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

Abstract

The present invention provides: a resin composition containing a polyimide which includes a repeating unit represented by formula (A-1) and has a radical-polymerizable group; a cured product obtained by curing said resin composition; a layered product that includes said cured product; a method for producing said cured product; a method for producing said layered product; a method for producing a semiconductor device, which includes said method for producing said cured product; a semiconductor device that includes said cured product; and a polyimide which has a repeating unit represented by formula (A-2) and a repeating unit represented by formula (A-3).

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, polyimide is 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 polyamic acid ester composition characterized by comprising 100 parts by mass of a polyamic acid ester (A) consisting only of specific repeating units, 1 to 40 parts by mass of a photoinitiator (B), 30 to 1500 parts by mass of a solvent (C), and 0 to 150 parts by mass of another polyamic acid ester (D) consisting only of different specific repeating units.

[0005] International Publication No. 2008 / 123583

[0006] Conventionally, cured products containing polyimide have been obtained by imidizing polyimide precursors such as polyamic acid esters with heat. However, there is a demand to manufacture the above cured products at low temperatures. For example, when the above cured product is used as an insulating film in a device, it is desirable to avoid exposing the circuits, elements, etc., contained in the device to high temperatures. From this perspective, in order to manufacture cured products at low temperatures, we considered using pre-ring-closed polyimide instead of polyimide. This embodiment has the advantage that thermal imidization is unnecessary or the amount of imidization required is small, so cured products can be manufactured at low temperatures. However, polyimide absorbs exposure light such as ultraviolet light more than polyimide precursors, and there was a problem that the focus margin was narrow in patterning of cured products by exposure and development. Here, with the miniaturization of patterns and the diversification of desired pattern shapes, there is a need for films formed from resin compositions containing polyimide so that even if the focus of the exposure light is shifted in the depth direction, the pattern shape formed after development does not easily become reverse-tapered. In this specification, even if the focus of the exposure light is shifted in the depth direction, a film is obtained in which the pattern shape formed after development is less likely to be in the opposite taper shape, and this is also referred to as obtaining a film with a wide focus margin.

[0007] The present invention aims to provide a resin composition that yields a film with a wide focus margin, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for manufacturing the cured product, a method for manufacturing the laminate, a method for manufacturing a semiconductor device including the method for manufacturing the cured product, and a semiconductor device containing the cured product. The present invention also aims to provide a novel polyimide.

[0008] Examples of typical embodiments of the present invention are shown below. <1> A resin composition comprising a polyimide having a repeating unit represented by the following formula (A-1) and a radical polymerizable group. In formula (A-1), X １ represents a tetravalent organic group, Y １represents a group represented by any one of the following formulas (Y-1) to (Y-11). In formulas (Y-1) to (Y-4), R １ each independently represents a hydrogen atom or a substituent, and at least one of R １ is an electron-withdrawing group, and * represents the bonding site with the nitrogen atom. In formulas (Y-5) to (Y-7), R ２ each independently represents a hydrogen atom or a substituent having no radical polymerizable group, and A １ is any one of -C(=O)-, -S(=O) ２ -, -S(=O)-, -C(R ３ ) ２ -, and R ３ is a hydrogen atom or a substituent, and * represents the bonding site with the nitrogen atom. In formula (Y-8), R ２ each independently represents a hydrogen atom or a substituent, R ４ each independently represents a substituent, R ５ each independently represents a substituent, L １ is a single bond or a divalent linking group, and * represents the bonding site with the nitrogen atom. In formula (Y-9), R ６ each independently represents a hydroxy group, an alkoxy group, a cyano group, a formyl group, -C(=O)NR Ｙ１ ２ , -C(=O)OR Ｙ２ , -C(=O)R Ｙ２ , an alkenyl group, an alkynyl group or an alkyl group having 2 or more carbon atoms which may have a substituent, R Ｙ１ is a hydrogen atom or a substituent, R Ｙ２ represents an organic group, R ７ each independently represents a hydrogen atom or a substituent, and any one of R ７ represents the bonding position with the nitrogen atom in formula (A-1), and R ８ each independently represents a hydrogen atom or a substituent, and any one of R ８ represents the bonding position with the nitrogen atom in formula (A-1). In formula (Y-10), R ７ each independently represents a hydrogen atom or a substituent, and R ７One of these represents the bonding position with the nitrogen atom in formula (A-1), and R ８ Each is independently a hydrogen atom or a substituent, and R ８ One of these represents the bonding position with the nitrogen atom in formula (A-1), and R ９ Each of these is independently an alkyl group which may have substituents. In formula (Y-11), R １０ Each of these is independently an alkyl group which may have substituents, and R １１ Each is independently a hydrogen atom or a substituent, and R １１ One of the following is an organic group, R １１ One of these represents the bonding position with the nitrogen atom in formula (A-1), and R １２ Each is independently a hydrogen atom or a substituent, and R １２ One of the following is an organic group, R １２ One of the following represents the bond position with the nitrogen atom in formula (A-1). <2> Y in formula (A-1) above １ The resin composition according to <1>, wherein is either formula (Y-12) or (Y-13) below. In formula (Y-12), R １３ Each is independently a hydrogen atom or a substituent, and R １４ Each of these is independently an alkyl group, an alkoxy group, or an aryl group, L ２ is a divalent linking group, and * represents the bond site with the nitrogen atom. In formula (Y-13), R １５ Each of these is independently an alkyl group which may have substituents, and R １６ Each is independently a hydrogen atom or a substituent. <3> The resin composition according to <1>, wherein the absorbance of a 0.10 g / L NMP solution of the polyimide at a wavelength of 365 nm is 0.070 or less. <4> The resin composition according to any one of <1> to <3>, wherein the radical polymerizable group in the polyimide is an aromatic vinyl group. <5> X in formula (A-1) １ A resin composition according to any one of <1> to <4>, wherein the group is represented by the following formula (AA-1). In formula (AA-1), * represents a bonding site with a carbonyl group. <6> The above polyimide is Y １ The repeating unit represented by formula (A-1) is a structure that can be expressed by any of formulas (Y-3) to (Y-8), and Y １ A resin composition according to any one of <1> to <5>, wherein the polyimide comprises a repeating unit represented by formula (A-1) having a structure represented by any one of formulas (Y-1) to (Y-2) and formulas (Y-9) to (Y-11). <7> A resin composition according to any one of <1> to <6>, wherein the polyimide comprises a polyimide having a repeating unit represented by the following formula (A-2) and a repeating unit represented by formula (A-3). In formula (A-2), X ２ represents a tetravalent organic group, Y ２ represents a group represented by any of the above formulas (Y-1) to (Y-11). In formula (A-3), X ３ represents a tetravalent organic group, Y ３ X is a group that does not correspond to any of the above formulas (Y-1) to (Y-11), and is a divalent group having radical polymerizability. <8> X in the above polyimide ２ and X ３ The resin composition according to <7>, wherein at least one of the groups is represented by the following formula (AA-1). In formula (AA-1), * represents the bonding site with the carbonyl group. <9> Y in the above polyimide ３A resin composition according to <7> or <8>, wherein the radical polymerizable group contained therein is an aromatic vinyl group. <10> A resin composition according to any one of <1> to <9>, wherein the content of the group represented by any one of formulas (Y-1) to (Y-11) in the polyimide is 0.25 to 1.70 mmol / g. <11> A resin composition according to any one of <1> to <10> used for forming an interlayer insulating film for a redistribution layer. <12> A cured product obtained by curing the resin composition according to any one of <1> to <11>. <13> A laminate comprising two or more layers made of the cured product according to <12>, with a metal layer between any of the layers made of the cured product. <14> A method for producing a cured product, comprising a film forming step of applying the resin composition according to any one of <1> to <11> onto a substrate to form a film. <15> A method for producing a cured product according to <14>, comprising an exposure step of selectively exposing the film and a developing step of developing the film using a developer to form a pattern. <16> A method for producing a cured product according to <14> or <15>, comprising a heating step of heating the above film to 50 to 450°C. <17> A method for producing a laminate, comprising a method for producing a cured product according to any one of <14> to <16>. <18> A method for producing a semiconductor device, comprising a method for producing a cured product according to any one of <14> to <16>. <19> A semiconductor device comprising the cured product according to <12>. <20> A polyimide having repeating units represented by the following formula (A-2) and repeating units represented by formula (A-3). In formula (A-2), X ２ represents a tetravalent organic group, Y ２ represents a group represented by any of the following formulas (Y-1) to (Y-11). In formula (A-3), X ３ represents a tetravalent organic group, Y ３ This group is a divalent group having radical polymerizability and does not fall under any of the following formulas (Y-1) to (Y-11). In equations (Y-1) to (Y-4), R １ Each of these independently represents a hydrogen atom or a substituent, R １ At least one of the groups is an electron-withdrawing group, and * represents the bonding site with the nitrogen atom. In equations (Y-5) to (Y-7), R２ Each of these independently represents a substituent that does not have a hydrogen atom or a radical polymerizable group, R １ At least one of them is an electron-withdrawing group, A １ -C(=O)-, -S(=O) ２ -, -S(=O)-, -C(R ３ ) ２ - is one of the following, R ３ * represents a hydrogen atom or substituent, and * represents a bond site with a nitrogen atom. In formula (Y-8), R ２ Each is independently a hydrogen atom or a substituent, and R ４ Each of these independently represents a substituent, R ５ Each of these independently represents a substituent, L １ represents a single bond or a divalent linking group, and * represents the bond site with the nitrogen atom. In formula (Y-9), R ６ These are independently a hydroxyl group, an alkoxy group, a cyano group, a formyl group, and -C(=O)NR Ｙ１ ２ , -C (=O) OR Ｙ２ , -C(=O)R Ｙ２ R is an alkenyl group, an alkynyl group, or an alkyl group having 2 or more carbon atoms which may have substituents. Ｙ１ R is a hydrogen atom or substituent. Ｙ２ represents an organic group, R ７ Each is independently a hydrogen atom or a substituent, and R ７ One of these represents the bonding position with the nitrogen atom in formula (A-2), and R ８ Each is independently a hydrogen atom or a substituent, and R ８ One of these represents the bond position with the nitrogen atom in formula (A-2). In formula (Y-10), R ７ Each is independently a hydrogen atom or a substituent, and R ７ One of these represents the bonding position with the nitrogen atom in formula (A-2), and R ８ Each is independently a hydrogen atom or a substituent, and R ８ One of these represents the bonding position with the nitrogen atom in formula (A-2), and R ９Each is independently an alkyl group which may have a substituent. In formula (Y-11), R １０ Each is independently an alkyl group which may have a substituent, and R １１ Each is independently a hydrogen atom or a substituent, and R １１ Any one of them is an organic group, and R １１ Any one of them represents the bonding position with the nitrogen atom in formula (A-2), and R １２ Each is independently a hydrogen atom or a substituent, and R １２ Any one of them is an organic group, and R １２ Any one of them represents the bonding position with the nitrogen atom in formula (A-2).

[0009] According to the present invention, there are provided a resin composition capable of obtaining a film with a wide focus margin, 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, the present invention provides a novel polyimide.

