursors, polybenzoxazoles, polyamideimide precursors, 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, polyester resins, and resins corresponding thereto. Examples of the other polyimide precursors, other polyimides, polybenzoxazole precursors, polybenzoxazoles, polyamideimide precursors, and polyamideimides include the compounds described in paragraphs 0017 to 0138 of International Publication No. 2022 / 145355. The above description is incorporated herein.

[0114] When the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 1% by mass or more, even more preferably 2% by mass or more, still more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total solid content of the resin composition. In the resin composition of the present invention, the content of the other resins is preferably 80% by mass or less, more preferably 75% by mass or less, still more preferably 70% by mass or less, even more preferably 60% by mass or less, and still more preferably 50% by mass or less, based on the total solid content of the resin composition. As a preferred embodiment of the resin composition of the present invention, an embodiment in which the content of the other resins is a low content can also be adopted. In the above embodiment, the content of the other resins is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, even more preferably 5% by mass or less, and still more preferably 1% by mass or less, based on the total solid content of the resin composition. The lower limit of the above content is not particularly limited, and it may be 0% by mass or more. The resin composition of the present invention may contain only one kind of other resin or may contain two or more kinds of other resins. When two or more kinds are contained, the total amount is preferably within the above range.

[0115] <Polymerizable compound> The resin composition of the present invention preferably contains a polymerizable compound.

[0116] The melting point of the polymerizable compound is preferably 60°C or lower. The above melting point is the melting point at 1 atm, more preferably 40°C or lower, and still more preferably 25°C or lower. By setting the above melting point to 60°C or lower, the coating film becomes more likely to flow during drying and heating, and the flatness of the cured product can be improved.

[0117] Examples of the polymerizable compound include a polymerizable compound having a radical polymerizable group (radical crosslinking agent) or other crosslinking agents.

[0118] [Radical Crosslinking Agent] The resin composition of the present invention preferably contains a radical crosslinking agent. The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group containing an ethylenically unsaturated bond. Examples of the above-mentioned groups containing an ethylenically unsaturated bond include vinyl group, allyl group, vinylphenyl group, (meth)acryloyl group, maleimide group, and (meth)acrylamide group. Among these, (meth)acryloyl group, (meth)acrylamide group, and vinylphenyl group are preferred, and from the viewpoint of reactivity, the (meth)acryloyl group is more preferred.

[0119] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, and more preferably a compound having two or more. The radical crosslinking agent may also have three or more ethylenically unsaturated bonds. As for the compound having two or more ethylenically unsaturated bonds, it is preferable that it has 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and even more preferably a compound having 2 to 6. From the viewpoint of the film strength of the resulting pattern (cured product), it is also preferable that the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds.

[0120] 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.

[0121] Specific examples of radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyhydric amine compounds. Addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, or sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxys, and dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids are also suitably used. Addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having leaving substituents such as halogeno groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also suitable. As another example, it is also possible to use a group of compounds in which the above-mentioned unsaturated carboxylic acids are replaced with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc. For specific examples, refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0122] The radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples of compounds having a boiling point of 100°C or higher under normal pressure include the compounds described in paragraph 0203 of International Publication No. 2021 / 112189. This information is incorporated herein by reference.

[0123] Other preferred radical crosslinking agents include the radical polymerizable compounds described in paragraphs 0204-0208 of International Publication No. 2021 / 112189. This information is incorporated herein by reference.

[0124] Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), and structures in which the (meth)acryloyl groups of these are linked via ethylene glycol residues or propylene glycol residues. These oligomer types can also be used.

[0125] Commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate having four ethylene oxy chains; SR-209, 231, and 239, difunctional methacrylates having four ethylene oxy chains (all manufactured by Sartomer Co., Ltd.); DPCA-60, a hexafunctional acrylate having six pentylene oxy chains; and TPA-330, a trifunctional acrylate having three isobutylene oxy chains (both manufactured by Nippon Kayaku Co., Ltd.); and urethane oligomers. Examples include UAS-10, UAB-140 (both manufactured by Nippon Paper Industries), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (all manufactured by Kyoeisha Chemical Co., Ltd.), and Bremmer PME400 (manufactured by NOF Corporation).

[0126] Suitable radical crosslinking agents include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Unexamined Patent Publication No. 51-037193, Japanese Unexamined Patent Publication No. 02-032293, and Japanese Unexamined Patent Publication No. 02-016765, as well as urethane compounds having an ethylene oxide-based skeleton as described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418. Compounds having an amino or sulfide structure within the molecule, as described in Japanese Unexamined Patent Publication No. 63-277653, Japanese Unexamined Patent Publication No. 63-260909, and Japanese Unexamined Patent Publication No. 01-105238, can also be used as radical crosslinking agents.

[0127] The radical crosslinking agent may be a radical crosslinking agent having an acidic group such as a carboxyl group or a phosphate group. The radical crosslinking agent having an acidic group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent obtained by reacting the unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group. Particularly preferred is a radical crosslinking agent obtained by reacting the unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group, wherein the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include M-510 and M-520, which are polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

[0128] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mg KOH / g, and more preferably 1 to 100 mg KOH / g. When the acid value of the radical crosslinking agent is within the above range, it exhibits excellent handling properties during manufacturing and excellent developability. It also exhibits good polymerization properties. The above acid value is measured in accordance with the description in JIS K 0070:1992.

[0129] As radical crosslinking agents, radical crosslinking agents having at least one selected from the group consisting of urea bonds and urethane bonds (hereinafter also referred to as "crosslinking agent U") are also preferred. Examples of crosslinking agent U include compounds described in paragraphs 0133 to 0143 of International Publication No. 2023 / 190064. This content is incorporated herein by reference.

[0130] As radical crosslinking agents having an isocyanuric ring structure, compounds having two or three radical polymerizable groups are preferred, and compounds having three are more preferred. Examples of radical crosslinking agents having an isocyanuric ring structure include, but are not limited to, tris(2-acryloyloxyethyl) isocyanurate, tris(2-methacryloyloxyethyl) isocyanurate, isocyanurate EO (ethylene oxide) modified diacrylate, isocyanurate EO modified triacrylate, and compounds with the following structures. In the following structures, n independently represents an integer from 1 to 20, and R represents a divalent linking group.

[0131] From the viewpoint of pattern resolution and film stretchability, it is preferable to use a bifunctional methacrylate or acrylate in the resin composition. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, and 1,6-methyl-1,5-pentanediol diacrylate. Xanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, ethylene oxide (EO) adduct diacrylate of bisphenol A, ethylene oxide (EO) adduct dimethacrylate of bisphenol A, propylene oxide (PO) adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid EO-modified dimethacrylate, and other bifunctional acrylates and bifunctional methacrylates having urethane bonds can be used. Two or more of these can be mixed and used as needed. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate in which the formula weight of the polyethylene glycol chain is about 200. From the viewpoint of suppressing warping of the pattern (cured product), a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent in the resin composition of the present invention.Preferably used as monofunctional radical crosslinking agents include (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate; N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam; and allyl glycidyl ether. To suppress volatilization before exposure, compounds with a boiling point of 100°C or higher under normal pressure are also preferred as monofunctional radical crosslinking agents. Other examples of bifunctional or more functional radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0132] If a radical crosslinking agent is included, the content of the radical crosslinking agent is preferably more than 0% by mass and 60% by mass or less, relative to the total solid content of the resin composition. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0133] A single radical crosslinking agent may be used alone, or two or more may be used in combination. When two or more agents are used in combination, it is preferable that their total amount be within the above range.

[0134] [Other Crosslinking Agents] The resin composition of the present invention may also preferably contain other crosslinking agents different from the radical crosslinking agents described above. Other crosslinking agents refer to crosslinking agents other than the radical crosslinking agents described above, and are preferably compounds having multiple groups in the molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products upon exposure to a photoacid generator or photobase generator, and more preferably compounds having multiple groups in the molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products by the action of an acid or base. The acid or base is preferably an acid or base generated from a photoacid generator or photobase generator in the exposure step. Examples of other crosslinking agents include the compounds described in paragraphs 0179 to 0207 of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0135] The resin composition of the present invention preferably further contains a photosensitive agent. The photosensitive agent is preferably a photopolymerization initiator or a photoacid generator, and more preferably a photopolymerization initiator.

[0136] [Photopolymerization Initiator] The resin composition of the present invention preferably contains a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular restrictions on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible region is preferred. Alternatively, it may be an activator that acts with a photoexcited sensitizer to generate active radicals.

[0137] The photoradical polymerization initiator is present in an amount of at least about 50 L / mol with a wavelength in the range of about 240 to 800 nm (preferably 330 to 500 nm). －１ ・cm －１ It is preferable that the compound contains at least one compound having a molar extinction coefficient. The molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure it using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0138] Any known compound can be used as a photoradical polymerization initiator. Examples include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron arene complexes. For further details, please refer to paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015 / 199219, which are incorporated herein by reference. Furthermore, examples include paragraphs 0065 to 0111 of Japanese Patent Publication No. 2014-130173, the compounds described in Japanese Patent No. 6301489, the peroxide-based photopolymerization initiators described in MATERIAL STAGE 37-60p, vol. 19, No. 3, 2019, the photopolymerization initiators described in International Publication No. 2018 / 221177, the photopolymerization initiators described in International Publication No. 2018 / 110179, the photopolymerization initiators described in Japanese Patent Publication No. 2019-043864, the photopolymerization initiators described in Japanese Patent Publication No. 2019-044030, and the peroxide-based initiators described in Japanese Patent Publication No. 2019-167313, the contents of which are incorporated herein by reference.

[0139] Examples of ketone compounds include the compounds described in paragraph 0087 of Japanese Patent Publication No. 2015-087611, the contents of which are incorporated herein by reference. Among commercially available products, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

[0140] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used as photoradical polymerization initiators. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Application Publication No. 10-291969 and an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, and this is incorporated herein by reference.

[0141] As α-hydroxyketone initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF) can be used.

[0142] As α-aminoketone initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.

[0143] As aminoacetophenone initiators, acylphosphine oxide initiators, and metallocene compounds, for example, compounds described in paragraphs 0161 to 0163 of International Publication No. 2021 / 112189 can also be suitably used. This is incorporated herein by reference.

[0144] More preferably, oxime compounds are used as photoradical polymerization initiators. Using oxime compounds makes it possible to more effectively improve the exposure latitude. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.

[0145] Specific examples of the oxime compound include the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-080068, the compounds described in JP-A-2006-342166, the compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), the compounds described in J. C. S. Perkin II (1979, pp. 156-162), the compounds described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), the compounds described in JP-A-2000-066385, the compounds described in JP-T-2004-534797, the compounds described in JP-A-2017-019766, the compounds described in Patent No. 6065596, the compounds described in International Publication No. 2015 / 152153, the compounds described in International Publication No. 2017 / 051680, the compounds described in JP-A-2017-198865, the compounds described in paragraphs 0025 to 0038 of International Publication No. 2017 / 164127, the compounds described in International Publication No. 2013 / 167515, etc. The contents are incorporated herein.

[0146] Preferred oxime compounds include, for example, compounds having the following structures, 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one. In the resin composition, it is particularly preferable to use an oxime compound as a photo radical polymerization initiator. The oxime compound as a photo radical polymerization initiator has a linking group of >C=N-O-C(=O)- in the molecule.

[0147]

[0148] Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04, IRGACURE OXE 05 (all manufactured by BASF), ADEKA optomer N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in Japanese Patent Publication No. 2012-014052), TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA Arclus NCI-730, NCI-831, and ADEKA Arclus NCI-930 (manufactured by ADEKA Corporation), DFI-091 (manufactured by Daito Chemix Co., Ltd.), and SpeedCure. PDO (manufactured by SARTOMER ARKEMA) is one example. Additionally, oxime compounds with the following structures can be used.

[0149] As photoradical polymerization initiators, for example, oxime compounds having a fluorene ring as described in paragraphs 0169-0171 of International Publication No. 2021 / 112189, oxime compounds having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring, and oxime compounds having a fluorine atom may be used. Also, oxime compounds having a nitro group as described in paragraphs 0208-0210 of International Publication No. 2021 / 020359, oxime compounds having a benzofuran skeleton, and oxime compounds in which a substituent having a hydroxyl group is attached to the carbazole skeleton may be used. These contents are incorporated herein by reference.

[0150] In addition, compounds described in paragraphs 0113 to 0117 of Japanese Patent Publication No. 2023-058585 may be used as photopolymerization initiators. This description is incorporated into the present specification.

[0151] If the resin composition contains a photopolymerization initiator, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass, based on the total solid content of the resin composition. The resin composition may contain only one type of photopolymerization initiator or two or more types. If two or more types of photopolymerization initiators are contained, it is preferable that the total amount is within the above range. In addition, since photopolymerization initiators may also function as thermal polymerization initiators, crosslinking by the photopolymerization initiator may be further advanced by heating with an oven or hot plate, etc.

[0152] [Sensitizer] The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and enters an electronically excited state. When the sensitizer enters an electronically excited state, it comes into contact with thermal radical polymerization initiators, photoradical polymerization initiators, etc., causing electron transfer, energy transfer, and heat generation. As a result, the thermal radical polymerization initiators and photoradical polymerization initiators undergo chemical changes and decompose, generating radicals, acids, or bases. Suitable sensitizers include compounds such as benzophenone, Michlaz ketone, coumarin, pyrazole azo, anilino azo, triphenylmethane, anthraquinone, anthracene, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo compounds.Examples of sensitizers include Michla's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyrideneindanone, and p-dimethylaminobenzylideneindanone. Non, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin Phosphorus, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylate ethyl), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, diethylaminobenzoate Examples include soamyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazol, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, etc. Other sensitizing dyes may also be used. For details on sensitizing dyes, refer to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which are incorporated herein by reference.

[0153] If the resin composition contains a sensitizer, the sensitizer content is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass, based on the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more types.

[0154] [Chain Transfer Agents] The resin compositions of the present invention may contain chain transfer agents. Chain transfer agents are defined, for example, on pages 683-684 of the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, Japan, 2005). Examples of chain transfer agents include -S-S- and -SO2 molecules. ２ Compounds containing -S-, -N-O-, SH, PH, SiH, and GeH, as well as dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthanthate compounds having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization, are used. These can generate radicals by donating hydrogen to low-activity radicals, or by generating radicals after oxidation and deprotonation. Thiol compounds are particularly preferred.

[0155] Furthermore, the chain transfer agent may be a compound described in paragraphs 0152-0153 of International Publication No. 2015 / 199219, which is incorporated herein by reference.

[0156] If the resin composition contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total solid content of the resin composition. There may be only one type of chain transfer agent, or there may be two or more types. If there are two or more types of chain transfer agents, it is preferable that their total content is within the above range.

[0157] Furthermore, a preferred embodiment of the present invention is that the resin composition of the present invention contains two or more polymerization initiators as polymerization initiators. Specifically, it is preferable that the resin composition of the present invention contains a photopolymerization initiator and a thermal polymerization initiator described later, or contains the above-mentioned photoradical polymerization initiator and photoacid generator.

[0158] By including a photopolymerization initiator and a thermal polymerization initiator described later, pattern formation by exposure becomes possible, and radical polymerization also proceeds more easily during curing by the heating process described later, which may improve performance such as chemical resistance. When including a photopolymerization initiator and a thermal polymerization initiator described later, the content ratio of the thermal polymerization initiator is preferably 20 to 70% by mass, and more preferably 30 to 60% by mass, relative to the total content of the photopolymerization initiator and the thermal polymerization initiator.

[0159] The inclusion of a photoradical polymerization initiator and a photoacid generator may improve performance such as resolution. When a photopolymerization initiator and a photoacid generator are included, the content ratio of the photoacid generator is preferably 20 to 70% by mass, and more preferably 30 to 60% by mass, relative to the total content of the photopolymerization initiator and the photoacid generator.

[0160] [Thermal Polymerization Initiators] Examples of thermal polymerization initiators include thermal radical polymerization initiators. Thermal radical polymerization initiators are compounds that generate radicals using thermal energy, thereby initiating or promoting the polymerization reaction of polymerizable compounds. By adding thermal radical polymerization initiators, the polymerization reaction of resins and polymerizable compounds can be advanced, thereby further improving solvent resistance.

[0161] Examples of thermal radical polymerization initiators include the compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554, the details of which are incorporated herein by reference.

[0162] If a thermal polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.5 to 15% by mass, based on the total solid content of the resin composition. Only one thermal polymerization initiator may be included, or two or more may be included. If two or more thermal polymerization initiators are included, the total amount is preferably within the above range.

[0163] [Photoacid Generator] The resin composition of the present invention may contain a photoacid generator. Examples of photoacid generators include the compounds described in paragraphs 0268 to 0282 of Japanese Patent Application Publication No. 2023-106364. The above description is incorporated herein by reference.

[0164] The content of the photoacid generator is preferably 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, even more preferably 0.5 to 10% by mass, even more preferably 0.5 to 3% by mass, and even more preferably 0.5 to 1.2% by mass, based on the total solid content of the resin composition. The photoacid generator may be used alone or in combination of multiple types. In the case of a combination of multiple types, it is preferable that their total amount be within the above range. It is also preferable to use it in combination with a sensitizer in order to impart photosensitivity to a desired light source.

[0165] <Base Generator> The resin composition of the present invention may contain a base generator. Here, a base generator is a compound that can generate a base by physical or chemical action. Preferred base generators include thermal base generators and photobase generators. In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition contains a base generator. By containing a thermal base generator in the resin composition, the cyclization reaction of the precursor can be promoted by heating, for example, resulting in good mechanical properties and chemical resistance of the cured product, and thus good performance as an interlayer insulating film for redistribution layers contained in semiconductor packages, for example. The base generator may be an ionic base generator or a nonionic base generator. Examples of bases generated from the base generator include secondary amines and tertiary amines. The base generator is not particularly limited, and known base generators can be used. Examples of known base generators include carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, amineimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, α-lactone ring derivative compounds, phthalimide derivative compounds, and acyloxyimino compounds.

[0166] When the resin composition contains a base generating agent, the amount of base generating agent is preferably 0.1 to 50 parts by mass per 100 parts by mass of resin in the resin composition. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less. One or more types of base generating agents can be used. When two or more types are used, it is preferable that the total amount is within the above range.

[0167] <Solvent> The resin composition of the present invention preferably contains a solvent. Any known solvent can be used. An organic solvent is preferred. Examples of organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0168] Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, γ-valerolactone, alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl esters of 3-alkyloxypropionates (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-A Suitable examples include alkyl esters of alkyloxypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.).

[0169] Suitable ethers include, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0170] Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucocenone, and dihydrolevoglucocenone.

[0171] Suitable cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0172] As an example of a sulfoxide, dimethyl sulfoxide is a suitable choice.

[0173] Suitable amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0174] Suitable ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0175] Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenylcarbinol, n-amyl alcohol, methylamyl alcohol, and diacetone alcohol.

[0176] From the viewpoint of improving the properties of the coated surface, it is also preferable to use a mixture of two or more solvents.

[0177] In the present invention, one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, levoglucocenone, and dihydrolevoglucocenone, or a mixed solvent composed of two or more of these, is preferred. The combination of dimethyl sulfoxide and γ-butyrolactone, the combination of dimethyl sulfoxide and γ-valerolactone, the combination of 3-methoxy-N,N-dimethylpropionamide and γ-butyrolactone, the combination of 3-methoxy-N,N-dimethylpropionamide, γ-butyrolactone and dimethyl sulfoxide, or the combination of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred. Another preferred embodiment of the present invention is to further add toluene to these combined solvents in an amount of about 1 to 10% by mass relative to the total mass of the solvent. In particular, from the viewpoint of storage stability of the resin composition, an embodiment containing γ-valerolactone as the solvent is also a preferred embodiment of the present invention. In such embodiments, the content of γ-valerolactone relative to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. Furthermore, the upper limit of the above content is not particularly limited and may be 100% by mass. The above content can be determined by considering the solubility of specific resins and other components contained in the resin composition. Furthermore, when dimethyl sulfoxide and γ-valerolactone are used in combination, it is preferable to contain 60 to 90% by mass of γ-valerolactone and 10 to 40% by mass of dimethyl sulfoxide relative to the total mass of the solvent, more preferably 70 to 90% by mass of γ-valerolactone and 10 to 30% by mass of dimethyl sulfoxide, and even more preferably 75 to 85% by mass of γ-valerolactone and 15 to 25% by mass of dimethyl sulfoxide.

[0178] Furthermore, the resin composition of the present invention preferably contains a solvent having a boiling point of 50°C to 300°C at 1 atmosphere, and more preferably contains a solvent having a boiling point of 100°C to 260°C. In the present invention, the boiling point of the solvent is the boiling point at 1 atmosphere. According to this embodiment, it is believed that a cured product with excellent solvent removal properties and excellent resolution can be obtained. The boiling point is preferably 150°C or higher, more preferably 180°C or higher, and even more preferably 200°C or higher. The upper limit of the boiling point is preferably 250°C or lower, more preferably 240°C or lower, and even more preferably 230°C or lower. Furthermore, the resin composition of the present invention preferably contains two or more solvents having a boiling point of 100 to 260°C, more preferably two or more solvents having a boiling point of 150 to 250°C, and even more preferably two or more solvents having a boiling point of 180 to 230°C. Furthermore, the content of solvents with a boiling point of 100 to 260°C is preferably 40% by mass or more, more preferably 45% by mass or more, and even more preferably 50% by mass or more, based on the total mass of the composition. If two or more solvents with a boiling point of 100 to 260°C are included, it is preferable that their total amount be within the above range.

[0179] From the viewpoint of coatability, the solvent content is preferably such that the total solid content concentration of the resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, even more preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass. The solvent content can be adjusted according to the desired thickness of the coating film and the application method. If two or more solvents are included, it is preferable that their total is within the above range.

[0180] <Metal Adhesion Enhancers> The resin composition of the present invention preferably contains a metal adhesion enhancer from the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc. Examples of metal adhesion enhancers include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, amino compounds, and the like.

[0181] [Silane Coupling Agents] Examples of silane coupling agents include the compounds described in paragraph 0316 of International Publication No. 2021 / 112189 and the compounds described in paragraphs 0067 to 0078 of Japanese Patent Publication No. 2018-173573, the contents of which are incorporated herein by reference. It is also preferable to use two or more different silane coupling agents, as described in paragraphs 0050 to 0058 of Japanese Patent Publication No. 2011-128358. The following compounds are also preferable as silane coupling agents. In the following formulas, Me represents a methyl group and Et represents an ethyl group. R below represents a structure derived from a blocking agent in a blocked isocyanate group. The blocking agent can be selected according to the elimination temperature, but examples include alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, and active methylene compounds. For example, from the viewpoint of wanting to set the elimination temperature to 160 to 180°C, caprolactam is preferred. Examples of commercially available compounds of this type include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0182]

[0183] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- Examples include (aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, and 3-trimethoxysilylpropyl succinic anhydride. These can be used individually or in combination of two or more. In addition, oligomeric compounds having multiple alkoxysilyl groups can be used as silane coupling agents. Examples of such oligomeric compounds include compounds containing repeating units represented by the following formula (S-1). In formula (S-1), R Ｓ１ represents a monovalent organic group, R Ｓ２ R represents a hydrogen atom, a hydroxyl group, or an alkoxy group, and n represents an integer between 0 and 2. Ｓ１It is preferable that the structure includes polymerizable groups. Examples of polymerizable groups include groups having ethylenically unsaturated bonds, epoxy groups, oxetanyl groups, benzoxazolyl groups, blocked isocyanate groups, amino groups, etc. Examples of groups having ethylenically unsaturated bonds include vinyl groups, allyl groups, isoallyl groups, 2-methylallyl groups, groups having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl group), (meth)acrylamide groups, (meth)acryloyloxy groups, etc., with vinylphenyl groups, (meth)acrylamide groups, or (meth)acryloyloxy groups being preferred, vinylphenyl groups or (meth)acryloyloxy groups being more preferred, and (meth)acryloyloxy groups being even more preferred. Ｓ２ n is preferably an alkoxy group, and more preferably a methoxy group or an ethoxy group. n represents an integer from 0 to 2, and is preferably 1. Here, the structures of the repeating units represented by multiple formulas (S-1) contained in the oligomer-type compound may all be the same. Here, it is preferable that n is 1 or 2 in at least one of the repeating units represented by multiple formulas (S-1) contained in the oligomer-type compound, more preferably that n is 1 or 2 in at least two, and even more preferably that n is 1 in at least two. Commercial products can be used as such oligomer-type compounds, and an example of a commercial product is KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0184] [Aluminum-based adhesive aids] Examples of aluminum-based adhesive aids include aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), and ethyl acetate aluminum diisopropylate.

[0185] Other metal adhesion modifiers that can be used include the compounds described in paragraphs 0046 to 0049 of Japanese Patent Publication No. 2014-186186 and the sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Publication No. 2013-072935, the details of which are incorporated herein by reference.

[0186] The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. A value above the lower limit ensures good adhesion between the pattern and the metal layer, while a value below the upper limit ensures good heat resistance and mechanical properties of the pattern. Only one type of metal adhesion improver may be used, or two or more types may be used. If two or more types are used, it is preferable that their total value is within the above range.

[0187] <Migration Inhibitor> The resin composition of the present invention preferably further contains a migration inhibitor. By including a migration inhibitor, for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, the migration of metal ions originating from the metal layer (or metal wiring) into the film can be effectively suppressed.

[0188] While there are no particular limitations on the migration inhibitors, examples include compounds having heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, and 6H-pyran ring, triazine ring), thioureas and compounds having sulfanyl groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

[0189] As migration inhibitors, ion trapping agents that capture anions such as halogen ions can also be used.

[0190] Other migration inhibitors that can be used include the rust inhibitor described in paragraph 0094 of Japanese Patent Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Publication No. 2009-283711, the compounds described in paragraph 0052 of Japanese Patent Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Publication No. 2012-194520, and the compounds described in paragraph 0166 of International Publication No. 2015 / 199219, the details of which are incorporated herein by reference.

[0191] Specific examples of migration inhibitors include the following compounds.

[0192]

[0193] Among these, the resin composition of the present invention preferably contains a compound having an azole structure (azole compound), and more preferably contains an azole compound and the silane coupling agent described above.

[0194] When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass, based on the total solid content of the resin composition.

[0195] There may be only one type of migration inhibitor, or there may be two or more types. If there are two or more types of migration inhibitors, it is preferable that their total number is within the above range.

[0196] <Light Absorbers> The resin composition of the present invention may also preferably contain a compound (light absorber) whose absorbance at the exposure wavelength decreases upon exposure. Examples of light absorbers include the compounds described in paragraphs 0159 to 0183 of International Publication No. 2022 / 202647 and the compounds described in paragraphs 0088 to 0108 of Japanese Patent Application Publication No. 2019-206689. These contents are incorporated herein by reference.

[0197] <Polymerization Inhibitor> The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, and metal compounds.