[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, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, by using an HLC-8420GPC (manufactured by Tosoh Corporation) and connecting Guard Column SuperAW-H, TSKgel SuperAWM-H, and TSKgel SuperAWM-H (all manufactured by Tosoh Corporation) in series in that order 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. Furthermore, 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 the laminate is described as "above" or "below," it is sufficient that other layers are above or below the reference layer among the multiple layers of interest. In other words, 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. Unless otherwise specified in this specification, a composition may contain two or more compounds corresponding to each component included in the composition. Unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component. Unless otherwise specified in this specification, the temperature is 23°C, the atmospheric pressure is 101,325 Pa (1 atm), and the relative humidity is 50% RH. In this specification, a preferred embodiment combination is a more preferred embodiment.

[0011] (Resin Composition) The resin composition of the present invention contains a polyimide that includes a repeating unit represented by formula (A-1) and has radical polymerizable groups. Hereinafter, the polyimide that includes a repeating unit represented by formula (A-1) and has radical polymerizable groups will also be referred to as the "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] According to the resin composition of the present invention, a film with a wide focus margin can be obtained. The mechanism by which the above effect is obtained is unknown, but it is presumed to be as follows.

[0014] In recent years, there has been a growing demand for low-temperature curing properties in insulating films used for redistribution in semiconductor packages (back-end processes). It has been found that by using a resin composition containing polyimide that is already imidized, rather than conventional polyamic acid esters, process-based imidization becomes unnecessary, and low-temperature curing properties can be imparted. The inventors have found that such polyimide-containing resin compositions have low light transmittance, and when the focus of the exposure light is shifted, the pattern tends to become reverse-tapered, meaning there is room for improvement in the narrow focus margin. The resin composition of the present invention contains structures represented by formulas (Y-1) to (Y-11). The structures related to formulas (Y-1) to (Y-7) contain electron-withdrawing groups and specific linking groups, which leads to an electron deficiency in the aromatic ring and a large HOMO-LUMO energy gap. Therefore, it is believed that the transmittance of exposure light is high, and even if the focus of the exposure light is shifted, a pattern with a non-reverse-tapered shape can be obtained. The structures related to equations (Y-8) to (Y-11) are thought to have high transmittance of exposure light and, even if the focus of the exposure light is shifted, a pattern shape that is not reverse-tapered can be obtained because the conjugation between the aromatic ring and the imide ring is broken due to the twisting of the structure caused by steric hindrance.

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

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

[0017] <Specific Resin> The resin composition of the present invention includes a polyimide (specific resin) that contains a repeating unit represented by formula (A-1) and has radical polymerizable groups.

[0018] In the present invention, polyimide refers to a resin having repeating units containing imide groups in its molecular chain, and preferably a resin having repeating units containing imide ring structures in 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 groups in its main chain, and more preferably a resin having repeating units containing imide ring structures in its main chain. In this specification, "main chain" refers to the relatively longest bonding chain in the resin molecule, and "side chain" refers to the other bonding chains. In this specification, imide group refers to a structure represented by *-C(=O)N(-*)C(=O)-*, where * represents a bonding site with another structure, preferably a bonding site with a carbon atom, and more preferably a bonding site with a quaternary carbon atom. In this specification, imide ring structure refers to a ring structure that includes all two carbon atoms and nitrogen atoms in the above imide as ring members. The imide ring structure is preferably a five-membered ring. In addition to imide groups, polyimide may also be a so-called polyamide imide, which has amide bonds in its molecular chain. In this specification, an amide bond refers to a structure represented by *-C(=O)N(-#)-*, where * represents a bonding site with another structure, preferably a bonding site with a carbon atom. Furthermore, # 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.

[0019] [Radical Polymerizable Groups] The specified resin has radical polymerizable groups. It is believed that the presence of radical polymerizable groups increases the glass transition temperature of the resulting cured product. Specific examples of radical polymerizable groups include groups having ethylenically unsaturated bonds. Examples of groups having ethylenically unsaturated bonds include vinyl groups, allyl groups, isoallyl groups, 2-methylallyl groups, (meth)acryloyl groups (especially (meth)acryloyloxy groups, methacrylamide groups, etc.), aromatic vinyl groups (e.g., vinylphenyl groups), maleimide groups, etc. (meth)acryloyl groups or aromatic vinyl groups are preferred, and aromatic vinyl groups are more preferred, and vinylphenyl groups are even more preferred, from the viewpoint of high depolymerization temperature and excellent heat resistance. In this specification, an aromatic vinyl group refers to a group in which a hydrogen atom in an aromatic group is substituted with a vinyl group. By the specified resin containing aromatic vinyl groups and any of the groups represented by formulas (Y-1) to (Y-11), a photosensitive film with excellent resolution and a wide focus margin can be obtained. Aromatic vinyl groups have a large radical e value and stable radicals, resulting in lower radical polymerization reactivity compared to (meth)acryloxy groups and the like. As a result, it is thought that, for example, hole pattern burying due to radical diffusion is suppressed. Furthermore, by including a group represented by any of the above formulas (Y-1) to (Y-11) in the specific resin, the light transmittance is improved, and the exposure latent image is less likely to become inversely tapered. Therefore, when an aromatic vinyl group is included and a group represented by any of the above formulas (Y-1) to (Y-11) is included, the radical polymerization reaction region viewed from the film cross-section becomes closer to a rectangle. As a result, it is thought that the post-development pattern is less likely to become inversely tapered, and resolution and focus margin are significantly improved.

[0020] Because the specific resin has radical polymerizable groups, the resin composition of the present invention preferably contains a radical polymerization initiator, and more preferably contains a radical polymerization initiator and a radical crosslinking agent. Furthermore, a sensitizer may be included as needed. A negative-type photosensitive film can be formed from such a resin composition, for example.

[0021] The content (polymerizable group value) of the radically polymerizable group relative to the total mass of the specific resin is preferably 0.1 to 4.0 mmol / g, more preferably 0.2 to 2.0 mmol / g, and still more preferably 0.2 to 1.5 mmol / g. For example, the content of the vinylphenyl group in the resin in the composition can be calculated by the following method. The calculation method is the same for other polymerizable groups and radically polymerizable groups. Add 1 g of the composition to 50 g of methanol or water for crystallization, precipitate the specific resin, and filter. Collect the filtrate, dissolve it in 3.0 g of THF (tetrahydrofuran), add this to 50 g of methanol or water for crystallization, filter, and dry at 40 °C for 20 hours. After dissolving 0.1 g of the specific resin dried above in 0.9 g of deuterated dimethyl sulfoxide, １ Measure by 1H-NMR and calculate the amount of vinylphenyl groups. １ The integration number of 1H-NMR is 640 times. For example, use tetramethylsilane as the reference substance, １ From the ratio of the integrated intensity of the peak near 5.0 to 7.0 ppm derived from the vinylphenyl group in the 1H-NMR chart and the integrated intensity of the peak derived from the reference substance, the amount of the reference substance, and the amount of the specific resin above, the molar amount of the vinylphenyl group in the specific resin can be calculated. For the molar amounts of other structures, they can be measured by calculating the integrated intensity of the peaks corresponding to each structure.

[0022] [Repeating unit represented by formula (A-1)] The specific resin contains a repeating unit represented by the following formula (A-1). In formula (A-1), X １ represents a tetravalent organic group, and Y １ represents a group represented by any one of the following formulas (Y-1) to (Y-11). In formulas (Y-1) to (Y-4), R １ each independently represents a hydrogen atom or a substituent, and at least one of R １ is an electron-withdrawing group, and * represents the bonding site with the nitrogen atom. In formulas (Y-5) to (Y-7), R ２ each independently represents a hydrogen atom or a substituent having no radically polymerizable group, and A １-C(=O)-, -S(=O) ２ -, -S(=O)-, -C(R ３ ) ２ - is one of the following, R ３ * represents a hydrogen atom or substituent, and * represents a bond site with a nitrogen atom. In formula (Y-8), R ２ Each is independently a hydrogen atom or a substituent, and R ４ Each of these independently represents a substituent, R ５ Each of these independently represents a substituent, L １ represents a single bond or a divalent linking group, and * represents the bond site with the nitrogen atom. In formula (Y-9), R ６ These are independently a hydroxyl group, an alkoxy group, a cyano group, a formyl group, and -C(=O)NR Ｙ１ ２ , -C (=O) OR Ｙ２ , -C(=O)R Ｙ２ R is an alkenyl group, an alkynyl group, or an alkyl group having 2 or more carbon atoms which may have substituents. Ｙ１ R is a hydrogen atom or substituent. Ｙ２ represents an organic group, R ７ Each is independently a hydrogen atom or a substituent, and R ７ One of these represents the bonding position with the nitrogen atom in formula (A-1), and R ８ Each is independently a hydrogen atom or a substituent, and R ８ One of these represents the bond position with the nitrogen atom in formula (A-1). In formula (Y-10), R ７ Each is independently a hydrogen atom or a substituent, and R ７ One of these represents the bonding position with the nitrogen atom in formula (A-1), and R ８ Each is independently a hydrogen atom or a substituent, and R ８ One of these represents the bonding position with the nitrogen atom in formula (A-1), and R ９ Each of these is independently an alkyl group which may have substituents. In formula (Y-11), R １０ Each of these is independently an alkyl group which may have substituents, and R １１ Each is independently a hydrogen atom or a substituent, and R１１ One of the following is an organic group, R １１ One of these represents the bonding position with the nitrogen atom in formula (A-1), and R １２ Each is independently a hydrogen atom or a substituent, and R １２ One of the following is an organic group, R １２ One of these represents the bonding position with the nitrogen atom in formula (A-1).

[0023] Furthermore, a specific resin is Y １ The repeating unit represented by formula (A-1) is a structure that can be expressed by any of formulas (Y-3) to (Y-8), and Y １ Another preferred embodiment of the present invention is one in which a repeating unit represented by formula (A-1) is a structure represented by any of formulas (Y-1) to (Y-2) and formulas (Y-9) to (Y-11). According to the above embodiment, since the specific resin contains a structure represented by any of formulas (Y-3) to (Y-8) which is a relatively soft structure and a highly transparent structure, and a structure represented by any of formulas (Y-1) to (Y-2) and formulas (Y-9) to (Y-11) which is a relatively rigid structure and a highly transparent structure, it is considered that in addition to improving the focus margin, the resulting cured product will also have excellent elongation at break.

[0024] -X １ - In formula (A-1), X １ The number of carbon atoms is preferably 4 or more, more preferably 4 to 50, and even more preferably 6 to 40. In formula (A-1), X １ Preferably, the structure is one of the structures represented by formulas (2a) to (2e) below, or a structure that includes the structure obtained by removing four hydrogen atoms from the structure represented by formula (2f) below. In formulas (2a) to (2e), *1 to *4 represent the bonding sites with the carbonyl group in formula (A-1), respectively. In formula (2c), L １ and L ２ is a divalent linking group. In equation (2f), n1 is a non-negative integer.

[0025] In formula (2c), L １ and L ２ Each is independent of the other, -CH２ It is preferable that it be - or -O-.