[0198] Specific polymerization inhibitor compounds include those described in paragraph 0310 of International Publication No. 2021 / 112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenoxazine, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]nona-2-ene-N,N-dioxide, etc. This information is incorporated herein by reference. The following compounds are also used.

[0199] If the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass, based on the total solid content of the resin composition.

[0200] There may be only one polymerization inhibitor or two or more. If there are two or more polymerization inhibitors, it is preferable that their total number is within the above range.

[0201] <Other Additives> The resin composition of the present invention may optionally contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, photoacid generators, anti-aggregation agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliary agents (e.g., defoamers, flame retardants, etc.), to the extent that the effects of the present invention are obtained. By appropriately including these components, properties such as film properties can be adjusted. These components can be described, for example, in paragraphs 0183 onwards of Japanese Patent Application Publication No. 2012-003225 (paragraph 0237 of the corresponding US Patent Application Publication No. 2013 / 0034812), paragraphs 0101 to 0104, 0107 to 0109 of Japanese Patent Application Publication No. 2008-250074, and these contents are incorporated herein. When these additives are included, their total content is preferably 3% by mass or less of the solid content of the resin composition of the present invention.

[0202] [Surfactants] Various surfactants can be used as surfactants, such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0203] By incorporating a surfactant into the resin composition of the present invention, the liquid properties (especially the fluidity) of the prepared coating liquid composition are further improved, and the uniformity of the coating thickness and the liquid-saving properties can be further enhanced. Specifically, when forming a film using a coating liquid containing a surfactant, the interfacial tension between the surface to be coated and the coating liquid decreases, improving the wettability to the surface to be coated and improving the coatability to the surface to be coated. Therefore, it is possible to more favorably form a uniform film with less thickness variation.

[0204] Examples of fluorinated surfactants include the compounds described in paragraph 0328 of International Publication No. 2021 / 112189, which are incorporated herein by reference. Fluorinated polymer compounds can also be preferably used as fluorinated surfactants, which include repeating units derived from a (meth)acrylate compound having a fluorine atom and repeating units derived from a (meth)acrylate compound having two or more (preferably five or more) alkylene oxy groups (preferably ethylene oxy groups, propylene oxy groups). Examples include the following compounds.

[0205] The weight-average molecular weight of the above compound is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. As a fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in its side chain can also be used. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of Japanese Patent Application Publication No. 2010-164965, the contents of which are incorporated herein by reference. Examples of commercially available products include Megafac RS-101, RS-102, RS-718K, etc., manufactured by DIC Corporation.

[0206] The fluorine content in the fluorinated surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. Fluorinated surfactants with a fluorine content within this range are effective in terms of uniformity of coating film thickness and liquid saving, and also have good solubility in the composition.

[0207] Examples of silicone-based surfactants, hydrocarbon-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants include the compounds described in paragraphs 0329-0334 of International Publication No. 2021 / 112189, respectively, which are incorporated herein by reference.

[0208] One type of surfactant may be used, or two or more types may be used in combination. The surfactant content is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, relative to the total solid content of the composition.

[0209] [Inorganic Particles] Examples of inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.

[0210] The average particle diameter of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, even more preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. The above average particle diameter of the inorganic particles is the primary particle diameter and also the volume-average particle diameter. The volume-average particle diameter can be measured, for example, by dynamic light scattering using Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurement is difficult, it can also be measured by centrifugal sedimentation light transmission, X-ray transmission, or laser diffraction / scattering.

[0211] [Organotitanium Compounds] By including organotitanium compounds in the resin composition, a resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

[0212] Suitable organotitanium compounds include those in which an organic group is bonded to a titanium atom via covalent or ionic bonds. Specific examples of organotitanium compounds are shown in I) to VII) below: I) Titanium chelate compounds: Titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability for the resin composition and yield a good curing pattern. Specific examples include titanium bis(triethanolamine)diisopropoxide, titanium di(n-butoxide)bis(2,4-pentanedione), titanium diisopropoxidebis(2,4-pentanedione), titanium diisopropoxidebis(tetramethylheptanedione), titanium diisopropoxidebis(ethylacetoacetate), etc. II) Tetraalkoxy titanium compounds: For example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearaloxide, titanium tetrakis[bis{2,2-(alyloxymethyl)butoxide}], etc. III) Titanocene compounds: For example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium, etc. IV) Monoalkoxy titanium compounds: For example, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc. V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc.VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate. VII) Titanate coupling agents: For example, isopropyltridodecylbenzenesulfonyl titanate.

[0213] In particular, from the viewpoint of better chemical resistance, the organotitanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds. Titanium diisopropoxide bis(ethyl acetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium are preferred.

[0214] Furthermore, it is preferable to include a compound represented by the following formula (T-1) as an organotitanium compound, or in place of an organotitanium compound. In equation (T-1), M is titanium, zirconium, or hafnium, l1 is an integer from 0 to 2, l2 is 0 or 1, l1 + l2 × 2 is an integer from 0 to 2, m is an integer from 0 to 4, n is an integer from 0 to 2, l1 + l2 + m + n × 2 = 4, R １１ Each of these is independently a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenoxy group, R １２ R is a substituted or unsubstituted hydrocarbon group, ２ Each of these is an independent group containing a structure represented by the following formula (T-2), and R ３ Each of these is an independent group containing a structure represented by the following formula (T-2), and X Ａ Each of these is independently either an oxygen atom or a sulfur atom. In formula (T-2), X １ ~X ３ Each of these independently represents -C(-*)= or -N=, where * represents a bonding site with another structure, and # represents a bonding site with a metal atom.

[0215] In formula (T-1), from the viewpoint of storage stability of the composition, M is preferably titanium. In formula (T-1), an embodiment in which l1 and l2 are 0 is also one of the preferred embodiments of the present invention. In formula (T-1), m is preferably 2 or 4, and more preferably 2. In formula (T-1), n ​​is preferably 1 or 2, and more preferably 1. Here, in formula (T-1), it is also preferable that l1 and l2 are 0 and m is 0, 2, or 4.

[0216] In formula (T-1), from the viewpoint of the stability of the specific metal complex, R １１ A substituted or unsubstituted cyclopentadienyl ligand is preferred. Also, R １１ The cyclopentadienyl group, alkoxy group, and phenoxy group in the compound may be substituted, but an unsubstituted configuration is also a preferred embodiment of the present invention.

[0217] In formula (T-1), R １２ R is preferably a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrocarbon group having 2 to 10 carbon atoms. １２ The hydrocarbon group in may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but an aromatic hydrocarbon group is preferred. The aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, but a saturated aliphatic hydrocarbon group is preferred. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and even more preferably a phenylene group. １２ The substituents in are preferably monovalent substituents, such as halogen atoms. １２ If is an aromatic hydrocarbon group, it may have an alkyl group as a substituent. Among these, in formula (T-1), R １２ It is preferable that R is an unsubstituted phenylene group. １２ The phenylene group in this is preferably a 1,2-phenylene group.

[0218] In equation (T-1), m is 2 or greater, and R ２ If there are two or more of them, then the two or more R２ The structures of each may be the same or different. In equation (T-1), n ​​is 2 or greater, and R ３ If there are two or more of them, then the two or more R ３ The structures of each may be the same or different.

[0219] In formula (T-2), X １ ~X ３ Each of these independently represents -C(-*)= or -N=, preferably at least one represents -C(-*)=, and more preferably at least two represent -C(-*)=.

[0220] Specific examples of compounds represented by formula (T-1) include, but are not limited to, the compound corresponding to I-3 in the examples.

[0221] When an organic titanium compound is included, its content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the specific resin. When the content is 0.05 parts by mass or more, the heat resistance and chemical resistance of the resulting cured pattern are better, and when it is 10 parts by mass or less, the storage stability of the composition is better.

[0222] When an organic titanium compound is included, its content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin. When the content is 0.05 parts by mass or more, the heat resistance and chemical resistance of the resulting cured pattern are better, and when it is 10 parts by mass or less, the storage stability of the composition is better.

[0223] Other additives include the compounds described in paragraphs 0249-0282 and 0316-0358 of International Publication No. 2022 / 145355. The foregoing description is incorporated herein by reference.

[0224] <Characteristics of the Resin Composition> The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of coating film thickness, 1,000 mm ２ / s~12,000mm ２ / s is preferred, and 2,000 mm ２ / s~10,000mm ２ / s is more preferable, 2,500 mm ２ / s~8,000mm ２ / s is even more preferable. Within the above range, it becomes easier to obtain a highly uniform coating film. 1,000 mm ２ If the temperature is 1 / s or higher, it is easy to coat the film with the required thickness, for example, as an insulating film for rewiring, and 12,000 mm ２ If the rate is less than or equal to / s, a coating with excellent properties can be obtained on the coated surface.

[0225] When a film with a thickness of 5 μm is formed using the resin composition of the present invention, the transmittance of the film at a wavelength of 365 nm is preferably 15% or more, more preferably 20% or more, and even more preferably 25% or more. The upper limit of the transmittance is not particularly limited and may be 100%. The film can be obtained, for example, by coating a silicon wafer with the resin composition of the present invention and then drying it at 100°C for 5 minutes. The transmittance can be measured using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer).

[0226] <Restrictions on the substances contained in the resin composition> The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.

[0227] From the viewpoint of insulating properties, the metal content of the resin composition of the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but excludes metals included as complexes between organic compounds and metals. If multiple metals are included, it is preferable that the sum of these metals is within the above range.

[0228] Furthermore, methods for reducing metal impurities unintentionally included in the resin composition of the present invention include selecting raw materials with a low metal content as the raw materials constituting the resin composition of the present invention, performing filter filtration on the raw materials constituting the resin composition of the present invention, and performing distillation under conditions in which contamination is suppressed as much as possible by lining the inside of the apparatus with polytetrafluoroethylene or the like.

[0229] When considering the application of the resin composition of the present invention as a semiconductor material, the halogen atom content 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, the halogen atoms present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferable that the total amount of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above ranges. A preferred method for adjusting the halogen atom content is ion exchange treatment.

[0230] Conventional containers can be used as containers for the resin composition of the present invention. To suppress the incorporation of impurities into the raw materials and the resin composition of the present invention, it is also preferable to use multilayer bottles with an inner wall constructed of six types of resin in six layers, or bottles with a seven-layer structure of six types of resin. Examples of such containers include the container described in Japanese Patent Application Publication No. 2015-123351.

[0231] <Cured product of the resin composition> A cured product of the resin composition of the present invention can be obtained by curing the resin composition of the present invention. The cured product of the present invention is a cured product obtained by curing the resin composition. The curing of the resin composition is preferably done by heating, with a heating temperature of 120°C to 400°C being more preferably, 140°C to 380°C being even more preferably, and 170°C to 350°C being particularly preferred. The form of the cured product of the resin composition is not particularly limited and can be selected according to the application, such as in the form of a film, rod, sphere, or pellet. In the present invention, the cured product is preferably in the form of a film. By pattern processing of the resin composition, the shape of the cured product can also be selected according to the application, such as forming a protective film on the wall surface, forming via holes for conductivity, adjusting impedance, capacitance or internal stress, or providing a heat dissipation function. The film thickness of the cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less. The shrinkage rate when the resin composition of the present invention is cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage rate refers to the percentage change in volume of the resin composition before and after curing, and can be calculated using the following formula: Shrinkage rate [%] = 100 - (Volume after curing ÷ Volume before curing) × 100

[0232] <Characteristics of the Cured Resin Composition> The imidization reaction rate of the cured resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, the cured product may have excellent mechanical properties. The elongation at break of the cured resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more. The glass transition temperature (Tg) of the cured resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and even more preferably 230°C or higher.

[0233] <Preparation of Resin Composition> The resin composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited and can be carried out by conventionally known methods. Mixing methods include mixing with a stirring blade, mixing with a ball mill, and mixing by rotating a tank. The temperature during mixing is preferably 10 to 30°C, and more preferably 15 to 25°C.

[0234] For the purpose of removing foreign matter such as dirt and fine particles from the resin composition of the present invention, filtration using a filter is preferable. The filter pore size is preferably, for example, 5 μm or less, more preferably 1 μm or less, even more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. If the filter material is polyethylene, it is more preferably HDPE (high-density polyethylene). The filter may be one that has been pre-washed with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or in parallel. When multiple types of filters are used, filters with different pore sizes or materials may be combined. As an example of a connection configuration, an HDPE filter with a pore size of 1 μm is connected in series as the first stage, and an HDPE filter with a pore size of 0.2 μm is connected in series as the second stage. Furthermore, various materials may be filtered multiple times. When filtering multiple times, circulating filtration may be used. Furthermore, filtration may be performed under pressure. When filtration is performed under pressure, the pressure applied is preferably, for example, 0.01 MPa to 1.0 MPa, more preferably 0.03 MPa to 0.9 MPa, even more preferably 0.05 MPa to 0.7 MPa, and even more preferably 0.05 MPa to 0.5 MPa. In addition to filtration using a filter, impurity removal treatment using an adsorbent may also be performed. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, known adsorbents can be used. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. After filtration using a filter, the resin composition filled into bottles may be subjected to a degassing step by placing it under reduced pressure.

[0235] (Method for Manufacturing Cured Products) The method for manufacturing cured products of the present invention preferably includes a film-forming step of applying a resin composition onto a substrate to form a film. The method for manufacturing cured products more preferably includes the film-forming step, an exposure step of selectively exposing the film formed in the film-forming step, and a developing step of developing the film exposed in the exposure step using a developer to form a pattern. The method for manufacturing cured products particularly preferably includes the film-forming step, the exposure step, the developing step, and at least one of a heating step of heating the pattern obtained in the developing step and a post-development exposure step of exposing the pattern obtained in the developing step. Furthermore, the method for manufacturing cured products may also preferably include the film-forming step and a step of heating the film. Details of each step will be described below.

[0236] <Membrane Formation Process> The resin composition of the present invention can be used in a membrane formation process in which it is applied to a substrate to form a film. The method for producing a cured product of the present invention preferably includes a membrane formation process in which the resin composition is applied to a substrate to form a film.

[0237] [Substrate] The type of substrate can be appropriately determined according to the application and is not particularly limited. Examples of substrates include semiconductor manufacturing substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon; quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, reflective films; metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metal, and substrates in which a metal layer is formed by, for example, plating or vapor deposition); paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, molded substrates, and electrode plates for plasma display panels (PDPs). Semiconductor manufacturing substrates are particularly preferred, and silicon substrates, Cu substrates, and molded substrates are more preferred. These substrates may have layers such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) on their surface. The shape of the substrate is not particularly limited and may be circular or rectangular. If the substrate is circular, for example, a diameter of 100 to 450 mm is preferred, and 200 to 450 mm is more preferred. If it is rectangular, for example, the length of the shorter side is preferred to be 100 to 1000 mm, and 200 to 700 mm is more preferred. As the substrate, for example, a plate-shaped, preferably panel-shaped, substrate (substrate) is used.

[0238] When a resin composition is applied to the surface of a resin layer (for example, a layer made of cured material) or a metal layer to form a film, the resin layer or metal layer serves as the substrate.

[0239] Coating is a preferred method for applying the resin composition onto a substrate. Specific application methods include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating, or inkjet coating are preferred, and from the viewpoint of uniformity of film thickness and productivity, spin coating and slit coating are more preferred. By adjusting the solid content concentration of the resin composition and the coating conditions according to the application method, a film of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected depending on the shape of the substrate; for circular substrates such as wafers, spin coating, spray coating, and inkjet coating are preferred, while for rectangular substrates, slit coating, spray coating, and inkjet coating are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. Alternatively, a method can be applied in which a coating film, which has been formed in advance on a temporary support using the above application method, is transferred onto the substrate. Regarding the transfer method, the manufacturing methods described in paragraphs 0023, 0036-0051 of Japanese Patent Application Publication No. 2006-023696 and paragraphs 0096-0108 of Japanese Patent Application Publication No. 2006-047592 can be suitably used. Furthermore, a step to remove excess film from the edges of the substrate may be performed. Examples of such steps include edge bead rinsing (EBR) and back rinsing. A pre-wetting step may also be employed in which various solvents are applied to the substrate before applying the resin composition to improve the wettability of the substrate before applying the resin composition.

[0240] <Drying Process> After the film formation process (layer formation process), the film may be subjected to a drying process to remove the solvent from the formed film (layer). That is, the method for producing a cured product of the present invention may include a drying process for drying the film formed in the film formation process. The drying process is preferably performed after the film formation process and before the exposure process. The drying temperature of the film in the drying process is preferably 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. Drying may also be performed under reduced pressure. The drying time is exemplified as 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.

[0241] <Exposure Process> The above film may be subjected to an exposure process in which the film is selectively exposed. The method for manufacturing the cured product may include an exposure process in which the film formed by the film formation process is selectively exposed. Selective exposure means exposing a part of the film. By selective exposure, exposed areas (exposed parts) and unexposed areas (unexposed parts) are formed in the film. The amount of exposure is not particularly limited as long as the resin composition of the present invention can be cured, but for example, it may be 50 to 10,000 mJ / cm in terms of exposure energy at a wavelength of 365 nm. ２ Preferably, 200 to 8,000 mJ / cm² ２ This is preferable.

[0242] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, with 240 to 550 nm being preferred.

[0243] In relation to the light source, the exposure wavelength can be found in: (1) semiconductor lasers (wavelengths 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-line (wavelength 436nm), h-line (wavelength 405nm), i-line (wavelength 365nm), broad (three wavelengths: g, h, i), (4) excimer lasers, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F ２Examples of exposures include (5) excimer laser (wavelength 157 nm), (6) extreme ultraviolet light; EUV (wavelength 13.6 nm), (7) YAG laser with second harmonic 532 nm and third harmonic 355 nm. For the resin composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferred, and exposure with the i-line is more preferred from the viewpoint of exposure sensitivity. The exposure method is not particularly limited, and any method in which at least a part of the film made of the resin composition of the present invention is exposed is acceptable, but examples include exposure using a photomask and exposure by laser direct imaging.

[0244] <Post-exposure heating step> The above film may be subjected to a heating step after exposure (post-exposure heating step). That is, the method for producing a cured product of the present invention may include a post-exposure heating step in which the film exposed in the exposure step is heated. The post-exposure heating step can be performed after the exposure step and before the development step. The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, and more preferably 60°C to 120°C. The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, and more preferably 1 minute to 10 minutes. The heating rate in the post-exposure heating step is preferably 1 to 12°C / min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. The heating rate may also be changed as appropriate during heating. The heating means in the post-exposure heating step is not particularly limited, and known hot plates, ovens, infrared heaters, etc., can be used. Furthermore, it is preferable to carry out the heating process in a low-oxygen atmosphere by flowing inert gases such as nitrogen, helium, or argon through the system.

[0245] <Development Process> The film after exposure may be subjected to a development process in which a pattern is formed by developing it with a developer. That is, the method for manufacturing a cured product of the present invention may include a development process in which a pattern is formed by developing the film exposed in the exposure process with a developer. By developing, one of the exposed and unexposed parts of the film is removed, and a pattern is formed. Here, development in which the unexposed part of the film is removed by the development process is called negative development, and development in which the exposed part of the film is removed by the development process is called positive development.

[0246] [Developer] Developers used in the developing process include alkaline aqueous solutions or developers containing organic solvents.

[0247] When the developer is an alkaline aqueous solution, the basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. For example, the basic compounds described in paragraph 0300 of International Publication No. 2023 / 190064 can be used, and TMAH is more preferred. The description in paragraph 0300 of International Publication No. 2023 / 190064 is incorporated herein by reference. The content of the basic compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass, based on the total mass of the developer.

[0248] If the developer contains an organic solvent, the organic solvent may be one of the compounds described in paragraph 0387 of International Publication No. 2021 / 112189. This is incorporated herein by reference. Suitable alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutylcarbinol, triethylene glycol, etc., and suitable amides include N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc.

[0249] When the developer contains an organic solvent, one or more organic solvents may be used in mixture form. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide is more preferred, and a developer containing cyclopentanone is particularly preferred.

[0250] When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Alternatively, the above content may be 100% by mass.

[0251] If the developer contains an organic solvent, it may further contain at least one of a basic compound and a base generator. At least one of the basic compound and base generator in the developer may penetrate the pattern, improving performance such as the pattern's elongation at break.

[0252] As for the basic compound, organic bases are preferred from the viewpoint of reliability when remaining in the cured film (adhesion to the substrate when the cured product is further heated). As for the basic compound, basic compounds having an amino group are preferred, and primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amides, etc. are preferred, but in order to promote the imidation reaction, primary amines, secondary amines, tertiary amines or ammonium salts are preferred, secondary amines, tertiary amines or ammonium salts are more preferred, secondary amines or tertiary amines are even more preferred, and tertiary amines are particularly preferred. As for the basic compound, from the viewpoint of the mechanical properties of the cured product (elongation at break), it is preferable that it does not remain in the cured film (the resulting cured product), and from the viewpoint of promoting cyclization, it is preferable that the amount remaining before heating does not decrease easily due to vaporization, etc. Therefore, the boiling point of the basic compound is preferably 30°C to 350°C, more preferably 80°C to 270°C, and even more preferably 100°C to 230°C at atmospheric pressure (101,325 Pa). The boiling point of the basic compound is preferably higher than the boiling point of the organic solvent contained in the developer, minus 20°C, and more preferably higher than the boiling point of the organic solvent contained in the developer. For example, if the boiling point of the organic solvent is 100°C, the basic compound used is preferably 80°C or higher, and more preferably 100°C or higher. The developer may contain only one basic compound, or it may contain two or more basic compounds.

[0253] Specific examples of 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), DACO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, butanediamine, and 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.

[0254] The preferred embodiment of the base generator is the same as the preferred embodiment of the base generator contained in the above-described composition. In particular, the base generator is preferably a thermal base generator.

[0255] When the developer contains at least one of a basic compound and a base generator, the content of the basic compound or base generator is preferably 10% by mass or less, and more preferably 5% by mass or less, relative to the total mass of the developer. The lower limit of the above content is not particularly limited, but for example, 0.1% by mass or more is preferred. When the basic compound or base generator is solid in the environment in which the developer is used, the content of the basic compound or base generator is also preferably 70 to 100% by mass, relative to the total solid content of the developer. The developer may contain only one of the basic compound and the base generator, or it may contain two or more. When there are two or more of the basic compound and the base generator, it is preferable that their total is within the above range.

[0256] The developing solution may further contain other components. Examples of other components include known surfactants and known defoamers.

[0257] [Method of supplying developer] There are no particular restrictions on the method of supplying the developer as long as a desired pattern can be formed. These include immersing a substrate on which a film has been formed in the developer, paddle development in which the developer is supplied to the film formed on the substrate using a nozzle, or a method of continuously supplying the developer. There are no particular restrictions on the type of nozzle, and examples include straight nozzles, shower nozzles, spray nozzles, etc. From the viewpoint of developer penetration, removal of non-image areas, and manufacturing efficiency, a method of supplying the developer with a straight nozzle or a method of continuously supplying it with a spray nozzle is preferred, and from the viewpoint of developer penetration into the image area, a method of supplying with a spray nozzle is more preferred. In addition, a step may be adopted in which the developer is continuously supplied with a straight nozzle, the substrate is spun to remove the developer from the substrate, and after spin drying, the developer is supplied again with a straight nozzle, and the substrate is spun to remove the developer from the substrate. This step may be repeated multiple times. Examples of methods of supplying the developer in the development process include a step in which the developer is continuously supplied to the substrate, a step in which the developer is kept in a nearly stationary state on the substrate, a step in which the developer is vibrated on the substrate with ultrasound, etc., and a step that combines these.

[0258] The development time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the developer solution during development is not particularly specified, but is preferably 10 to 45°C, and more preferably 18 to 30°C.

[0259] In the developing process, after processing with the developer, the pattern may be further washed (rinsed) with a rinsing solution. Alternatively, methods such as supplying the rinsing solution before the developer in contact with the pattern dries completely may be employed.

[0260] [Rinsing Solution] If the developer is an alkaline aqueous solution, water can be used as the rinsing solution. If the developer contains an organic solvent, a solvent different from the solvent contained in the developer (for example, water, or an organic solvent different from the organic solvent contained in the developer) can be used as the rinsing solution.

[0261] When the rinsing solution contains an organic solvent, the organic solvent can be the same as the organic solvent exemplified above when the developer contains an organic solvent. Preferably, the organic solvent in the rinsing solution is different from the organic solvent in the developer, and more preferably, it is an organic solvent with lower pattern solubility than the organic solvent in the developer.

[0262] If the rinsing solution contains an organic solvent, one or more organic solvents may be used in mixture form. The organic solvents are preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME, more preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME, and even more preferably cyclohexanone and PGMEA.

[0263] When the rinsing solution contains an organic solvent, the amount of the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, relative to the total mass of the rinsing solution. Alternatively, the amount of the organic solvent may be 100% by mass, relative to the total mass of the rinsing solution.

[0264] The rinsing solution may contain at least one of a basic compound and a base generating agent. While not particularly limited, if the developer contains an organic solvent, a configuration in which the rinsing solution contains an organic solvent and at least one of a basic compound and a base generating agent is also a preferred embodiment of the present invention. Examples of basic compounds and base generating agents included in the rinsing solution include those exemplified above as basic compounds and base generating agents that may be included when the developer contains an organic solvent, and the preferred embodiment is similar. The basic compound and base generating agent included in the rinsing solution should be selected considering factors such as their solubility in the solvent in the rinsing solution.

[0265] When the rinse solution contains at least one of a basic compound and a base generating agent, the content of the basic compound or base generating agent is preferably 10% by mass or less, and more preferably 5% by mass or less, relative to the total mass of the rinse solution. The lower limit of the above content is not particularly limited, but for example, 0.1% by mass or more is preferred. If the basic compound or base generating agent is solid in the environment in which the rinse solution is used, the content of the basic compound or base generating agent is also preferably 70 to 100% by mass, relative to the total solid content of the rinse solution. When the rinse solution contains at least one of a basic compound and a base generating agent, the rinse solution may contain only one of the basic compound and base generating agent, or it may contain two or more. When there are two or more of the basic compound and base generating agent, it is preferable that their total is within the above range.

[0266] The rinse solution may further contain other components. Examples of other components include known surfactants and known defoaming agents.

[0267] [Method of supplying rinsing solution] There are no particular restrictions on the method of supplying the rinsing solution as long as a desired pattern can be formed. These include immersing the substrate in the rinsing solution, supplying the rinsing solution to the substrate by pouring the solution, supplying the rinsing solution to the substrate with a shower, and continuously supplying the rinsing solution onto the substrate using means such as a straight nozzle. From the viewpoint of the penetration of the rinsing solution, the removal of non-image areas, and manufacturing efficiency, there are methods of supplying the rinsing solution with a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuous supply with a spray nozzle is preferred, and from the viewpoint of the penetration of the rinsing solution into the image area, the method of supplying with a spray nozzle is more preferred. There are no particular restrictions on the type of nozzle, and examples include straight nozzles, shower nozzles, spray nozzles, etc. That is, the rinsing process is preferably a process of supplying the rinsing solution to the film after exposure using a straight nozzle or continuously supplying it, and it is more preferable to supply the rinsing solution using a spray nozzle. Possible methods for supplying the rinsing solution in the rinsing process include a process in which the rinsing solution is continuously supplied to the substrate, a process in which the rinsing solution is kept in a nearly stationary state on the substrate, a process in which the rinsing solution is vibrated on the substrate using ultrasound or the like, and a process that combines these methods.