[0026] The hydrogen atoms in formulas (2a) to (2e) may be substituted with substituents, such as alkyl groups and alkyl halides, and are preferably C1-C4 alkyl groups or C1-C4 alkyl halides, with methyl groups or trifluoromethyl groups being more preferred. An alkyl halide is a group in which at least one hydrogen atom of an alkyl group is substituted with a halogen atom. The halogen atom is preferably F or Cl, with F being more preferred.

[0027] In formula (2f), n1 is preferably an integer between 0 and 5, more preferably between 0 and 2, and even more preferably 0 or 1. １ However, if the group includes a structure obtained by removing four hydrogen atoms from the structure represented by formula (2f), then X １ It is preferable that the group is represented by the following formula (2f-1). In the following formula, * is X in formula (A-1). １ This represents the bonding sites with the four carbonyl groups to which it is bonded. Furthermore, the definition of n1 and preferred embodiments are as described above. The hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.

[0028] Also, X １ It is also preferable that the structure includes a structure obtained by removing two or more hydrogen atoms from the structure represented by any of the formulas (V-1) to (V-4). In formula (V-2), R Ｘ１ Each of these is independently a hydrogen atom or an alkyl group which may have a substituent. 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.

[0029] 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 to be -, and even more preferable to 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.

[0030] 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 (A-1). １ This represents the bonding sites with the four carbonyl groups to which it is bonded. Furthermore, the hydrogen atoms in the structure below may be further substituted with known substituents such as hydrocarbon groups.

[0031] 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). In the following formula, * is X in formula (A-1). １ This represents the bonding sites with the four carbonyl groups to which it is bonded. Also, R Ｘ１ The definition and preferred embodiments are as described above. Furthermore, the hydrogen atoms in these structures may be further substituted with known substituents such as hydrocarbon groups.

[0032] 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 (A-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 embodiments are as described above. Furthermore, the hydrogen atoms in these structures may be further substituted with known substituents such as hydrocarbon groups.

[0033] 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, * is X in formula (A-1). １ This represents the bonding sites with the four carbonyl groups to which it is bonded. Furthermore, the hydrogen atoms in the structure below may be further substituted with known substituents such as hydrocarbon groups.

[0034] In particular, X in (A-1) １ Preferably, the group is represented by the following formula (AA-1). In formula (AA-1), * represents a bonding site with a carbonyl group.

[0035] Other, X １ This may be a tetracarboxylic acid residue remaining after the removal of the anhydride group from the tetracarboxylic dianhydride described in paragraphs 0055 to 0057 of Japanese Patent Application Publication No. 2023-003421.

[0036] Also, X １ It is preferable that the structure does not contain imide bonds. Also, X １ It is also preferable that the structure does not contain urethane bonds, urea bonds, and 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.

[0037] -Y １ - In formula (A-1), Y １ The group is represented by one of the following formulas (Y-1) to (Y-11).

[0038] <<Equation (Y-1)>> In Equation (Y-1), R １ Each of these independently represents a hydrogen atom or a substituent, R １ At least one of them is an electron-withdrawing group, and * represents the bonding site with the nitrogen atom. In formula (Y-1), R １ If it is an electron-withdrawing group, the electron-withdrawing group may be an alkyl halide, an alkylcarbonyl group, or -C(=O)N(R Ｎ ) ２ , -C(=O)O(R Ｃ ), preferably a cyano group, a nitro group or a halogen atom, and an alkylcarbonyl group, -C(=O)N(R Ｎ ) ２ , -C(=O)O(R Ｃ ), a cyano group or a halogen atom is more preferred. The above alkyl halide may be any alkyl group in which at least some of the hydrogen atoms are substituted with halogen atoms, and it is preferable that all of the hydrogen atoms are substituted with halogen atoms. Furthermore, as the halogen atom, F or Cl is preferred, and F is more preferred. As the above alkyl halide, an alkyl halide having 1 to 4 carbon atoms is preferred, an alkyl halide having 1 or 2 carbon atoms is more preferred, and -CF ３The above alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 10 carbon atoms, more preferably an alkylcarbonyl group having 2 to 5 carbon atoms, and more preferably a methylcarbonyl group. The above R Ｎ Each of these independently represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and still more preferably a hydrogen atom. Ｃ The substituent represents a monovalent substituent, preferably a hydrocarbon group, more preferably an alkyl group, and even more preferably a methyl group. The halogen atom is preferably F or Cl, and more preferably F.

[0039] R when it is not an electron-withdrawing group １ The preferred element is a hydrogen atom, an alkyl group, or an aryl group; a hydrogen atom or an alkyl group is more preferred; and a hydrogen atom is even more preferred.

[0040] <<Equations (Y-2) to (Y-4)>> In equations (Y-2) to (Y-4), R １ A preferred embodiment is R in formula (Y-1) １ This is similar to the preferred embodiment.

[0041] Specific examples of structures represented by formulas (Y-1) to (Y-4) are shown below, but the present invention is not limited to these.

[0042] <<Equation (Y-5)>> In Equation (Y-5), R ２ Each of these independently represents a hydrogen atom or a substituent that does not have a radical polymerizable group, and it is preferable that both are hydrogen atoms. ２ When A is a substituent, examples of substituents include alkyl groups, aryl groups, halogen atoms, etc. In formula (Y-5), A １ -C(=O)-, -S(=O) ２ -, -S(=O)-, -C(R ３ ) ２ - is one of the following, R ３ is a hydrogen atom or substituent, -C(=O)-, -S(=O) ２ It is preferable that it is - or -S (=O)-, and more preferably -C (=O)-. The above R３ R is preferably a hydrogen atom. ３ When the substituent is a substituent, examples of substituents include alkyl groups, aryl groups, halogen atoms, and so on.

[0043] <<Equations (Y-6) to (Y-7)>> In equations (Y-6) to (Y-7), R ２ A １ , R ３ Preferred embodiments include, respectively, R in formula (Y-5). ２ A １ , R ３ This is similar to the preferred embodiment.

[0044] Specific examples of structures represented by formulas (Y-5) to (Y-7) are shown below, but the present invention is not limited to these.

[0045] <<Equation (Y-8)>> In Equation (Y-8), R ２ Each of these is independently a hydrogen atom or a substituent, and it is preferable that both are hydrogen atoms. ２ When R is a substituent, examples of substituents include alkyl groups, aryl groups, halogen atoms, etc. In formula (Y-8), R ４ Each of these independently represents a substituent, preferably an alkyl group, alkoxy group, aryl group, or halogen atom, more preferably an alkyl group, alkoxy group, or aryl group, even more preferably an alkyl group, and particularly preferably a methyl group or ethyl group. As the alkyl group, a C1-C10 alkyl group is preferred, a C1-C4 alkyl group is more preferred, and a methyl group or ethyl group is particularly preferred. As the aryl group, an aromatic hydrocarbon group is preferred, and a phenyl group is more preferred. As the alkoxy group, a C1-C10 alkoxy group is preferred, and a C1-C4 alkoxy group is even more preferred. As the halogen atom, F or Cl is preferred, and F is more preferred. In formula (Y-8), R ５ A preferred embodiment is R ４ This is similar to the preferred embodiment. In formula (Y-8), L １ is a single bond or a divalent linking group, and is a single bond or -C(R Ｃ２ ) ２- is preferable. R Ｃ２ is a hydrogen atom or a substituent, preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0046] Specific examples of the structure represented by formula (Y-8) are shown below, but the present invention is not limited to these.

[0047] <<Equation (Y-9)>> In Equation (Y-9), R ６ These are independently a hydroxyl group, an alkoxy group, a cyano group, a formyl group, and -C(=O)NR Ｙ１ ２ , -C (=O) OR Ｙ２ , -C(=O)R Ｙ２ , an alkenyl group, an alkynyl group, or an alkyl group with two or more carbon atoms which may have substituents, an alkoxy group, a cyano group, -C(=O)R Ｙ２ , -C(=O)NR Ｙ１ ２ A C2 or more alkyl group, which may have substituents, is more preferable. ６ The alkoxy group in is preferably an alkoxy group having 1 to 10 carbon atoms, and more preferably an alkoxy group having 1 to 4 carbon atoms. Ｙ１ Each of these is independently preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom. As the alkyl group, a C1-C10 alkyl group is preferred, and a C1-C4 alkyl group is more preferred. As the aryl group, an aromatic hydrocarbon group is preferred, and a phenyl group is more preferred. Ｙ２ The group is preferably an alkyl group or an aryl group, and more preferably an alkyl group. As the alkyl group, a C1-C10 alkyl group is preferred, a C1-C4 alkyl group is even more preferred, and a methyl group is particularly preferred. As the aryl group, an aromatic hydrocarbon group is preferred, and a phenyl group is more preferred. ６ In this compound, the alkenyl group is preferably an alkenyl group having 2 to 11 carbon atoms, more preferably an alkenyl group having 2 to 5 carbon atoms, and more preferably a vinyl group or an allyl group. ６In this compound, the alkynyl group is preferably an alkynyl group having 2 to 11 carbon atoms, more preferably an alkynyl group having 2 to 5 carbon atoms, and more preferably an ethynyl group or a propane-2-yin-1-yl group. ６ The alkyl group which may have substituents is preferably an alkyl group having 2 to 20 carbon atoms which may have substituents, more preferably an alkyl group having 2 to 10 carbon atoms which may have substituents, even more preferably an alkyl group having 2 to 6 carbon atoms which may have substituents, and particularly preferably an ethyl group, propyl group, isopropyl group, butyl group, pentyl group, or hexyl group which may have substituents. Examples of substituents in the alkyl group above include aryl groups and halogen atoms.

[0048] In formula (Y-9), R ７ Each of these is preferably a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxy group, or a halogen atom. As the alkyl group, C1-C10 alkyl groups are preferred, C1-C4 alkyl groups are more preferred, and a methyl group is even more preferred. As the alkoxy group, C1-C10 alkoxy groups are preferred, C1-C4 alkoxy groups are more preferred, and a methoxy group is even more preferred. As the halogen atom, fluorine, chlorine, or bromine atoms are preferred, and fluorine is even more preferred.

[0049] In formula (Y-9), R ８ A preferred embodiment is R ７ This is similar to the preferred embodiment.

[0050] <<Equation (Y-10)>> In equation (Y-10), R ７ and R ８ Preferred embodiments include, respectively, R in formula (Y-9). ７ and R ８ This is similar to a preferred embodiment. In formula (Y-10), R ９Each of these is independently an alkyl group which may have substituents, preferably an alkyl group having 1 to 10 atoms which may have substituents, more preferably an alkyl group having 1 to 4 atoms which may have substituents, and even more preferably a methyl group or an ethyl group. Examples of substituents in the alkyl group include aryl groups and halogen atoms.

[0051] <<Equation (Y-11)>> In Equation (Y-11), R １０ A preferred embodiment is R in formula (Y-10). ９ This is similar to a preferred embodiment. In formula (Y-11), R １１ and R １２ Preferred embodiments include, respectively, R in formula (Y-9). ７ and R ８ This is similar to the preferred embodiment.

[0052] Specific examples of structures represented by formulas (Y-9) to (Y-11) are shown below, but the present invention is not limited to these.