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

[0269] The developing process may include a step of bringing the processing solution into contact with the pattern after processing with the developer or after washing the pattern with the rinsing solution. Alternatively, methods such as supplying the processing solution before the developer or rinsing solution in contact with the pattern has completely dried may be employed.

[0270] Examples of the above-mentioned treatment solution include a treatment solution containing at least one of water and an organic solvent, and at least one of a basic compound and a base generating agent. Preferred embodiments of the organic solvent and at least one of the basic compound and base generating agent are the same as preferred embodiments of the organic solvent and at least one of the basic compound and base generating agent used in the rinse solution described above. The method of supplying the treatment solution to the pattern can be the same as the method of supplying the rinse solution described above, and the preferred embodiments are also the same.

[0271] The content of basic compounds or base generators in the treatment solution is preferably 10% by mass or less, and more preferably 5% by mass or less, relative to the total mass of the treatment solution. The lower limit of the above content is not particularly limited, but for example, it is preferably 0.1% by mass or more. Furthermore, if the basic compound or base generator is solid in the environment in which the treatment solution is used, the content of basic compounds or base generators is also preferably 70 to 100% by mass, relative to the total solid content of the treatment solution. When the treatment solution contains at least one of basic compounds and base generators, the treatment solution may contain only one type of basic compound or base generator, or it may contain two or more types. When there are two or more types of basic compounds and base generators, it is preferable that their total is within the above range.

[0272] <Heating Step> The pattern obtained by the developing step (or the pattern after rinsing, if a rinsing step is performed) may be subjected to a heating step in which the pattern obtained by the developing step is heated. That is, the method for producing a cured product of the present invention may include a heating step in which the pattern obtained by the developing step is heated. Furthermore, the method for producing a cured product of the present invention may include a heating step in which a pattern obtained by another method without performing a developing step, or a film obtained by a film formation step is heated. In the heating step, resins such as polyimide precursors are cyclized to become resins such as polyimide. In addition, crosslinking of unreacted crosslinkable groups in specific resins or crosslinking agents other than specific resins also proceeds. The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, even more preferably 150 to 250°C, even more preferably 160 to 250°C, and particularly preferably 160 to 230°C.

[0273] In addition, the heating step can be carried out, for example, by the method described in paragraphs 0326 to 0332 of International Publication No. 2023 / 190064. This description is incorporated into the present specification. Preferably, the heating step is a step in which the heating promotes the cyclization reaction of the polyimide precursor within the pattern by the action of a base generated from the base generating agent.

[0274] In the heating process, heating is preferably carried out at a heating rate of 1 to 12°C / minute from the initial heating temperature to the maximum heating temperature. More preferably, the heating rate is 2 to 10°C / minute, and even more preferably 3 to 10°C / minute. By setting the heating rate to 1°C / minute or more, it is possible to prevent excessive volatilization of acid or solvent while ensuring productivity, and by setting the heating rate to 12°C / minute or less, it is possible to alleviate residual stress in the cured product. In addition, in the case of an oven capable of rapid heating, it is preferable to carry out heating at a heating rate of 1 to 8°C / second from the initial heating temperature to the maximum heating temperature, more preferably 2 to 7°C / second, and even more preferably 3 to 6°C / second.

[0275] The starting temperature for heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The starting temperature for heating refers to the temperature at which the process of heating to the maximum heating temperature is initiated. For example, when the resin composition of the present invention is applied to a substrate and then dried, this is the temperature of the film (layer) after drying, and it is preferable to start the heating process from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition.

[0276] The heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

[0277] In particular, when forming a multilayer laminate, from the viewpoint of interlayer adhesion, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, and especially preferably 120°C or higher. The upper limit of the above heating temperature is preferably 350°C or lower, more preferably 250°C or lower, and even more preferably 240°C or lower.

[0278] Heating may be carried out in stages. For example, the process may involve raising the temperature from 25°C to 120°C at a rate of 3°C / min, holding at 120°C for 60 minutes, raising the temperature from 120°C to 180°C at a rate of 2°C / min, and holding at 180°C for 120 minutes. It is also preferable to treat the film while irradiating it with ultraviolet light, as described in U.S. Patent No. 9,159,547. Such a pretreatment process can improve the properties of the film. The pretreatment process is preferably carried out for a short time of about 10 seconds to 2 hours, and more preferably for 15 seconds to 30 minutes. The pretreatment process may consist of two or more steps; for example, the first pretreatment step may be carried out in the range of 100 to 150°C, followed by the second pretreatment step in the range of 150 to 200°C. Furthermore, the film may be cooled after heating, and in this case, the cooling rate is preferably 1 to 5°C / min.

[0279] The heating process is preferably carried out in a low-oxygen atmosphere, such as by flowing an inert gas like nitrogen, helium, or argon, or under reduced pressure, from the viewpoint of preventing the decomposition of specific resins. The oxygen concentration is preferably 50 ppm (by volume) or less, and more preferably 20 ppm (by volume) or less. The heating means in the heating process is not particularly limited, but examples include hot plates, infrared furnaces, electric ovens, hot air ovens, and infrared ovens.

[0280] <Post-development exposure step> The pattern obtained in the development step (or the pattern after rinsing, if a rinsing step is performed) may be subjected to a post-development exposure step in which the pattern after the development step is exposed, either in place of the heating step or in addition to the heating step. That is, the method for producing a cured product of the present invention may include a post-development exposure step in which the pattern obtained in the development step is exposed. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or it may include only one of the heating step and the post-development exposure step. In the post-development exposure step, for example, a reaction in which the cyclization of a polyimide precursor or the like proceeds due to photosensitivity of the photobase generator can be promoted. In the post-development exposure step, it is sufficient for at least a part of the pattern obtained in the development step to be exposed, but it is preferable for the entire pattern to be exposed. The amount of exposure in the post-development exposure step is 50 to 20,000 mJ / cm in terms of exposure energy at the wavelength to which the photosensitive compound is sensitive. ２ Preferably, 100 to 15,000 mJ / cm² ２ This is more preferable. The post-development exposure step can be performed, for example, using the light source in the exposure step described above, and it is preferable to use broadband light.

[0281] <Metal Layer Formation Process> The pattern obtained by the development process (preferably one that has been subjected to at least one of the heating process and the post-development exposure process) may be subjected to a metal layer formation process in which a metal layer is formed on the pattern. That is, the method for producing a cured product of the present invention preferably includes a metal layer formation process in which a metal layer is formed on the pattern obtained by the development process (preferably one that has been subjected to at least one of the heating process and the post-development exposure process).

[0282] The metal layer is not particularly limited, and existing metal species can be used, with examples including copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals, with copper and aluminum being more preferred, and copper being even more preferred.

[0283] The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, methods described in Japanese Patent Publication No. 2007-157879, Japanese Patent Publication No. 2001-521288, Japanese Patent Publication No. 2004-214501, Japanese Patent Publication No. 2004-101850, U.S. Patent No. 7,888,181, and U.S. Patent No. 9,177,926 can be used. For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and methods combining these can be considered. More specifically, patterning methods combining sputtering, photolithography and etching, and patterning methods combining photolithography and electroplating can be mentioned. Preferred embodiments of plating include electroplating using copper sulfate or copper cyanide plating solutions.

[0284] The thickness of the metal layer is preferably 0.01 to 50 μm at the thickest part, and more preferably 1 to 10 μm.

[0285] <Applications> The manufacturing method of the cured product of the present invention, or the fields in which the cured product can be applied, include insulating films for electronic devices, interlayer insulating films for redistribution layers, and stress buffer films. Other applications include sealing films, substrate materials (base films and coverlays for flexible printed circuit boards, interlayer insulating films), or etching to form patterns on insulating films for the above-mentioned mounting applications. For more information on these applications, please refer to, for example, Science & Technology Co., Ltd., "High-Functionality and Application Technologies of Polyimides," April 2008, supervised by Masaaki Kakimoto; CMC Technical Library, "Fundamentals and Development of Polyimide Materials," November 2011; and the Japan Polyimide and Aromatic Polymer Research Association, ed., "Latest Polyimide Fundamentals and Applications," NTS, August 2010.

[0286] The method for manufacturing the cured product of the present invention, or the cured product of the present invention, can also be used for manufacturing printing plates such as offset plates or screen printing plates, for etching molded parts, and for manufacturing protective lacquers and dielectric layers in electronics, particularly microelectronics.

[0287] (Laminate and Method for Manufacturing a Laminate) The laminate of the present invention refers to a structure having multiple layers made of the cured product of the present invention. The laminate is a laminate containing two or more layers made of the cured product, and may be a laminate with three or more layers. Of the two or more layers made of the cured product included in the above laminate, at least one is made of the cured product of the present invention, and from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product due to the above shrinkage, it is also preferable that all the layers made of the cured product included in the above laminate are made of the cured product of the present invention.

[0288] In other words, the method for manufacturing the laminate of the present invention preferably includes a method for manufacturing the cured product of the present invention, and more preferably includes repeating the method for manufacturing the cured product of the present invention multiple times.

[0289] The laminate of the present invention preferably comprises two or more layers made of cured material, with a metal layer preferably included between any of the layers made of cured material. The metal layer is preferably formed by the metal layer formation step described above. That is, the method for manufacturing the laminate of the present invention preferably further includes a metal layer formation step of forming a metal layer on a layer made of cured material, which is performed multiple times during the manufacturing process of the cured material. The preferred embodiment of the metal layer formation step is as described above. As the laminate, for example, a laminate is preferred that includes at least three layers in which a first layer made of cured material, a metal layer, and a second layer made of cured material are laminated in this order. It is preferable that both the first layer made of cured material and the second layer made of cured material are layers made of cured material of the present invention. The resin composition of the present invention used to form the first layer made of cured material and the resin composition of the present invention used to form the second layer made of cured material may have the same composition or may have different compositions. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.

[0290] <Lamination Process> The method for manufacturing a laminate of the present invention preferably includes a lamination process. The lamination process is a series of steps that include performing, in this order, at least one of the following on the surface of a pattern (resin layer) or metal layer: (a) film formation process (layer formation process), (b) exposure process, (c) development process, (d) heating process, and post-development exposure process. However, the method may also involve repeating at least one of the following: (a) film formation process and (d) heating process and post-development exposure process. Furthermore, at least one of the following: (d) heating process and post-development exposure process may be followed by (e) metal layer formation process. Needless to say, the lamination process may further include the above-mentioned drying process and the like as appropriate.

[0291] If further lamination is performed after the lamination process, a surface activation treatment step may be performed after the exposure step, the heating step, or the metal layer formation step. Plasma treatment is an example of a surface activation treatment. Details of the surface activation treatment will be described later.

[0292] The above lamination process is preferably performed 2 to 20 times, and more preferably 2 to 9 times. For example, a configuration with 2 to 20 resin layers, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferred, and a configuration with 2 to 9 resin layers is even more preferred. Each of the above layers may have the same composition, shape, film thickness, etc., or they may be different.

[0293] In the present invention, it is particularly preferable to form a cured product (resin layer) of the resin composition of the present invention so as to cover the metal layer after providing the metal layer. Specifically, examples include repeating the steps in the order of (a) film formation, (b) exposure, (c) development, (d) heating and post-development exposure, and (e) metal layer formation, or repeating the steps in the order of (a) film formation, (d) heating and post-development exposure, and (e) metal layer formation. By alternately performing the lamination step of stacking the resin composition layer (resin layer) of the present invention and the metal layer formation step, the resin composition layer (resin layer) and the metal layer of the present invention can be alternately stacked.

[0294] (Surface Activation Treatment Step) The manufacturing method of the laminate of the present invention preferably includes a surface activation treatment step in which at least a portion of the metal layer and the resin composition layer is surface activated. The surface activation treatment step is usually performed after the metal layer formation step, but after the development step (preferably after at least one of the heating step and the post-development exposure step), the surface activation treatment step may be performed on the resin composition layer before the metal layer formation step. The surface activation treatment may be performed only on at least a portion of the metal layer, or only on at least a portion of the resin composition layer after exposure, or on at least a portion of both the metal layer and the resin composition layer after exposure. It is preferable to perform the surface activation treatment on at least a portion of the metal layer, and more preferably to perform the surface activation treatment on a portion or all of the area on the surface of the metal layer where the resin composition layer is formed. By performing the surface activation treatment on the surface of the metal layer in this way, the adhesion with the resin composition layer (film) provided on its surface can be improved. It is also preferable to perform the surface activation treatment on a portion or all of the resin composition layer (resin layer) after exposure. Thus, by performing a surface activation treatment on the surface of the resin composition layer, the adhesion between the surface-activated layer and the metal layer or resin layer provided on the surface-activated layer can be improved. In particular, when the resin composition layer is cured, such as when performing negative type development, it is less susceptible to damage from the surface treatment and adhesion is easily improved. The surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of International Publication No. 2021 / 112189. This content is incorporated herein by reference.

[0295] (Semiconductor Devices and Methods for Manufacturing the Same) The present invention also discloses semiconductor devices including a cured product or a laminate of the present invention. Furthermore, the present invention also discloses a method for manufacturing a semiconductor device including a method for manufacturing a cured product or a laminate of the present invention. Specific examples of semiconductor devices in which the resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer can be found in paragraphs 0213 to 0218 and Figure 1 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0296] (Polyimide) The resin of the present invention comprises a structure represented by the following formula (A-1). In formula (A-1), Z １ Q represents the group shown in the following formula (AA-1), and １ ~Q ８ Each of these independently represents a hydrogen atom or a monovalent organic group, n represents an integer from 0 to 2, m represents an integer from 0 to 2, n + m is 2, and when n is 2, there are two Qs. １ ~Q ４ These can be the same or different, and if m is 2, there are two Qs. ５ ~Q ８ Each of them may be the same or different, Q １ ~Q ４ At least two of them may bond together to form a ring structure, Q ５ ~Q ８ At least two of them may bond together to form a ring structure, L １ Each of these independently represents -O-, -C(=O)O-, or -S-, L ２ Each of the symbols independently represents -O-, -C(=O)O-, or -S-, and each of the symbols independently represents a bonding site with a nitrogen atom. In formula (AA-1), G １ ~G ８ Any two of these are L in equation (A-1) １ or L ２ This represents the bonding site with other G １ ~G ８ Each of these independently represents a hydrogen atom or a monovalent organic group.

[0297] Preferred embodiments of the resin of the present invention are the same as preferred embodiments of the specific resin described above. Preferred embodiments of formula (A-1) in the resin of the present invention are the same as preferred embodiments of these formulas in the specific resin in the resin composition of the present invention described above. Other preferred embodiments of the resin of the present invention are the same as preferred embodiments of the specific resin described above.

[0298] In particular, the resin of the present invention preferably contains repeating units represented by formula (1-1) above. Furthermore, the resin of the present invention preferably contains repeating units represented by formula (1-2) above.

[0299] Y in equation (1-1) １ It is preferable that the structure includes the structure represented by formula (A-1).

[0300] Here, the sum of a and b in equation (1-1) is 1 or greater, and there are a + b R １ In at least one of the equations, A in equation (R-1) １ Preferably, at least one of the groups is a vinylphenyl group, a maleimide group, a (meth)acryloyl group, a vinyl group, an allyl group, an epoxy group, or a group containing these, and more preferably a vinylphenyl group.

[0301] Also, the m+n Rs in equation (1-2) ２ In at least one of the equations, A in equation (R-2) ２ Preferably, at least one of the groups is a vinylphenyl group, a maleimide group, a (meth)acryloyl group, a vinyl group, an allyl group, an epoxy group, or a group containing these, and more preferably a vinylphenyl group.

[0302] The present invention will be described in more detail below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

[0303] <Synthesis Example> [Synthesis of 3-Chloropropyl Methacrylate] Dissolve 25.00 g (264 mmol) of 3-chloropropanol, 25.1 g (316.8 mmol) of pyridine, and 150 g of tetrahydrofuran in a flask and cool to -10°C to 0°C. Then, add 29.03 g (277.2 mmol) of methacrylate chloride dropwise over 30 minutes using a dropping funnel, raise the temperature to 20°C to 25°C, and stir for 3 hours. Next, the reaction solution was transferred to a 2 L separatory funnel, diluted with 1 L of ethyl acetate, washed twice with 500 mL of water, twice with 300 mL of 0.5 N (0.5 mol / L) hydrochloric acid aqueous solution, twice with 500 mL of saturated sodium bicarbonate solution, and then washed with 500 mL of saturated saline solution. After drying with magnesium sulfate, 0.02 g of p-methoxyphenol was added, and the solvent was removed using an evaporator to obtain 40 g of 3-chloropropyl methacrylate.

[0304] [Synthesis of DN-1] In a flask equipped with a stirrer, condenser, and thermometer, 16.07 g (100 mmol) of 1,5-dihydroxynaphthalene (Tokyo Chemical Industries Co., Ltd.) and 28.93 g (205 mmol) of 4-fluoronitrobenzene (Tokyo Chemical Industries Co., Ltd.) were dissolved in 80 g of N-methylpyrrolidone, and 30.41 g (220 mmol) of potassium carbonate was added. Subsequently, the reaction mixture was heated to 105°C, stirred for 5 hours, and then cooled to 40°C. The above reaction mixture was crystallized in 500 mL of methanol, and while stirring, 500 mL of saturated sodium bicarbonate solution and 500 mL of pure methanol were added in that order, stirred for 1 hour, and the crystals were filtered. Subsequently, the crystals were reslurred with 1 L of water, filtered, and then vacuum dried at 70°C for 20 hours to obtain 35 g of DN-1. The fact that it is DN-1 is １ This was confirmed by 1H-NMR spectroscopy. １ The NMR data is shown below. １ NMR data: (Deuterated dimethyl sulfoxide, 400 MHz, internal standard: tetramethylsilane) δ (ppm) = 7.21–7.23 (d, 4H), 7.42–7.44 (d, 2H), 7.62–7.66 (t, 2H), 7.86–7.89 (d, 2H), 8.27–8.29 (d, 4H)

[0305] [Synthesis of DN-2 to DN-16] DN-2 to DN-16 were synthesized using the same method as DN-1, except that the raw materials were changed.

[0306] [Synthesis of DA-1] In a flask equipped with a stirrer, condenser, and thermometer, 10.24 g (191.4 mmol) of ammonium chloride and 10.45 g (174 mmol) of acetic acid were dissolved in 60 mL of water. Subsequently, 49.2 g (880 mmol) of reduced iron, 35.0 g (87.0 mmol) of DN-1, and 240 mL of isopropyl alcohol were added, and the mixture was stirred for 1 hour. Next, the reaction mixture was heated to 80°C and stirred for 6 hours, after which it was filtered while being washed with tetrahydrofuran using a Nutsche filter lined with Celite. The above filtrate was evaporated to remove all solvents except water, crystallized in 2 L of saturated sodium bicarbonate water, filtered, and then re-slurred twice with 2 L of water. Dissolved in 1 L of tetrahydrofuran, 30 g of activated carbon was added, the mixture was stirred at 60°C for 1 hour, and filtered while being washed with tetrahydrofuran using a Nutsche filter lined with Celite. The above filtrate was evaporated to remove the solvent, and the crystals were vacuum-dried at 80°C for 20 hours to obtain 40 g of DA-1. The fact that it is DA-1 is... １ This was confirmed by 1H-NMR spectroscopy. １ NMR data: (Deuterated dimethyl sulfoxide, 400 MHz, internal standard: tetramethylsilane) δ (ppm) = 5.02 (s, 4H), 6.62–6.44 (d, 4H), 6.72–6.74 (d, 2H), 6.82–6.84 (d, 4H), 7.37–7.41 (t, 2H), 7.86–7.88 (d, 2H)

[0307] [Synthesis of DA-2 to DA-16] DA-2 to DA-16 were synthesized in the same manner as DA-1, except that the raw materials were changed to DN-2 to DN-16 as described above.

[0308] [Synthesis Example SP-1: Synthesis of Polyimide (SP-1)] In a flask equipped with a stirrer, condenser, and thermometer, 20.00 g (38.42 mmol) of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride was dissolved in 120 g of N-methylpyrrolidone (NMP) while removing moisture. Subsequently, while washing with 30 g of NMP, 3.864 g (17.87 mmol) of HAB (4,4'-diamino-3,3'-dihydroxybiphenyl, manufactured by Wakayama Seika Co., Ltd.), 6.118 g (17.87 mmol) of the DA-1 synthesized above, 1.072 g (5.379 mmol) of 4-amino-4'-methyldiphenyl ether, and 10 g of toluene were added. After stirring for 15 minutes, the mixture was reacted at 200°C for 5 hours under nitrogen flow and then cooled to 25°C. Next, 9.97 g (65.3 mmol) of 4-(chloromethyl)styrene, 13.3 g (96.1 limoles) of potassium carbonate, 1.91 g (11.5 mmol) of potassium iodide, and 0.2 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical were added, and the mixture was reacted at an internal temperature of 90°C for 10 hours. After cooling to 25°C, the mixture was diluted with 150 g of tetrahydrofuran, and the salts in the reaction solution were filtered through filter paper. Subsequently, the reaction solution was added dropwise to a mixture of 1.4 L of methanol and 0.6 L of water, stirred for 15 minutes, and the polyimide resin was filtered. Next, the resin was re-slurred with 1 L of water, filtered, re-slurred again with 1 L of methanol, filtered, and dried under reduced pressure at 40°C for 8 hours. Next, the dried resin was dissolved in 400 g of tetrahydrofuran, and 40 g of ion exchange resin (MB-1: Organo) was added. The mixture was stirred for 4 hours, and after filtering out the ion exchange resin, the polyimide resin was precipitated in 2 L of methanol and stirred for 15 minutes. The polyimide resin was filtered to obtain polyimide resin (SP-1), which was dried under reduced pressure at 4°C for 1 day. The weight-average molecular weight of the obtained polyimide resin SP-1 was 40,100, and the number-average molecular weight was 16,400. The structure of the repeating units is as follows: １ The structure was determined from the 1H-NMR spectrum. In the structure below, the subscripts of the repeating units represent the molar ratio of each repeating unit.

[0309] [Synthesis Examples SP-2 to SP-10, SP-14, SP-15: Synthesis of Polyimides (SP-2 to SP-10, SP-14 to SP-19)] SP-2 to SP-10 and SP-14 to SP-19 were synthesized using the same method as SP-1. The weight-average molecular weight and number-average molecular weight are listed in the table below. Each polyimide is a resin having repeating units represented by the following formula. The structure of the repeating unit is: １ The structure was determined from the 1H-NMR spectrum. In the structure below, the subscripts of the repeating units represent the molar ratio of each repeating unit.

[0310]

[0311] [Synthesis Example SP-11: Synthesis of Polyimide (SP-11)] In a flask equipped with a stirrer, condenser, and thermometer, 2.85 g (36.0 mmol) of pyridine and 13.47 g (29.9 mmol) of DA-7 (the above synthesized product) were dissolved in 70 g of N-methylpyrrolidone (NMP) while removing moisture, and the mixture was cooled to 0°C to 5°C. Subsequently, 3.158 g (15 mmol) of trimellitic anhydride chloride was dissolved in 50 g of N-methylpyrrolidone (NMP) and added dropwise over 1 hour in the range of -10°C to 0°C, stirred for 1 hour, and then stirred for a further 2 hours in the range of 20°C to 30°C. Next, 10.86 g (35 mmol) of 4,4'-oxydiphthalic anhydride, 3.481 g (16.10 mmol) of HAB (4,4'-diamino-3,3'-dihydroxybiphenyl, manufactured by Wakayama Seika Co., Ltd.), 2.156 g (8.0 mmol) of hexadecylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 10 mL of toluene were added while washing with 30 g of NMP. After stirring for 15 minutes, the mixture was reacted at 200°C for 4 hours under nitrogen flow and then cooled to 25°C. Next, 12.97 g (85 mmol) of 4-(chloromethyl)styrene, 17.28 g (125 limoles) of potassium carbonate, 2.49 g (15 mmol) of potassium iodide, and 0.3 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical were added, and the mixture was reacted at an internal temperature of 90°C for 14 hours. After cooling to 25°C, the mixture was diluted with 150 g of tetrahydrofuran, and the salts in the reaction solution were filtered out. Subsequently, the reaction solution was added dropwise to a mixture of 1.4 L of methanol and 0.6 L of water, stirred for 15 minutes, and the polyimide resin was filtered out. Next, the resin was re-slurred with 1 L of water, filtered, re-slurred again with 1 L of methanol, filtered, and dried under reduced pressure at 40°C for 8 hours. Next, the dried resin described above was dissolved in 400 g of tetrahydrofuran, and 40 g of ion exchange resin (MB-1: Organo) was added. The mixture was stirred for 4 hours, and after filtering out the ion exchange resin, the polyimide resin was precipitated in 2 L of methanol and stirred for 15 minutes. The polyimide resin was filtered to obtain the polyimide resin (SP-11), which was dried under reduced pressure at 45°C for 1 day. The weight-average molecular weight of the obtained polyamide-imide resin SP-11 was 29,800, and the number-average molecular weight was 12,600. The structure of the repeating units is as follows: １The structure was determined from the 1H-NMR spectrum. In the structure below, the subscripts of the repeating units represent the molar ratio of each repeating unit.

[0312] [Synthesis Example SP-12: Synthesis of Polyimide (SP-12)] In a flask equipped with a stirrer, condenser, and thermometer, 15.51 g (50.0 mmol) of 4,4'-oxydiphthalic anhydride and 0.1 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical were mixed with 80 g of N-methylpyrrolidone (NMP), while removing water. Next, 11.16 g (18.4 mmol) of DA-13, 13.20 g (27.6 mmol) of DA-4, and 1.53 g (8.00 mmol) of 4-heptylaniline were dissolved in 100 g of NMP. These were then added dropwise to the solution over 1 hour at a temperature of 10°C to 25°C, stirred for 2 hours at 20°C to 25°C, and then 18.2 g of pyridine and 14.7 g of acetic anhydride were added. The mixture was then reacted at 80°C for 4 hours. After the reaction was complete, the mixture was cooled to 25°C and diluted with 200 mL of tetrahydrofuran. Subsequently, the reaction mixture was added dropwise to a mixture of 2.0 L of methanol and 0.5 L of water, stirred for 15 minutes, and then the polyimide resin was filtered. Next, the resin was re-slurred with 1 L of water, filtered, re-slurred again with 1 L of methanol, filtered, and dried under reduced pressure at 40°C for 10 hours. Next, the dried resin was dissolved in a mixture of 350 g of tetrahydrofuran and 50 g of dimethyl sulfoxide. 40 g of ion exchange resin (MB-1: Organo Co., Ltd.) was added, and the mixture was stirred for 4 hours. After filtering out the ion exchange resin, the polyimide resin was precipitated in 2 L of methanol and stirred for 15 minutes. The polyimide resin was filtered and dried under reduced pressure at 45°C for 1 day to obtain polyimide resin (SP-12). The weight-average molecular weight of the obtained polyimide (SP-12) was 27,700, and the number-average molecular weight was 11,200. Polyimide (SP-12) is a resin having repeating units represented by the following formula (SP-12). The structure of the repeating unit is: １ The structure was determined from the 1H-NMR spectrum. In the structure below, the subscripts of the repeating units represent the molar ratio of each repeating unit.