[0053] <<Equation (Y-12) or Equation (Y-13)>> Y in Equation (A-1) １ It is preferable that it is either (Y-12) or (Y-13) as shown below. In formula (Y-12), R １３ Each is independently a hydrogen atom or a substituent, and R １４ Each of these is independently an alkyl group, an alkoxy group, or an aryl group, L ２ is a divalent linking group, and * represents the bond site with the nitrogen atom. In formula (Y-13), R １５ Each of these is independently an alkyl group which may have substituents, and R １６ Each of these is independently a hydrogen atom or a substituent.

[0054] In formula (Y-12), R １３ A preferred embodiment is R in formula (Y-8). ２ This is similar to a preferred embodiment. In formula (Y-12), R １４ A preferred embodiment is R in formula (Y-8). ４The preferred embodiment is the same as when is an alkyl group, an alkoxy group, or an aryl group. In particular, R １４ L is preferably an alkyl group, and more preferably a methyl group or an ethyl group. In formula (Y-12), L ２ is -C(R ３ ) ２ - is preferable. R ３ A preferred embodiment is R in the above formula (Y-5). ３ This is similar to the preferred embodiment.

[0055] In formula (Y-13), R １５ A preferred embodiment is R in formula (Y-10). ９ This is similar to a preferred embodiment. In formula (Y-13), R １６ A preferred embodiment is R in formula (Y-10). ７ This is similar to the preferred embodiment.

[0056] [Repeating units represented by formula (A-2) and formula (A-3)] The resin composition of the present invention preferably contains a polyimide as a specific resin having repeating units represented by the following formula (A-2) and formula (A-3). In formula (A-2), X ２ represents a tetravalent organic group, Y ２ represents a group represented by any of the above formulas (Y-1) to (Y-11). In formula (A-2), X ３ represents a tetravalent organic group, Y ３ This group is a divalent group having radical polymerizability and does not correspond to any of the above formulas (Y-1) to (Y-11).

[0057] In formula (A-2), X ２ and Y ２ A preferred embodiment is X in formula (A-1). １ and Y １ This is similar to the preferred embodiment. Furthermore, from the viewpoint of elongation at break, the specific resin is Y １ The repeating unit represented by equation (A-2) is a structure that can be expressed by any of equations (Y-3) to (Y-8), and Y １Another preferred embodiment of the present invention is one in which the repeating unit represented by formula (A-2) has a structure that is represented by any of formulas (Y-1) to (Y-2) and formulas (Y-9) to (Y-11).

[0058] In formula (A-3), X ３ A preferred embodiment is X in formula (A-1). １ This is similar to the preferred embodiment.

[0059] In formula (A-3), Y ３ The number of carbon atoms is preferably 4 or more, more preferably 4 to 50, and even more preferably 6 to 40. ３ It is also preferable that the structure is obtained by removing two or more hydrogen atoms from any of the structures represented by (V-1) to (V-9), and that at least one of the other hydrogen atoms is substituted with a group having a radical polymerizable group. In formula (V-2), R Ｘ１ Each of these is independently a hydrogen atom or an alkyl group which may have a substituent. 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-5), R Ｘ４ Each is independently a hydrogen atom or an alkyl group which may have substituents, and R Ｘ５ Each of these is independently an alkyl group which may have substituents.

[0060] In formula (V-2), R Ｘ１ The preferred embodiment is as described above. In formula (V-3), R Ｘ２ and R Ｘ３ The preferred embodiment is as described above. In formula (V-5), R Ｘ４ The hydrogen atom, alkyl group, or halogenated alkyl group is preferred, and the hydrogen atom, -CH ３ - or -CF ３ More preferably, a hydrogen atom or -CH ３ This is even more preferable. In formula (V-5), R Ｘ５Each of these groups is independently preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group.

[0061] Y ３ 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 ３ It is preferable that the group is represented by the following formula (V-1-2). In the following formula, * is Y in formula (A-3). ３ This represents the bonding site with the two nitrogen atoms to which it is bonded. Furthermore, at least one of the hydrogen atoms in the structure below is substituted with a group having a radical polymerizable group (preferably a group represented by formula (R-1) described later).

[0062] Y ３ 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 ３ 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 formula (A-3). ３ This represents the bonding site with the two nitrogen atoms to which it is bonded. Also, R Ｘ１ The preferred embodiment is as described above. Furthermore, at least one of the hydrogen atoms in the following structure is substituted with a group having a radical polymerizable group (preferably a group represented by formula (R-1) described later).

[0063] Y ３ 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 ３ 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 (A-3). ３ This represents the bonding site with the two nitrogen atoms to which it is bonded. Also, R Ｘ２ and R Ｘ３The preferred embodiment is as described above. Furthermore, at least one of the hydrogen atoms in the following structure is substituted with a group having a radical polymerizable group (preferably a group represented by formula (R-1) described later).

[0064] Y ３ 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 ３ It is preferable that the group is represented by the following formula (V-4-2). In the following formula, * is Y in formula (A-3). ３ This represents the bonding site with the two nitrogen atoms to which it is bonded. Furthermore, at least one of the hydrogen atoms in the structure below is substituted with a group having a radical polymerizable group (preferably a group represented by formula (R-1) described later).

[0065] Y ３ 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 ３ It is preferable that the group is represented by the following formula (V-5-2). In the following formula, * is Y in formula (A-3). ３ This represents the bonding site with the two nitrogen atoms to which it is bonded. Also, R Ｘ４ and R Ｘ５ The preferred embodiment is as described above. Furthermore, at least one of the hydrogen atoms in the following structure is substituted with a group having a radical polymerizable group (preferably a group represented by formula (R-1) described later).

[0066] Y ３ 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 ３ It is preferable that the group is represented by the following formula (V-6-2). In the following formula, * is Y in formula (A-3). ３ This represents the bonding site with the two nitrogen atoms to which it is bonded. Furthermore, at least one of the hydrogen atoms in the structure below is substituted with a group having a radical polymerizable group (preferably a group represented by formula (R-1) described later).

[0067] Y ３However, if the group includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-7), then Y ３ It is preferable that the group is represented by the following formula (V-7-2). In the following formula, * is Y in formula (A-3). ３ This represents the bonding site with the two nitrogen atoms to which it is bonded. Furthermore, at least one of the hydrogen atoms in the structure below is substituted with a group having a radical polymerizable group (preferably a group represented by formula (R-1) described later).

[0068] Y ３ 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 ３ It is preferable that the group is represented by the following formula (V-8-2). In the following formula, * is Y in formula (A-3). ３ This represents the bonding site with the two nitrogen atoms to which it is bonded. Furthermore, at least one of the hydrogen atoms in the structure below is substituted with a group having a radical polymerizable group (preferably a group represented by formula (R-1) described later).

[0069] Y ３ 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 ３ It is preferable that the group is represented by the following formula (V-9-2). In the following formula, * is Y in formula (A-3). ３ This represents the bonding site with the two nitrogen atoms to which it is bonded. Furthermore, at least one of the hydrogen atoms in the structure below is substituted with a group having a radical polymerizable group (preferably a group represented by formula (R-1) described later).

[0070] Also, Y ３ It is preferable that the structure does not contain an imide bond. Also, Y ３ It is preferable that the structure does not contain urethane bonds, urea bonds, and amide bonds. Furthermore, Y ３ It is preferable that the structure does not contain ester bonds. Among these, Y ３It is preferable that it does not contain imide bonds, urethane bonds, urea bonds, and amide bonds, and more preferably that it does not contain imide bonds, urethane bonds, urea bonds, amide bonds, and ester bonds.

[0071] Y ３ The structure included preferably has a group represented by the following formula (R-1) as a substituent, as a group having radical polymerizability. In formula (R-1), X Ｒ１ represents -O- or -C(=O)O-, L Ｒ１ represents a saturated aliphatic hydrocarbon group, A Ｒ１ represents a radical polymerizable group, a1 represents an integer greater than or equal to 1, and * represents a bonding site with other structures.

[0072] In formula (R-1), X Ｒ１ When is -C(=O)O-, the orientation of the bond is not particularly limited, but the oxygen atom is L Ｒ１ It is preferable that the bonding site is with . In formula (R-1), L Ｒ１ A is preferably a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, and more preferably a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms. In formula (R-1), A Ｒ１ The preferred embodiment of the radical polymerizable group in is the same as the preferred embodiment described above as the radical polymerizable group contained in the specific resin, and in particular the radical polymerizable group is preferably a (meth)acryloyl group (especially a (meth)acryloyloxy group, methacrylamide group, etc.), an aromatic vinyl group (e.g., a vinylphenyl group), or a maleimide group, and more preferably a (meth)acryloyloxy group or a vinylphenyl group. In formula (R-1), a1 is preferably an integer from 1 to 4, more preferably 1 or 2, and even more preferably 1.

[0073] In formula (R-1), L Ｒ１ A is an alkylene group having 1 to 4 carbon atoms, Ｒ１ In the above embodiment, L Ｒ１ A is a methylene group, Ｒ１An embodiment in which is a vinylphenyl group and a1 is 1 is also one of the preferred embodiments of the present invention.

[0074] Also, X ２ and X ３ Preferably, at least one of the components is a group represented by the following formula (AA-1). In formula (AA-1), * represents a bonding site with a carbonyl group.

[0075] Here, the above Y ３ It is preferable that the radical polymerizable group contained in is an aromatic vinyl group. Also, Y ３ Preferably, the radical polymerizable group contained in is introduced by including the group represented by the above formula (R-1) as a substituent.

[0076] [Repeating unit represented by formula (A-4)] The specified resin may contain a repeating unit represented by formula (A-4). In formula (A-4), X ４ represents a tetravalent organic group, Y ４ This group is a divalent group that does not correspond to any of the above formulas (Y-1) to (Y-11) and does not have a radical polymerizable group.

[0077] In formula (A-4), X ４ A preferred embodiment is X in formula (A-1). １ This is similar to the preferred embodiment. In formula (A-4), Y ４ A preferred embodiment is one in which the Y in formula (A-3) is not present except that it does not have a radical polymerizable group. ３ This is similar to the preferred embodiment.

[0078] Other, Y ４ This may be the basis described in paragraphs 0042 to 0053 of Japanese Patent Publication No. 2023-003421. Also, Y ４ It is preferable that the structure does not contain an imide bond. Also, Y ４ It is preferable that the structure does not contain urethane bonds, urea bonds, and amide bonds. Furthermore, Y ４ It is preferable that the structure does not contain ester bonds. Among these, Y ４It is preferable that it does not contain imide bonds, urethane bonds, urea bonds, and amide bonds, and more preferably that it does not contain imide bonds, urethane bonds, urea bonds, amide bonds, and ester bonds.

[0079] The content of any group represented by formula (Y-1) to (Y-11) in the specific resin is preferably 0.25 to 1.70 mmol / g, more preferably 0.30 to 1.65 mmol / g, and even more preferably 0.35 to 1.60 mmol / g. If the specific resin contains multiple types of groups represented by formula (Y-1) to (Y-11), it is preferable that the total content of the above multiple types of structures is within the above range. The above content is, １ It can be measured by structural analysis using H-NMR, etc.