[0313] [Synthesis Example SP-13: Synthesis of Polyimide (SP-13)] SP-13 was synthesized using the same method as SP-12. The weight-average molecular weight was 47,700 and the number-average molecular weight was 18,500. SP-13 is a resin having repeating units represented by the following formula. The structure of the repeating unit is: １ The structure was determined from the 1H-NMR spectrum. In the structure below, the subscripts of the repeating units represent the molar ratio of each repeating unit.

[0314] The polymerizability values ​​(C=C value) of SP-1 to SP-19 are shown in the table below. The polymerizability values ​​were calculated by the following method. The molar amount of vinylphenyl groups was measured by the following method. After dissolving 0.1 g of the specific resin in 0.9 g of deuterated dimethyl sulfoxide, １ The amount of vinylphenyl groups was calculated by measuring with 1H-NMR. １ The number of 1H-NMR cycles was set at 640. Tetramethylsilane was used as the reference substance. １ The molar amount of vinylphenyl groups in the specific resin was calculated from the ratio of the integrated intensity of the peak around 5.0–7.0 ppm derived from vinylphenyl groups in the 1H-NMR chart to the integrated intensity of the peak derived from the reference substance, the amount of the reference substance, and the amount of the specific resin. The molar amounts of other structures were also measured by calculating the integrated intensity of the peak corresponding to each structure using the same method as for the vinylphenyl groups.

[0315]

[0316] The following table shows the content (mass%) and content (mol / g) of the structure represented by formula (A-1) (A-1 structure) in SP-1 to SP-19. The content (mass%) of the A-1 structure was calculated using the following formula: Content (mass%) of the A-1 structure = Molecular weight of the A-1 structure / Total molecular weight of each repeating unit × 100 The content (mol / g) of the A-1 structure was calculated using the following method: After dissolving 0.1 g of the specific resin in 0.9 g of deuterated chloroform, １ The molar amount of the structure represented by formula (A-1) was calculated by measuring with 1H-NMR. １The number of 1H-NMR cycles was set at 640. Tetramethylsilane was used as the reference substance. １ The molar amount of structure A-1 in the specific resin was calculated from the ratio of the integrated intensity of the peak derived from the naphthylene group to the integrated intensity of the peak derived from the reference substance in the 1H-NMR chart, the amount of the reference substance, and the amount of the specific resin. The molar amounts of other structures were similarly measured by calculating the integrated intensity of the peak corresponding to each structure. Content of structure A-1 (moles / g) = Molar amount of structure A-1 (moles) / Number average molecular weight of the entire resin (g) × 100

[0317]

[0318]

[0319] [Synthesis of comparative compound A-1] In a flask equipped with a stirrer, condenser, and thermometer, 22.12 g (50.0 mmol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride was dissolved in 100 g of N-methylpyrrolidone (NMP) while removing moisture. Subsequently, while washing with 30 g of NMP, 3.892 g (18 mmol) of HAB (manufactured by Wakayama Seika Co., Ltd.), 4.271 g (27 mmol) of 1,5-diaminonaphthalene, 1.091 g (10.00 mmol) of p-aminophenol, and 10 g of toluene were added. After stirring for 15 minutes, the mixture was reacted at 200°C for 4 hours under nitrogen flow and then cooled to 25°C. Next, 13.78 g (85 mmol) of 3-chloropropyl methacrylate, 17.28 g (125 limoles) of potassium carbonate, 2.49 g (15 mmol) of potassium iodide, and 0.3 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical were added, and the mixture was reacted at an internal temperature of 90°C for 14 hours. After cooling to 25°C, the mixture was diluted with 150 g of tetrahydrofuran, and the salts in the reaction solution were filtered through filter paper. Subsequently, the reaction solution was added dropwise to a mixture of 1.4 L of methanol and 0.6 L of water, stirred for 15 minutes, and the polyimide resin was filtered. Next, the resin was re-slurred with 1 L of water, filtered, re-slurred again with 1 L of methanol, filtered, and dried under reduced pressure at 40°C for 8 hours. Next, the dried resin described above was dissolved in 400 g of tetrahydrofuran, and 40 g of ion exchange resin (MB-1: Organo) was added. The mixture was stirred for 4 hours, and after filtering out the ion exchange resin, the polyimide resin was precipitated in 2 L of methanol and stirred for 15 minutes. The polyimide resin was filtered to obtain polyimide resin (A-1), which was dried under reduced pressure at 45°C for 1 day. The weight-average molecular weight of the obtained polyimide resin A-1 was 20,200, and the number-average molecular weight was 8,300. The structure of the repeating units is as follows: １ The structure was determined from the 1H-NMR spectrum. In the structure below, the subscripts of the repeating units represent the molar ratio of each repeating unit.

[0320] <Examples and Comparative Examples> In each example, the components listed in the table below were mixed to obtain each resin composition. Similarly, in each comparative example, the components listed in the table below were mixed to obtain each comparative composition. Specifically, the content of each component listed in the table was the amount (parts by mass) indicated in the "Addition Amount" column of each column in the table. The obtained resin compositions and comparative compositions were pressure filtered using a polytetrafluoroethylene filter with a pore width of 0.5 μm. In the table, "-" indicates that the composition does not contain the corresponding component.

[0321]

[0322]

[0323] Details of each component listed in the table are as follows:

[0324] [Resin (cyclized resin or its precursor)] ・SP-1 to SP-19: SP-1 to SP-19 synthesized as described above ・A-1: The above synthesized product (for comparative example)

[0325] [Polymerizable Compounds] ・B-1: SR-209: SR-209 (manufactured by Sartomer) ・B-2: 1,9-nonanediol dimethacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) ・B-3: ADPH: dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., melting point: below 25°C) ・B-4: tris(2-acryloyloxyethyl) isocyanurate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0326] [Solvents] ・DMSO: Dimethyl sulfoxide ・GBL: γ-Butyrolactone ・NMP: N-methylpyrrolidone ・γ-Valerolactone: γ-Valerolactone ・3-MCH: 3-Methylcyclohexanone ・MDMPA: KJCMPA-100 (manufactured by KJ Chemicals Co., Ltd.) In the table, "DMSO / GBL" and "DMSO / γ-Valerolactone" indicate that DMSO and GBL were used in a mixing ratio (mass ratio) of DMSO:GBL = 20:80 and DMSO:γ-Valerolactone = 20:80, respectively. Furthermore, the descriptions "γ-valerolactone / 3-MCH" and "GBL / 3-MCH" indicate that a mixture was used with a mixing ratio (mass ratio) of γ-valerolactone:3-MCH = 80:20 and GBL:3-MCH = 80:20, respectively.

[0327] [Polymerization initiators (all are trade names)] ・C-1: IRGACURE OXE 01 (manufactured by BASF) ・C-2: IRGACURE OXE 02 (manufactured by BASF) ・C-3: IRGACURE OXE 03 (manufactured by BASF) ・C-4: Benzoyl peroxide (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0328] [Migration Inhibitors] ・E-1 to E-3: Compounds with the following structure

[0329] [Metal Adhesion Improvers] ・F-1: KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd.) ・F-2: KBM-9659 (manufactured by Shin-Etsu Chemical Co., Ltd.) ・F-3: X-12-1050 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0330] [Polymerization inhibitors] • G-1: 1,4-benzoquinone • G-2: 4-methoxyphenol • G-3: 1,4-dihydroxybenzene • G-4: Compound with the following structure G-5: 2-nitroso-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0331] [Metal complexes] ・I-1: TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd.) ・I-2: TC-401 (manufactured by Matsumoto Fine Chemical Co., Ltd.) ・I-3: Compound with the following structure

[0332] In each example, the resin compositions prepared were coated, dried, and the resulting films with a thickness of 5 μm exhibited a light transmittance of 15% or more at a wavelength of 365 nm. The films were obtained by coating a silicon wafer with the resin composition and then drying it at 100°C for 5 minutes. Transmittance was measured using a UV-Vis spectrophotometer (Varian Cary-5 spectrophotometer).

[0333] Furthermore, specific resins were obtained from each resin composition by the following method, and the polymerizability value, A-1 structure content (mass%), and A-1 structure content (mol / g) were measured by the method described above. The same values ​​as those listed in the table above were obtained.

[0334] <Evaluation> [Evaluation of Glass Transition Temperature] In each example and comparative example, each resin composition or comparative composition was applied to a silicon wafer by spin coating to form a resin composition layer. The silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100°C for 5 minutes to obtain a uniform resin composition layer with a thickness of approximately 15 μm on the silicon wafer. The entire surface of the obtained resin composition layer was subjected to a stepper (Nikon NSR 2005 i9C) with a pressure of 500 mJ / cm². ２The sample was exposed using i-line lithography with the specified exposure energy. The resin composition layer (resin layer) after exposure was heated in a nitrogen atmosphere at a heating rate of 10°C / min until it reached the temperature indicated in the "Temperature" column of the "Curing Conditions" section of the table, and then heated for the time indicated in the "Curing Time" column of the table. The cured resin layer (cured film) was immersed in a 4.9 mass% hydrofluoric acid aqueous solution to peel the cured film from the silicon wafer. 1 to 5 mg of the peeled film was weighed into an aluminum pan, and the weight loss was measured using a DSC-3500 manufactured by NETZSCH Japan Co., Ltd. under the following conditions. <Measurement Conditions> (1) The temperature was raised from 25°C to 300°C at a rate of 10°C / min. (2) The temperature was cooled from 300°C to below 25°C. (3) The temperature was raised from 25°C to 300°C at a rate of 10°C / min. (4) The temperature was cooled from 300°C to 25°C. The evaluation was carried out according to the evaluation criteria below, and the evaluation results are recorded in the "Glass Transition Temperature" column of the table. -Evaluation Criteria- A: The glass transition temperature was 270°C or higher. B: The glass transition temperature was between 230°C and less than 270°C. C: The glass transition temperature was less than 230°C.

[0335] [Evaluation of Elongation at Break] In each example and comparative example, each resin composition or comparative composition was applied to a silicon wafer by spin coating to form a resin composition layer. The silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100°C for 5 minutes to obtain a uniform resin composition layer with a thickness of approximately 15 μm on the silicon wafer. The entire surface of the obtained resin composition layer was subjected to a stepper (Nikon NSR 2005 i9C) with a pressure of 500 mJ / cm². ２The sample was exposed using i-line lithography with the specified exposure energy. The resin composition layer (resin layer) after exposure was heated in a nitrogen atmosphere at a heating rate of 10°C / min until it reached the temperature indicated in the "Temperature" column of the "Curing Conditions" section of the table. After reaching this temperature, it was heated for the time indicated in the "Curing Time" column of the table. The cured resin layer (cured film) was immersed in a 4.9 mass% hydrofluoric acid aqueous solution to peel the cured film from the silicon wafer. The peeled cured film was punched out using a punching machine to produce test specimens with a sample width of 3 mm and a sample length of 30 mm. The obtained test specimens were subjected to tensile testing using a Tensilon machine at a crosshead speed of 300 mm / min, under conditions of 25°C and 65% RH (relative humidity), and the longitudinal elongation at break of the test specimens was measured in accordance with JIS-K6251:2017. Each evaluation was performed five times, and the arithmetic mean of the elongation rate at fracture (elongation at break) of the test specimen was used as the index value. The above index value was evaluated according to the evaluation criteria below, and the evaluation results are recorded in the "Elongation at Break" column of the table. The higher the above index value, the better the film strength (elongation at break) of the resulting cured film. (Evaluation Criteria) A: The above index value was 60% or higher. B: The above index value was 50% or higher but less than 60%. C: The above index value was 40% or higher but less than 50%. D: The above index value was less than 40%.

[0336] [Evaluation of Insulation Reliability] The resin composition or comparative composition prepared in each example and comparative example was applied in layers to a copper substrate by spin coating to form a resin composition layer or comparative composition layer. The copper substrate on which the obtained resin composition layer or comparative composition layer was formed was dried on a hot plate at 100°C for 5 minutes to obtain a resin composition layer or comparative composition layer with a thickness of 5 μm and uniform thickness on the copper substrate. The resin composition layer or comparative composition layer on the copper substrate was subjected to a pressure test of 500 mJ / cm using a stepper (Nikon NSR 2005 i9C). ２Using a photomask with a 100 μm square non-mask area formed at an exposure energy of i-line, exposure was performed, followed by development for 60 seconds with the developer described in the "Development Method (Developer)" column of the table, and then rinsing with propylene glycol monomethyl ether acetate (PGMEA) to obtain a 100 μm square resin layer. Furthermore, the resin layer (pattern) was formed by heating in a heated oven under a nitrogen atmosphere at the temperature and curing time described in the "Curing Conditions" column of the table. After the above resin layer and copper substrate were left in a constant temperature bath at 175°C for 1000 hours, cross-sectional SEM (scanning microscope) measurements were performed to evaluate the void area ratio between the copper substrate and the resin layer. The void area ratio was calculated using the following formula: Void area ratio (%) = (Area of ​​voids observed by SEM measurement) / (Total area of ​​resin layer) × 100. The obtained void area ratio value was evaluated according to the following evaluation criteria. The evaluation results are described in the "Insulation Reliability" column of the table. The smaller the void area ratio, the better the reliability of the cured film after the HTS (High Temperature Storage-test). This means that voids are less likely to form between the metal layer and the cured material even after a long period of time, resulting in good insulation reliability. -Evaluation Criteria- A: The void area ratio was 0.2% or less. B: The void area ratio was greater than 0.2% but 0.5% or less. C: The void area ratio was greater than 0.5%.