[0080] [Absorbance] The absorbance of a 0.1 g / L NMP solution of a specific resin at a wavelength of 365 nm is preferably 0.070 or less, more preferably 0.065 or less, and even more preferably 0.060 or less. The above absorbance is the value at a path length of 1 cm. The above absorbance can be measured by preparing a 0.1 g / L NMP solution of the specific resin and measuring it with a spectrophotometer. If it is difficult to prepare a 0.1 g / L NMP solution of the specific resin, NMP solutions of different concentrations may be prepared, their absorbances measured, and converted.

[0081] [Content of Repeating Units] The molar content of repeating units represented by formula (A-1) is preferably 5 to 100 mol%, more preferably 10 to 100 mol%, and even more preferably 20 to 100 mol%, relative to the total molar content of repeating units in the specific resin. However, if the imidization rate described later is not 100%, at least one of the two imide rings contained in the repeating unit represented by formula (A-1) may be open. The content of this structure in which at least one ring is open is also included in the content of repeating units represented by formula (A-1) as described above. The same applies to the content of repeating units below.

[0082] The molar amount of repeating units represented by formula (A-2) is preferably 10 to 100 mol%, more preferably 10 to 80 mol%, and even more preferably 20 to 70 mol%, relative to the total molar amount of repeating units in the specific resin. The molar amount of repeating units represented by formula (A-3) is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, and even more preferably 30 to 70 mol%, relative to the total molar amount of repeating units in the specific resin. The total molar amount of repeating units represented by formula (A-2) and formula (A-3) is preferably 70 to 100 mol%, more preferably 80 to 100 mol%, and even more preferably 90 to 100 mol%, relative to the total molar amount of repeating units in the specific resin. The total molar content of the repeating units represented by formula (A-2), formula (A-3), and formula (A-4) is preferably 70 to 100 mol%, more preferably 80 to 100 mol%, and even more preferably 90 to 100 mol%, relative to the total molar content of repeating units in the specific resin.

[0083] [Imidification Rate] The imidification rate of the specified resin is preferably 70% or more, more preferably 80% or more, even more preferably 90% or more, even more preferably 95% or more, and particularly preferably 98% or more. The upper limit of the above imidification rate is not particularly limited and may be 100% or less.

[0084] In this invention, the imidization rate is a value calculated by the following method. The resin is dissolved in γ-butyrolactone, diluted to a viscosity of 2,000 mPa·s, and applied to a silicon wafer by spin coating to form a resin layer. If a resin layer cannot be formed due to reasons such as low solubility of the resin in γ-butyrolactone, the solvent may be changed to another solvent. Other solvents that can be used include solvents contained in the resin composition, such as NMP. The viscosity may also be changed as appropriate within an adjustable range. The silicon wafer to which the obtained resin layer has been applied is dried on a hot plate at 110°C for 5 minutes to obtain a resin layer with a uniform thickness of approximately 15 μm on the silicon wafer after film formation. Here, if only a resin solution with low viscosity can be obtained, and it is difficult to obtain a resin layer with a thickness of 15 μm, the film thickness may be changed as appropriate. For example, if the film thickness is 5 μm or more, a similar value for the imidization rate can be obtained. The above resin layer was measured using the ATR method with Nicoleti S20 (manufactured by Thermofisher), with a measurement range of 4000-700 cm. －１ The measurement was taken 50 times. 1380 cm －１ Nearby (1350-1450 cm) －１ (If there are multiple peaks, the peak height of the one with the highest peak intensity) and 1500 cm －１ Nearby (1460-1550 cm) －１ The imidization index A of the resin is calculated by dividing the value by the peak height of the peak with the maximum peak intensity (if there are multiple peaks) and heating the film at 350°C for 1 hour under a nitrogen atmosphere at a heating rate of 10°C / min. The imidization index B is calculated in the same manner and the value obtained by dividing the imidization index A by the imidization index B is calculated as the imidization rate of the resin. In measuring the imidization rate, the resin to be measured for imidization rate can be obtained from the composition by, for example, the following method: A solution of 1 g of the composition and 2 g of tetrahydrofuran is added to 50 g of methanol or water and crystallized to precipitate the resin, which is then filtered. The filtrate is collected, dissolved in 3.0 g of THF (tetrahydrofuran), added to 50 g of methanol or water and crystallized, filtered, and dried at 40°C for 20 hours to obtain the resin.

[0085] [Weight-average molecular weight] The weight-average molecular weight of the specific resin is preferably 2,500 or more, more preferably 4,000 or more, even more preferably 8,000 or more, particularly preferably 12,000 or more, even more preferably 16,000 or more, and even more preferably 20,000 or more. The upper limit of the above weight-average molecular weight is not particularly limited, but for example it is preferably 200,000 or less, more preferably 100,000 or less, even more preferably 70,000 or less, and particularly preferably 50,000 or less. The number-average molecular weight of the specific resin is preferably 1,500 or more, more preferably 3,000 or more, even more preferably 6,000 or more, and particularly preferably 10,000 or more. The upper limit of the above number-average molecular weight is not particularly limited, but for example it is preferably 50,000 or less, more preferably 45,000 or less, and even more preferably 35,000 or less. The degree of dispersion of a specific resin, expressed as weight-average molecular weight / number-average molecular weight, is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. The above degree of dispersion is not particularly limited, but is preferably 1.5 or more.

[0086] [Method for Manufacturing the Specific Resin] The specific resin may be manufactured, for example, by the method described in paragraphs 0134-0136 of International Publication No. 2022 / 145355. The above description is incorporated herein by reference. Alternatively, it may be synthesized by other known methods.

[0087] [Content] The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the resin composition. Furthermore, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition. The resin composition of the present invention may contain only one type of specific resin, or it may contain two or more types. When it contains two or more types, it is preferable that the total amount is within the above range.

[0088] The resin composition of the present invention may also preferably contain at least two types of resins. Specifically, the resin composition of the present invention may contain a total of two or more types of specific resins and other resins described later, or it may contain two or more specific resins, but it is preferable that it contains two or more specific resins. When the resin composition of the present invention contains two or more specific resins, for example, it is preferable that it contains two or more polyimides with different structures derived from dianhydrides.

[0089] <Other Resins> The resin composition of the present invention may contain the specified resin described above and other resins different from the specified resin (hereinafter also simply referred to as "other resins"). Examples of other resins include polyimide precursors different from the specified resin, polyimides, polybenzoxazole precursors, polybenzoxazoles, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, polyester resins, etc. For example, by further adding (meth)acrylic resin, a resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained. For example, in place of the polymerizable compound described later, or in addition to the polymerizable compound described later, a polymerizable compound with a high polymerizability value and a weight-average molecular weight of 20,000 or less (for example, the molar amount of polymerizable groups per 1 g of resin is 1 × 10) may be used.－３ By adding (meth)acrylic resin (in a quantity of mol / g or more) to the resin composition, the coatability of the resin composition, the solvent resistance of the pattern (cured product), and other properties can be improved.

[0090] If 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, even more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total solid content of the resin composition. If the resin composition of the present invention contains other resins, the content of the other resins is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on the total solid content of the resin composition. As a preferred embodiment of the resin composition of the present invention, the content of other resins can be low. In the above embodiment, the content of other resins is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the resin composition. The lower limit of the above content is not particularly limited and may be 0% by mass or more. The resin composition of the present invention may contain only one other resin, or it may contain two or more other resins. When it contains two or more other resins, it is preferable that the total amount is within the above range.

[0091] The resin composition of the present invention preferably further contains a polymerization initiator and a polymerizable compound, and more preferably further contains a photoradical polymerization initiator and a radical polymerizable compound. Each of these will be described below.

[0092] <Polymerizable Compounds> The resin composition of the present invention preferably contains polymerizable compounds. Examples of polymerizable compounds include radical crosslinking agents or other crosslinking agents.

[0093] [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.

[0094] 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.

[0095] 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.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] 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).

[0101] 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.

[0102] 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.

[0103] 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.

[0104] 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.

[0105] 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.

[0106] 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.

[0107] 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.

[0108] [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.

[0109] [Polymerization Initiator] The resin composition of the present invention preferably contains a polymerization initiator. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable to include a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular restrictions on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible region is preferred. Alternatively, it may be an activator that acts with a photoexcited sensitizer to generate active radicals.

[0110] 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.

[0111] 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.

[0112] 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.

[0113] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used as photoradical polymerization initiators. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Publication No. 10-291969 and an acylphosphine oxide-based initiator described in Japanese Patent Publication No. 4225898 can be used, and this is incorporated herein by reference.

[0114] 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.

[0115] 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.

[0116] 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.

[0117] 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.

[0118] Specific examples of oxime compounds include the compounds described in Japanese Patent Publication No. 2001-233842, Japanese Patent Publication No. 2000-080068, Japanese Patent Publication No. 2006-342166, the compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), the compounds described in J. C. S. Perkin II (1979, pp. 156-162), and Journal of Photopolymer Science and Examples include compounds described in Technology (1995, pp. 202-232), compounds described in Japanese Patent Publication No. 2000-066385, compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Publication No. 2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, compounds described in Japanese Patent Publication No. 2017-198865, compounds described in paragraphs 0025-0038 of International Publication No. 2017 / 164127, compounds described in International Publication No. 2013 / 167515, and others, the contents of which are incorporated herein by reference.

[0119] Preferred oxime compounds include, for example, compounds with the following structures, as well as 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropane-1-one, 2-(benzoyloxy(imino))-1-phenylpropane-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropane-1-one. In resin compositions, it is particularly preferable to use oxime compounds as photoradical polymerization initiators. Oxime compounds used as photoradical polymerization initiators have a >C=N-O-C(=O)- linking group in their molecule.

[0120]

[0121] Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (all manufactured by BASF), ADEKA optomer N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in Japanese Patent Publication No. 2012-014052), TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA Arclus NCI-730, NCI-831, and ADEKA Arclus NCI-930 (manufactured by ADEKA Corporation), DFI-091 (manufactured by Daito Chemix Co., Ltd.), and SpeedCure PDO (SARTOMER Examples include those manufactured by ARKEMA. Additionally, oxime compounds with the following structures can also be used.

[0122] 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.

[0123] 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.

[0124] 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.

[0125] [Sensitizer] The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and enters an electronically excited state. When the sensitizer enters an electronically excited state, it comes into contact with thermal radical polymerization initiators, photoradical polymerization initiators, etc., causing electron transfer, energy transfer, and heat generation. As a result, the thermal radical polymerization initiators and photoradical polymerization initiators undergo chemical changes and decompose, generating radicals, acids, or bases. Suitable sensitizers include compounds such as benzophenone, Michla's ketone, coumarin, pyrazole azo, anilino azo, triphenylmethane, anthraquinone, anthracene, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo compounds.Examples of sensitizers include 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.

[0126] 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.

[0127] [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.

[0128] 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.

[0129] 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.

[0130] 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.

[0131] 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.

[0132] 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.

[0133] [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.

[0134] 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.

[0135] 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. The resin composition may contain only one type of thermal polymerization initiator or two or more types. If two or more types of thermal polymerization initiators are included, it is preferable that the total amount is within the above range.

[0136] <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. 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, acyloxyimino compounds, and the like. Specific examples of nonionic base generators include the compounds described in paragraphs 0249-0275 of International Publication No. 2022 / 145355. The foregoing description is incorporated herein by reference.

[0137] Examples of base-generating agents include, but are not limited to, the following compounds.

[0138]

[0139] The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

[0140] Specific preferred compounds for ionic base generators include, for example, the compounds described in paragraphs 0148-0163 of International Publication No. 2018 / 038002.

[0141] Specific examples of ammonium salts include, but are not limited to, the following compounds.

[0142] Specific examples of iminium salts include, but are not limited to, the following compounds.

[0143] Furthermore, as a base-generating agent, it is preferable that the amino group is protected by a t-butoxycarbonyl group, from the viewpoint of storage stability and base generation by deprotection during curing.

[0144] Examples of amine compounds protected by a t-butoxycarbonyl group include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, and 2-amino-1,3-propanediol. Alcohol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzyl alcohol, diethanol Luamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidyl)-2-propanol, 1,4-butanol bis(3-aminopropyl) Examples include, but are not limited to, ethers, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybis(ethylamine), 1,14-diamino-3,6,9,12-tetraoxatetradecane, 1-aza-15-crown 5-ether, diethylene glycol bis(3-aminopropyl) ether, 1,11-diamino-3,6,9-trioxaundecane, or compounds in which the amino group of an amino acid or its derivative is protected by a t-butoxycarbonyl group.

[0145] 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.

[0146] <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.

[0147] 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.).

[0148] 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.

[0149] Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucocenone, and dihydrolevoglucocenone.

[0150] Suitable cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0151] As an example of a sulfoxide, dimethyl sulfoxide is a suitable choice.

[0152] 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.

[0153] Suitable ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0154] 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.

[0155] From the viewpoint of improving the properties of the coated surface, it is also preferable to use a mixture of two or more solvents.

[0156] 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.

[0157] 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.

[0158] <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.

[0159] [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.).

[0160]

[0161] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- Examples include (aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, and 3-trimethoxysilylpropyl succinic anhydride. These can be used individually or in combination of two or more. Furthermore, oligomeric compounds having multiple alkoxysilyl groups can also be used as silane coupling agents. Examples of such oligomeric compounds include compounds containing repeating units represented by the following formula (S-1). In formula (S-1), R Ｓ１ represents a monovalent organic group, R Ｓ２ R represents a hydrogen atom, a hydroxyl group, or an alkoxy group, and n represents an integer between 0 and 2. Ｓ１It is preferable that the structure includes polymerizable groups. Examples of polymerizable groups include groups having ethylenically unsaturated bonds, epoxy groups, oxetanyl groups, benzoxazolyl groups, blocked isocyanate groups, amino groups, etc. Examples of groups having ethylenically unsaturated bonds include vinyl groups, allyl groups, isoallyl groups, 2-methylallyl groups, aromatic vinyl groups (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 multiple repeating units represented by formula (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 multiple repeating units represented by formula (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. Commercially available products can be used as such oligomer-type compounds, and an example of a commercially available product is KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0162] [Aluminum-based adhesive aids] Examples of aluminum-based adhesive aids include aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), and ethyl acetate aluminum diisopropylate.

[0163] 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.

[0164] 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.

[0165] <Compound X1> The resin composition of the present invention may contain compound X1. Compound X1 is a compound having at least one structure selected from the group consisting of a 1,3-dicarbonyl structure and a β-hydroxycarbonyl structure, and having a molecular weight of 1,000 or less. Here, the 1,3-dicarbonyl structure refers to the structure represented by the following formula (DC-1), and the β-hydroxycarbonyl structure refers to the structure represented by the following formula (HC-1).

[0166] In formula (DC-1) or formula (HC-1), * and # each represent a bonding site with another structure. Here, * is preferably a bonding site with a carbon atom, oxygen atom, nitrogen atom, or sulfur atom. Also, # is preferably a bonding site with a hydrogen atom or carbon atom. Here, the structure represented by (DC-1) above may be in enol form as shown in formula (DC-2) below. Also, the structure represented by (HC-1) above may be in enol form as shown in formula (HC-2) below. In formula (DC-2) or formula (HC-2), * and # represent bonding sites with other structures, respectively. * is preferably a bonding site with a carbon atom, oxygen atom, nitrogen atom, or sulfur atom. # is preferably a bonding site with a hydrogen atom or carbon atom.

[0167] It is preferable that compound X1 does not contain metal atoms in its structure. Here, "metal atoms" does not include metalloid atoms such as silica. Furthermore, it is preferable that compound X1 is not coordinated to metal atoms in the resin composition.

[0168] [Molecular Weight] The molecular weight of compound X1 is 1,000 or less, preferably 100 to 500, more preferably 100 to 400, even more preferably 100 to 350, particularly preferably 100 to 300, and even more preferably 100 to 250.

[0169] [Specific Examples] Specific examples of compound X1 are not limited to those described below, but include compounds with the following structures.

[0170] [Content] The content of compound X1 relative to the total solid content of the resin composition of the present invention is preferably 0.01 to 30% by mass. The lower limit is more preferably 0.02% by mass or more, even more preferably 0.05% by mass or more, and particularly preferably 0.10% by mass or more. The upper limit is more preferably 20% by mass or less, even more preferably 10% by mass or less, and particularly preferably 5% by mass or less. Furthermore, an embodiment in which the content is 1% by mass or less is also one of the preferred embodiments of the present invention. Compound X1 may be used alone, or two or more may be used in combination. When two or more are used in combination, it is preferable that their total amount be within the above range.

[0171] <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.

[0172] 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.

[0173] As migration inhibitors, ion trapping agents that capture anions such as halogen ions can also be used.

[0174] 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.

[0175] Specific examples of migration inhibitors include the following compounds.

[0176]

[0177] 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 0.01 to 2.0% by mass, and even more preferably 0.01 to 1.0% by mass, based on the total solid content of the resin composition.

[0178] 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.

[0179] <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.

[0180] Specific examples of polymerization inhibitors include the compounds described in paragraph 0310 of International Publication No. 2021 / 112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenoxazine, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]nona-2-ene-N,N-dioxide, and the like. This information is incorporated herein by reference.

[0181] 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.

[0182] 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.

[0183] [Urea compounds, carbodiimide compounds, isourea compounds] From the viewpoint of elongation at break and adhesion to metal or resin layers, the resin composition of the present invention may contain at least one compound selected from the group consisting of compounds having a urea bond (urea compounds), compounds having a carbodiimide structure (carbodiimide compounds), and compounds having an isourea bond (isoureea compounds) (hereinafter also referred to as "urea compounds, etc."). Among these, the resin composition of the present invention preferably further contains a compound having a urea bond. The urea compounds, etc. referred to here do not include the polymerizable compounds and compounds corresponding to silane coupling agents as described above. Examples of urea compounds include the compounds, etc. described in paragraphs 0334 to 0339 of International Publication No. 2022 / 070730.

[0184] Specific examples of urea compounds include, but are not limited to, dicyclohexylurea, diisopropylurea, dicyclohexylcarbodiimide, diisopropylcarbodiimide, dicyclohexylisourea, and diisopropylisourea.

[0185] The total content of urea compounds, etc., is preferably 0.1 to 10.0 parts by mass, more preferably 0.5 to 8.0 parts by mass, and even more preferably 1.0 to 6.0 parts by mass, per 100 parts by mass of the specific resin. Urea compounds, etc., may be used individually or in combination of two or more types. When two or more bases are used in combination in the base-containing treatment solution, it is preferable that their total content be within the above range.

[0186] <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.

[0187] Furthermore, it is preferable to include a compound with the following structure as a light absorber.

[0188] The content of the light absorber relative to the total solid content of the resin composition of the present invention is not particularly limited, but is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 5% by mass.

[0189] <Other Additives> The resin composition of the present invention may optionally contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, photoacid generators, anti-aggregation agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliary agents (e.g., defoamers, flame retardants, etc.), to the extent that the effects of the present invention are obtained. By appropriately including these components, properties such as film properties can be adjusted. These components can be described, for example, in paragraphs 0183 onwards of Japanese Patent Application Publication No. 2012-003225 (paragraph 0237 of the corresponding U.S. Patent Application Publication No. 2013 / 0034812), paragraphs 0101 to 0104, 0107 to 0109 of Japanese Patent Application Publication No. 2008-250074, and the contents of these are incorporated herein. When these additives are incorporated, it is preferable that their total content be 3% by mass or less of the solid content of the resin composition of the present invention.

[0190] <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, an excellent coating film can be obtained on the coated surface.

[0191] <Restrictions on the substances contained in the resin composition> The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved. Furthermore, the lower limit of the water content of the resin composition is preferably 0.001% by mass or more, can be 0.05% by mass or more, and can be 0.5% by mass or more, from the viewpoint of reducing the effort required to manage storage conditions, adhesion, developability, etc. Specific examples of water content of the resin composition include, for example, 0.05% by mass, 0.2% by mass, and 1.4% by mass. Methods for maintaining the water content include adjusting the humidity in the storage conditions and reducing the porosity of the storage container during storage.

[0192] From the viewpoint of insulating properties and reliability, the metal content of the resin composition of the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Furthermore, from the viewpoint of reducing the effort required to reduce the metal content, mechanical properties, and adhesion, the lower limit of the metal content in the resin composition is preferably 0.001 ppm by mass or more, and can also be 0.01 ppm by mass or more. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, manganese, aluminum, titanium, cobalt, zinc, and tin, but excludes metals included as complexes between organic compounds and metals. When multiple metals are included, it is preferable that the total of these metals is within the above range. Specific examples of metal content include, for example, 0.002 ppm by mass, 0.05 ppm by mass, and 0.3 ppm by mass.

[0193] 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.

[0194] Considering its application as a semiconductor material, the halogen atom content of the resin composition of the present invention is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass, from the viewpoint of preventing wiring corrosion. In particular, the amount of halogen atoms present in the form of halogen ions is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Furthermore, from the viewpoint of reducing the effort required to reduce halogen ions, the lower limit of halogen ions in the resin composition can be 0.01 ppm by mass or more, or 0.1 ppm by mass or more. Specific examples of halogen ion amounts include, for example, 0.02 ppm by mass, 0.5 ppm by mass, and 2.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferable that the total amount of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above ranges. A preferred method for adjusting the halogen atom content is ion exchange treatment.

[0195] 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.

[0196] <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

[0197] <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.

[0198] <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 a conventionally known method. Examples of the mixing method include mixing by a stirring blade, mixing by a ball mill, and mixing by rotating a tank. The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.

[0199] For the purpose of removing foreign substances such as dust and fine particles in the resin composition of the present invention, it is preferable to perform filtration using a filter. As the filter, for example, the filter described in paragraph 0287 of International Publication No. 2023 / 190064 can be used. This description is incorporated herein.