[0337] [Evaluation of Surface Flatness] In each example and comparative example, each resin composition or comparative composition was applied to a silicon wafer by spin coating to form a resin composition layer. The silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100°C for 5 minutes to obtain a uniform resin composition layer with a thickness of approximately 10 μm on the silicon wafer. The difference X (μm) between the concave and convex parts of the obtained resin composition layer was measured using a scanning electron microscope (S-4800) (manufactured by Hitachi High-Technologies Corporation) and evaluated according to the following criteria. The evaluation results are listed in the "Surface Flatness" column of the table. A smaller difference (X) between the concave and convex parts indicates better surface flatness and is therefore preferable. -Evaluation Criteria- A: X was 0.2 μm or less. B: X was greater than 0.2 μm and 0.5 μm or less. C: X was greater than 0.5 μm.

[0338] [Resolution Evaluation] Each resin composition used in each example and comparative example, or the comparative composition, was applied in layers to the surface of a copper thin layer formed on a resin substrate, using a spin coating method. The layers were dried at 100°C for 5 minutes to form a resin composition layer with a thickness of 5 μm. After that, a stepper (FPA-3000 i5 (manufactured by Canon Corporation)) was used to evaluate the resolution at NA=0.50 and 300 mJ / cm². ２Exposure was performed using a hole pattern mask with hole patterns of 1 to 10 μm in diameter formed at 1 μm intervals, at a wavelength of 365 nm. Subsequently, development was performed with cyclopentanone for 15 seconds, rinsing with PGMEA for 30 seconds, and then heating was performed under a nitrogen atmosphere at a heating rate of 10°C / min, under conditions selected from 230°C for 3 hours, 200°C for 2 hours, or 170°C for 2 hours to obtain hole patterns of 1 to 10 μm. In each example or comparative example, the heating conditions selected are indicated in the "Curing Conditions" column of the table. The formed hole patterns were evaluated according to the following evaluation criteria. The evaluation results are indicated in the "Resolution" column of the table. Image analysis was performed using an SEM (scanning electron microscope), and if the residual film rate at the bottom of the holes was 1% or less, it was judged to be resolvable. The smaller the diameter of the hole pattern that can be formed, the better the resolution; for example, A or B is preferred. -Evaluation Criteria- A: Hole patterns with a diameter of 3 μm and 5 μm were resolvable. B: Hole patterns with a diameter of 3 μm could not be resolved, but hole patterns with a diameter of 5 μm were resolvable. C: Neither hole patterns with a diameter of 3 μm nor 5 μm could be resolved.

[0339] <Example 101> The resin composition used in Example 1 was applied in layers to the surface of a copper thin layer formed on a resin substrate by spin coating, and dried at 100°C for 4 minutes to form a resin composition layer with a thickness of 20 μm. Then, it was exposed using a stepper (Nikon Corporation, NSR1505 i6). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-and-space pattern and a line width of 10 μm). After exposure, it was heated at 100°C for 4 minutes. After the above heating, it was developed with cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain the layer pattern. Next, under a nitrogen atmosphere, the temperature was increased at a rate of 10°C / min until it reached 230°C, and then maintained at 230°C for 3 hours to form an interlayer insulating film for the redistribution layer. This interlayer insulating film for the redistribution layer had excellent insulating properties. Furthermore, when semiconductor devices were manufactured using these interlayer insulating films for redistribution layers, it was confirmed that they functioned without any problems.

[0340] <Examples 102 to 126> In Example 101, the resin composition was changed from that used in Example 1 to that used in Examples 2 to 126, respectively. Otherwise, the evaluation was the same as in Example 101. In all examples, the interlayer insulating film for the redistribution layer had excellent insulating properties. The semiconductor device operated without problems.

Claims

1. A resin composition containing a polyimide having a structure represented by the following formula (A-1). In formula (A-1), Z １ represents a group represented by the following formula (AA-1), and Q １ to Q ８ each independently represents a hydrogen atom or a monovalent organic group, n represents an integer from 0 to 2, m represents an integer from 0 to 2, n + m = 2, and when n = 2, two Q １ to Q ４ may be the same or different from each other, and when m = 2, two Q ５ to Q ８ may be the same or different from each other, Q １ to Q ４ at least two of them may combine to form a ring structure, and Q ５ to Q ８ at least two of them may combine to form a ring structure, L １ each independently represents -O-, -C(=O)O- or -S-, and L ２ each independently represents -O-, -C(=O)O- or -S-, and * each independently represents a bonding site with a nitrogen atom. In formula (AA-1), G １ to G ８ any two of them represent a bonding site with L １ or L ２ in formula (A-1), and the other G １ to G ８ each independently represents a hydrogen atom or a monovalent organic group.

2. The resin composition according to claim 1, wherein the resin has polymerizable groups.

3. The resin composition according to claim 2, wherein the polymerizable value of the resin is 0.2 to 3.0 mmol / g.

4. The resin composition according to any one of claims 1 to 3, wherein when a film with a thickness of 5 μm is formed using the resin composition, the transmittance of the film at a wavelength of 365 nm is 15% or more.

5. The resin composition according to any one of claims 1 to 3, wherein the resin comprises a repeating unit represented by the following formula (1-1). In formula (1-1), X １ represents an organic group with 4 or more carbon atoms, Y １ R represents an organic group with 4 or more carbon atoms. １ Each of these independently represents a structure expressed by the following formula (R-1), where a represents an integer from 0 to 4, b represents an integer greater than or equal to 0, and X １ and Y １ At least one of them includes a structure represented by formula (A-1). In formula (R-1), L １ represents a 1+1 valent linking group, A １ represents a polymerizable group, a1 represents an integer greater than or equal to 1, and * represents X in formula (1-1). １ or Y １ This represents the connection point.

6. The aforementioned Y １ The resin composition according to claim 5, wherein the structure is represented by formula (A-1).

7. The sum of a and b in equation (1-1) is 1 or greater, and there are a + b R １ In at least one of the equations, A in equation (R-1) １ The resin composition according to claim 5, wherein at least one of the groups is a vinylphenyl group, a maleimide group, a (meth)acryloyl group, a vinyl group, an allyl group, an epoxy group, or a group comprising these.

8. The sum of a and b in equation (1-1) is 1 or greater, and there are a + b R １ In at least one of the equations, A in equation (R-1) １ The resin composition according to claim 5, wherein at least one of the groups is a vinylphenyl group.

9. The resin composition according to claim 5, wherein the resin further comprises repeating units represented by the following formula (1-2). In formula (1-2), X ２ represents an organic group with 4 or more carbon atoms, Y ２ represents an organic group with 4 or more carbon atoms, X ２ and Y ２ None of them include the structure represented by formula (A-1), R ２ Each of these independently represents a structure expressed by equation (R-2), where m is an integer from 0 to 4, n is an integer greater than or equal to 0, and n+m is an integer greater than or equal to 1. In formula (R-2), L ２ represents a² + 1 valent linking group, A ２ represents a polymerizable group, a2 represents an integer greater than or equal to 1, and * represents X in formula (1-2). ２ or Y ２ This represents the connection point.

10. m+n Rs in equation (1-2) ２ In at least one of the equations, A in equation (R-2) ２ The resin composition according to claim 9, wherein at least one of the groups is a vinylphenyl group, a maleimide group, a (meth)acryloyl group, a vinyl group, an allyl group, an epoxy group, or a group comprising these.

11. m+n Rs in equation (1-2) ２ In at least one of the equations, A in equation (R-2) ２ The resin composition according to claim 9, wherein at least one of the groups is a vinylphenyl group.

12. X in equation (1-1) １ The resin composition according to claim 5, wherein each of the structures is obtained by removing two or more hydrogen atoms from a structure represented by any of the following formulas (V-1) to (V-4). In formula (V-2), R Ｘ１ Each of these is independently a hydrogen atom, an alkyl group, or an alkyl halide. In formula (V-3), R Ｘ２ and R Ｘ３ Each of these independently represents a hydrogen atom or a substituent, R Ｘ２ and R Ｘ３ They may combine to form a ring structure.

13. X in equation (1-2) ２ The resin composition according to claim 9, wherein each of the structures is obtained by removing two or more hydrogen atoms from a structure represented by any of the following formulas (V-1) to (V-4). In formula (V-2), R Ｘ１ Each of these is independently a hydrogen atom, an alkyl group, or an alkyl halide. In formula (V-3), R Ｘ２ and R Ｘ３ Each of these independently represents a hydrogen atom or a substituent, R Ｘ２ and R Ｘ３ They may combine to form a ring structure.

14. Y in equation (1-2) ２ The resin composition according to claim 9, wherein each of the structures is obtained by removing two or more hydrogen atoms from a structure represented by any of the following formulas (V-1) to (V-4). In formula (V-2), R Ｘ１ Each of these is independently a hydrogen atom, an alkyl group, or an alkyl halide. In formula (V-3), R Ｘ２ and R Ｘ３ Each of these independently represents a hydrogen atom or a substituent, R Ｘ２ and R Ｘ３ They may combine to form a ring structure.

15. The resin composition according to any one of claims 1 to 3, wherein the content of the structure represented by formula (A-1) relative to the mass of the resin is 0.1 to 2.0 mmol / g.

16. The resin composition according to any one of claims 1 to 3, further comprising a photosensitive agent.

17. The resin composition according to any one of claims 1 to 3, further comprising a polymerizable compound.

18. A resin composition according to any one of claims 1 to 3, comprising a solvent having a boiling point of 100 to 260°C at 1 atmosphere.

19. The resin composition according to claim 18, wherein the content of the solvent having a boiling point of 100 to 260°C is 40% by mass or more with respect to the total mass of the composition.

20. The resin composition according to claim 18, comprising two or more solvents having a boiling point of 100 to 260°C.

21. A resin composition according to any one of claims 1 to 3, used for forming an interlayer insulating film for a redistribution layer.

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

23. A laminate comprising two or more layers made of the cured product described in claim 22, wherein a metal layer is included between any of the layers made of the cured product.

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

25. A method for producing a cured product according to claim 24, comprising an exposure step of selectively exposing the above film and a developing step of developing the above film using a developer to form a pattern.

26. A method for producing a cured product according to claim 24, comprising a heating step of heating the above film to 50 to 450°C.

27. A method for manufacturing a laminate, comprising the method for manufacturing a cured product as described in claim 24.

28. A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured product according to claim 24.

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

30. A polyimide having the structure represented by the following formula (A-1). In formula (A-1), Z １ represents the group shown in the following formula (AA-1), and Q １ ~Q ８ Each of these independently represents a hydrogen atom or a monovalent organic group, n represents an integer from 0 to 2, m represents an integer from 0 to 2, n + m is 2, and when n is 2, there are two Qs. １ ~Q ４ These can be the same or different, and if m is 2, there are two Qs. ５ ~Q ８ Each of them may be the same or different, Q １ ~Q ４ At least two of them may bond together to form a ring structure, Q ５ ~Q ８ At least two of them may bond together to form a ring structure, L １ Each of these independently represents -O-, -C(=O)O-, or -S-, L ２ Each of the symbols independently represents -O-, -C(=O)O-, or -S-, and each of the symbols independently represents a bonding site with a nitrogen atom. In formula (AA-1), G １ ~G ８ Any two of these are L in equation (A-1) １ or L ２ This represents the bonding site with other G １ ~G ８ Each of these independently represents a hydrogen atom or a monovalent organic group.

31. The polyimide according to claim 30, comprising a repeating unit represented by the following formula (1-1). In formula (1-1), X １ represents an organic group having 4 or more carbon atoms, and Y １ represents an organic group having 4 or more carbon atoms, and R １ each independently represents a structure represented by the following formula (R-1), a represents an integer of 0 to 4, b represents an integer of 0 or more, and at least one of X １ and Y １ contains a structure represented by formula (A-1). In formula (R-1), L １ represents an a1 + 1-valent linking group, A １ represents a polymerizable group, a1 represents an integer of 1 or more, and * represents the bonding site with X １ or Y １ in formula (1-1).

32. The aforementioned Y １ The polyimide according to claim 31, wherein the structure is represented by formula (A-1).

33. The sum of a and b in equation (1-1) is 1 or greater, and there are a + b R １ In at least one of the equations, A in equation (R-1) １ The polyimide according to claim 31, wherein at least one of the groups is a vinylphenyl group.

34. The polyimide according to claim 31, further comprising a repeating unit represented by the following formula (1-2). In formula (1-2), X ２ represents an organic group having 4 or more carbon atoms, and Y ２ represents an organic group having 4 or more carbon atoms, and X ２ and Y ２ both do not contain the structure represented by formula (A-1), and R ２ each independently represents a structure represented by formula (R-2), m represents an integer of 0 to 4, n represents an integer of 0 or more, and n + m is an integer of 1 or more. In formula (R-2), L ２ represents a linking group having a valence of a2 + 1, A ２ represents a polymerizable group, a2 represents an integer of 1 or more, and * represents the bonding site with X ２ or Y ２ in formula (1-2).

35. m+n Rs in equation (1-2) ２ In at least one of the equations, A in equation (R-2) ２ The polyimide according to claim 34, wherein at least one of the groups is a vinylphenyl group.

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