[0200] (Method for Producing Cured Product) The method for producing a cured product of the present invention preferably includes a film-forming step of applying the resin composition onto a substrate to form a film. The method for producing a cured product more preferably includes the above film-forming step, an exposure step of selectively exposing the film formed by the film-forming step, and a development step of developing the film exposed by the exposure step using a developer to form a pattern. The method for producing a cured product is particularly preferably to include at least one of the above film-forming step, the above exposure step, the above development step, a heating step of heating the pattern obtained by the development step, and a post-exposure step of exposing the pattern obtained by the development step. Further, the method for producing a cured product preferably includes the above film-forming step and a step of heating the above film. Hereinafter, the details of each step will be described.

[0201] <Film-Forming Step> The resin composition of the present invention can be used in a film-forming step of applying it onto a substrate to form a film. The method for producing a cured product of the present invention preferably includes a film-forming step of applying the resin composition onto a substrate to form a film.

[0202] [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.

[0203] 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.

[0204] 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.

[0205] <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.

[0206] <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.

[0207] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, with 240 to 550 nm being preferred.

[0208] 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.

[0209] <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.

[0210] <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.

[0211] [Developer] Developers used in the developing process include alkaline aqueous solutions or developers containing organic solvents.

[0212] 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 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. The description in paragraph 0300 of International Publication No. 2023 / 190064 is incorporated herein by reference.

[0213] 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.

[0214] When the developer contains an organic solvent, one or more organic solvents can be used in mixture form. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide is more preferred, and a developer containing cyclopentanone is particularly preferred.

[0215] 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.

[0216] The developing solution may further contain other components. Examples of other components include known surfactants and known defoamers.

[0217] [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 it 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.

[0218] 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.

[0219] 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.

[0220] [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.

[0221] 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.

[0222] 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.

[0223] 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.

[0224] The rinse solution may further contain other components. Examples of other components include known surfactants and known defoaming agents.

[0225] [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.

[0226] 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.

[0227] <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 undergo cyclization 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. 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.

[0228] <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 detachment of acid-degradable groups proceeds by photosensitization of the photoacid generator can be promoted. In the post-development exposure step, it is sufficient for at least a part of the pattern obtained in the development step to be exposed, but it is preferable for the entire pattern to be exposed. The amount of exposure in the post-development exposure step is 50 to 20,000 mJ / cm in terms of exposure energy at the wavelength to which the photosensitive compound is sensitive. ２ Preferably, 100 to 15,000 mJ / cm² ２This 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.

[0229] <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).

[0230] 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.

[0231] The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, methods described in Japanese Patent Publication No. 2007-157879, Japanese Patent Publication No. 2001-521288, Japanese Patent Publication No. 2004-214501, Japanese Patent Publication No. 2004-101850, U.S. Patent No. 7888181B2, and U.S. Patent No. 9177926B2 can be used. For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and methods combining these can be considered. More specifically, patterning methods combining sputtering, photolithography and etching, and patterning methods combining photolithography and electroplating can be mentioned. Preferred embodiments of the plating include electroplating using copper sulfate or copper cyanide plating solutions.

[0232] The thickness of the metal layer is preferably 0.01 to 50 μm at the thickest part, and more preferably 1 to 10 μm.

[0233] <Use> As a method for producing a cured product of the present invention or an applicable field of the cured product, examples include an insulating film for an electronic device, an interlayer insulating film for a redistribution layer, a stress buffer film, and the like. In addition, there are sealing films, substrate materials (base films, coverlays, and interlayer insulating films for flexible printed boards), or patterning an insulating film for mounting applications as described above by etching. For these applications, reference can be made to, for example, "High Functionalization and Application Technology of Polyimide" by Science & Technology Co., Ltd., April 2008, supervised by Masaki Kakinuma, "Fundamentals and Development of Polyimide Materials" published by CMC Technical Library, November 2011, "Latest Polyimide Fundamentals and Applications" edited by the Japan Polyimide & Aromatic Polymer Research Society, NTS, August 2010, etc.

[0234] The method for producing a cured product of the present invention or the cured product of the present invention can also be used for the production of a printing surface such as an offset printing surface or a screen printing surface, the use of a molded part for etching, electronics, particularly the production of a protective lacquer and a dielectric layer in microelectronics.

[0235] (Laminate and method for producing laminate) The laminate of the present invention refers to a structure having a plurality of 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 laminated with three or more layers. Among the two or more layers made of the cured product contained in the above laminate, at least one is a layer made of the cured product of the present invention. From the viewpoint of suppressing the shrinkage of the cured product or the deformation of the cured product accompanying the above shrinkage, etc., it is also preferable that all the layers made of the cured product contained in the above laminate are layers made of the cured product of the present invention.

[0236] That is, the method for producing a laminate of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes repeating the method for producing a cured product of the present invention a plurality of times.

[0237] 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.

[0238] <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.

[0239] 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.

[0240] 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.

[0241] 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.

[0242] (Surface Activation Treatment Step) The manufacturing method of the laminate of the present invention preferably includes a surface activation treatment step in which at least a portion of the metal layer and the resin composition layer is surface activated. The surface activation treatment step is usually performed after the metal layer formation step, but after the development step (preferably after at least one of the heating step and the post-development exposure step), the surface activation treatment step may be performed on the resin composition layer before the metal layer formation step. The surface activation treatment may be performed only on at least a portion of the metal layer, or only on at least a portion of the resin composition layer after exposure, or on at least a portion of both the metal layer and the post-exposure resin composition layer. It is preferable to perform the surface activation treatment on at least a portion of the metal layer, and it is preferable to perform the surface activation treatment on a portion or all of the area on the surface of the metal layer where the resin composition layer is formed. By performing the surface activation treatment on the surface of the metal layer in this way, the adhesion to the resin composition layer (film) provided on its surface can be improved. It is also preferable to perform the surface activation treatment on a portion or all of the post-exposure resin composition layer (resin layer). By performing the surface activation treatment on the surface of the resin composition layer in this way, the adhesion to the metal layer and resin layer provided on the surface-activated surface can be improved. In particular, when developing negative film, if the resin composition layer is cured, it is less susceptible to damage from surface treatment and adhesion is easily improved. Surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of International Publication No. 2021 / 112189. This is incorporated herein by reference.

[0243] (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.

[0244] (Polyimide) The polyimide of the present invention has repeating units represented by the following formula (A-2) and repeating units represented by the following formula (A-3). In formula (A-2), X ２ represents a tetravalent organic group, Y ２ represents a group represented by any of the following formulas (Y-1) to (Y-11). In formula (A-3), X ３ represents a tetravalent organic group, Y ３ This group is a divalent group having radical polymerizability and does not fall under any of the following formulas (Y-1) to (Y-11). In equations (Y-1) to (Y-4), R １ Each of these independently represents a hydrogen atom or a substituent, R １ At least one of the groups is an electron-withdrawing group, and * represents the bonding site with the nitrogen atom. In equations (Y-5) to (Y-7), R ２ Each of these independently represents a substituent that does not have a hydrogen atom or a radical polymerizable group, R １ At least one of them is an electron-withdrawing group, A １ -C(=O)-, -S(=O) ２ -, -S(=O)-, -C(R ３ ) ２ - is one of the following, R ３ * represents a hydrogen atom or substituent, and * represents a bond site with a nitrogen atom. In formula (Y-8), R ２ Each is independently a hydrogen atom or a substituent, and R ４ Each of these independently represents a substituent, R ５ Each of these independently represents a substituent, L １ represents a single bond or a divalent linking group, and * represents the bond site with the nitrogen atom. In formula (Y-9), R ６ These are independently a hydroxyl group, an alkoxy group, a cyano group, a formyl group, and -C(=O)NR Ｙ１ ２ , -C (=O) OR Ｙ２ , -C(=O)R Ｙ２ R is an alkenyl group, an alkynyl group, or an alkyl group having 2 or more carbon atoms which may have substituents. Ｙ１R is a hydrogen atom or substituent. Ｙ２ represents an organic group, R ７ Each is independently a hydrogen atom or a substituent, and R ７ One of these represents the bonding position with the nitrogen atom in formula (A-2), and R ８ Each is independently a hydrogen atom or a substituent, and R ８ One of these represents the bond position with the nitrogen atom in formula (A-2). In formula (Y-10), R ７ Each is independently a hydrogen atom or a substituent, and R ７ One of these represents the bonding position with the nitrogen atom in formula (A-2), and R ８ Each is independently a hydrogen atom or a substituent, and R ８ One of these represents the bonding position with the nitrogen atom in formula (A-2), and R ９ Each of these is independently an alkyl group which may have substituents. In formula (Y-11), R １０ Each of these is independently an alkyl group which may have substituents, and R １１ Each is independently a hydrogen atom or a substituent, and R １１ One of the following is an organic group, R １１ One of these represents the bonding position with the nitrogen atom in formula (A-2), and R １２ Each is independently a hydrogen atom or a substituent, and R １２ One of the following is an organic group, R １２ One of these represents the bonding position with the nitrogen atom in formula (A-2).

[0245] Preferred embodiments of the repeating units represented by formula (A-2) and formula (A-3) in the polyimide of the present invention are the same as preferred embodiments of the repeating units represented by formula (A-2) and formula (A-3) in the specific resin of the present invention described above. Preferred embodiments of the polyimide of the present invention are the same as preferred embodiments of the specific resin of the present invention described above, except that they are limited to including the repeating units represented by formula (A-2) and formula (A-3).

[0246] 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.

[0247] <Method for producing specific resins> [Synthesis Example 1: Synthesis of polyimide (resin P-2)] 30.5 g of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride is dissolved in 49 g of N-methylpyrrolidone (NMP) to obtain a solution. Subsequently, 3.5 g of 3,3'-dihydroxybenzidine, 11.8 g of 4,4'-methylenebis(2,6-diethylaniline), and 0.9 g of p-aminophenol are dissolved in 154 g of NMP, and 20 mL of toluene is added. While maintaining a temperature of 40°C or below, the above diamine solution is added dropwise to the acid anhydride solution over 1 hour, and then the reaction is carried out at 200°C for 4 hours. During the reaction, reflux and dehydration were carried out using a Dean-Stark strainer. After the reaction is complete, the mixture is cooled to 25°C. To the above reaction solution, 0.90 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 22.3 g of 4-chloromethylstyrene, 24.3 g of potassium carbonate powder, 2.9 g of potassium iodide, and 68 g of NMP were added, and the mixture was reacted at 95°C for 2 hours. After the reaction was complete, the mixture was cooled to 25°C, diluted with 400 mL of tetrahydrofuran, the solids were removed by filtration, and the mixture was then washed with 200 mL of tetrahydrofuran. Subsequently, the reaction solution was added dropwise to a mixture of 2.0 liters of methanol and 0.9 L of water, stirred for 60 minutes, and then the polyimide resin was filtered. After filtration, the mixture was dried under reduced pressure at 40°C for 15 hours. Next, the dried resin is dissolved in 450 mL of tetrahydrofuran, and 0.22 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical is added and dissolved. Then, 65 g of ion exchange resin (MB-1: Organo) is added, and the mixture is stirred for 2 hours. After removing the ion exchange resin by filtration, the polyimide resin is precipitated in 2.0 liters of methanol and stirred for 60 minutes. The polyimide resin is obtained by filtration and dried under reduced pressure at 40°C for 20 hours to obtain 47.2 g of polyimide resin P-2. The weight-average molecular weight of the obtained resin P-2 is 27,000. The structure of the repeating unit is: １The molecular weight is determined from the 1H-NMR spectrum. In the structures below, the subscripts of the repeating units represent the molar ratio of each repeating unit. Unless otherwise specified, the weight-average molecular weight of the following resins was measured by the following method. A high-speed GPC instrument HLC-8420GPC (manufactured by Tosoh Corporation) was used, with a TSK guard column Super AW-H (4.6 mm × 35 mm) as the guard column and two TSKgel Super AWM-H (4.6 mm × 150 mm) columns connected in series for GPC measurement. NMP (N-methyl-2-pyrrolidone) was used as the eluent. Polystyrene PS-1, manufactured by AMR, was used as the standard.

[0248] [Synthesis Examples 2-36: Synthesis of Polyimides (Resins P-1, P-3-P-36)] Resins P-1, P-3-P-36 were synthesized in the same manner as in Synthesis Example 1, except for appropriately adjusting the types and equivalent amounts of substrates and reagents. The weight-average molecular weight (Mw) of resins P-2-P-36 was 27,000. For P-20, resins P-20 with weight-average molecular weights (Mw) of 10,000, 15,000, 18,000, 22,000, 35,000, 45,000, 60,000, and 100,000 were synthesized by adjusting the amount of diamine used. １ H-NMR confirmed that the structures of resins P-2 to P-36 are represented by the following formulas (P-2) to (P-36). In the following structures, the subscripts in parentheses represent the molar ratio of each repeating unit.

[0249] [Synthesis Example PC-1: Synthesis of Resin PC-1] Resin PC-1 is synthesized using the same method as in Synthesis Example 1. The weight-average molecular weight (Mw) of resin PC-1 is 27,000. １ H-NMR confirms that the structure of resin PC-1 is represented by the following formula (PC-1). In the structure below, the subscripts in parentheses represent the molar ratio of each repeating unit.

[0250] <Examples and Comparative Examples> In each example, the components listed in the table below are mixed to obtain each resin composition. In the comparative example, the components listed in the table below are mixed to obtain a comparative composition. Specifically, the content (amount blended) of each component listed in the table other than the solvent is the amount (parts by mass) indicated in the "parts by mass" column of each column in the table. The solvent content (amount blended) is set so that the solid content concentration of the composition is equal to the value (mass%) of "solid content concentration (mass%)" in the table, and the ratio (mass ratio) of the content of each solvent to the total mass of the solvent is the ratio indicated in the "ratio" column in the table. The obtained resin compositions and comparative compositions are subjected to pressure filtration using a polytetrafluoroethylene filter with a pore width of 0.8 μm. In the table, "-" indicates that the composition does not contain the corresponding component.

[0251]

[0252]

[0253]

[0254]

[0255]

[0256]

[0257]

[0258]

[0259]

[0260] Details of each component listed in the table are as follows:

[0261] [Resins] ・P-1 to P-36, PC-1: Resins P-1 to P-36 and resin PC-1 obtained by the above synthesis example. P-1 to P-36 are resins that fall under the category of specific resins.

[0262] [Polymerizable Compounds] ・M-1 to M-4: Compounds with the following structures; in the following structures, the subscript in parentheses indicates the number of repetitions.

[0263] [Photopolymerization Initiators] ・I-1 to I-8: Compounds with the following structures

[0264] [Polymerization inhibitors] ・B-1 to B-10: Compounds with the following structure

[0265] [Silane coupling agents (metal adhesion modifiers)] ・C-1 to C-5: Compounds with the following structures.

[0266] [Migration Inhibitors] ・D-1 to D-5: Compounds with the following structure

[0267] [Additives] ・E-1 to E-4: Compounds with the following structure ・E-5: BYK-333 (manufactured by BYK) ・E-6 to E-8: Compounds with the following structure

[0268] [Solvents] GBL: γ-butyrolactone, CP: cyclopentanone, γ-valerolactone, NMP: N-methyl-2-pyrrolidone, MDMPA: KJCMPA-100 (manufactured by KJ Chemicals Co., Ltd.), toluene: toluene, CH: cyclohexanone

[0269] <Evaluation> [Measurement of absorbance] For resins P-1 to P-25, a 0.1 g / L NMP solution was prepared for each, and the absorbance at a wavelength of 365 nm was measured using a spectrophotometer. The absorbance for each was 0.070 or less.

[0270] [Evaluation of Focus Margin] Each resin composition or comparative composition prepared in each example and comparative example is applied to an 8-inch silicon wafer by spin coating to form a coated film. The silicon wafer to which the obtained coated film is applied is dried on a hot plate at 100°C for 5 minutes to form a resin composition layer of uniform thickness of 8 μm on the silicon wafer. In the example where "M" is indicated in the exposure conditions column, a mask with a circular pattern of 5 μm in diameter is formed on this resin composition layer, and exposure is performed at 500 mJ / cm using an i-line stepper FPA-3030iWa (NA=0.16) (manufactured by Canon). ２The exposure energy is used to expose the material with light of the exposure wavelength (nm) listed in the "Exposure Wavelength (nm)" column of the table. In the example where "D" is written in the "Exposure Conditions" column, a direct exposure device (Adtec DE-6UH III) is used as the light source, and laser direct imaging exposure is performed on the above circular area without using a photomask. During these exposures, the focus is moved 2 μm at a time, with the film surface as the reference point towards the bottom of the film. After that, the material is developed with cyclopentanone for 60 seconds and rinsed with PGMEA to obtain a resin layer. In the example where a numerical value is written in the "Cure Temperature (°C)" column, a hot plate is used to heat the resin composition layer after exposure at a heating rate of 10°C / min under a nitrogen atmosphere until it reaches the temperature listed in the "Cure Temperature (°C)" column of the table, and then the temperature is maintained for the time listed in the "Cure Time (min)" column of the table to obtain a cured product. In the cases where "IR" is written in the "Cure Temperature (°C)" column, an infrared lamp heating device (Advance Riko Co., Ltd., RTP-6) is used to heat the resin film obtained in each example in a nitrogen atmosphere at a heating rate of 10°C / min until it reaches 230°C, and then maintain the above temperature for the time specified in "Cure Time (min)" in the table to obtain a cured product. The pattern shape of the obtained cured product is observed under an optical microscope, and the maximum value of the focus position where a circular pattern with a diameter of 5 ± 1 μm is formed is determined as the focus margin and evaluated according to the following criteria. The evaluation results are recorded in the "Focus Margin" column of the table below. The wider the focus margin (the larger the value), the greater the tolerance for the focus position and the more desirable the result. -Evaluation Criteria- A: Focus margin is 15 μm or more. B: Focus margin is 12 μm or more and less than 15 μm. C: Focus margin is 8 μm or more and less than 12 μm. D: Focus margin is less than 8 μm.

[0271] [Evaluation of Elongation at Break] The resin composition or comparative composition prepared in each example and comparative example is 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 is formed is 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 10 μm on the copper substrate. In the example where "M" is written in the exposure conditions column, the resin composition layer or comparative composition layer on the copper substrate is exposed using a photomask with a rectangular area of ​​3 mm width and 30 mm length, and a stepper is used as the light source at 500 mJ / cm². ２The material is exposed with light of the exposure wavelength (nm) listed in the "Exposure Wavelength (nm)" column of the table, using the specified exposure energy. In the example where "D" is written in the "Exposure Conditions" column, a direct exposure apparatus (Adtec DE-6UH III) is used as the light source, and laser direct imaging exposure is performed on the rectangular area without using a photomask. After that, the material is developed with cyclopentanone for 60 seconds and rinsed with PGMEA to obtain a resin layer. In the example where a numerical value is written in the "Cure Temperature (°C)" column, the resin composition layer after exposure is heated using a hot plate in a nitrogen atmosphere at a heating rate of 10°C / min until it reaches the temperature listed in the "Cure Temperature (°C)" column of the table, and then the temperature is maintained for the time specified in the "Cure Time (min)" column of the table to obtain a cured product. In the cases where "IR" is written in the "Cure Temperature (°C)" column, the resin film obtained in each example is heated in a nitrogen atmosphere at a heating rate of 10°C / min using an infrared lamp heating device (Advance Riko Co., Ltd., RTP-6), and after reaching 230°C, the above temperature is maintained for the time specified in the "Cure Time (min)" in the table to obtain a cured product. The cured resin layer (cured product) is immersed in a 4.9 mass% hydrofluoric acid aqueous solution, and the cured product (test piece) is peeled off the silicon wafer. The longitudinal elongation of the peeled cured product (test piece with a sample width of 3 mm and a sample length of 30 mm) is measured in accordance with JIS K 6251:2017 using a tensile testing machine (Tensilon) under conditions of a crosshead speed of 300 mm / min, 25°C, and 65% RH (relative humidity). Each measurement is performed five times, and the arithmetic mean of the elongation rate at fracture (elongation at break) of the test specimen at the time of fracture during the five measurements is used as the index value. Evaluation is performed according to the evaluation criteria below, and the evaluation results are recorded in the "Elongation at Break" column of the table. The larger the index value, the better the film strength of the cured product. -Evaluation Criteria- A: The above index value is 60% or more. B: The above index value is 50% or more and less than 60%. C: The above index value is 40% or more and less than 50%. D: The above index value is less than 40%.

[0272] [Evaluation of Glass Transition Temperature] The Tg of the test specimen prepared in the "Evaluation of Elongation at Breaking" above will be measured using DMA850 (TA Instruments). Specifically, the temperature conditions of the cured material will be changed in the following order (1) to (2) and the glass transition temperature will be measured. (1) Heat from 25°C to 350°C at a rate of 5°C / min. (2) Cool from 350°C to 25°C. The obtained Tg will be evaluated according to the evaluation criteria below. The evaluation results will be recorded in the "Cured Film Tg" column of the table. -Evaluation Criteria- A: Glass transition temperature is 200°C or higher. B: Glass transition temperature is 180°C or higher and less than 200°C. C: Glass transition temperature is less than 180°C.

[0273] [Heat Resistance Evaluation] The thermal decomposition temperature (Td) of the test specimen prepared in the "Evaluation of Elongation at Breaking" above was determined by simultaneous thermal mass-differential thermal analysis (TG-DTA). The measurement conditions were a heating rate of 10°C / min and nitrogen flow rate of 50 ml / min. Under the above conditions, the temperature at which the mass of the test specimen becomes 95% of its original mass (assuming the mass before measurement is 100% by mass) was measured as the 5% mass loss temperature. The evaluation was performed according to the evaluation criteria below, and the evaluation results were recorded in the "Cured Film Td" column of the table. -Evaluation Criteria- A: The 5% mass loss temperature is 350°C or higher. B: The 5% mass loss temperature is less than 350°C.

[0274] From the above results, it can be seen that the resin composition of the present invention yields a film with a wide focus margin. The comparative composition according to Comparative Example 1 does not contain the specific resin. It can be seen that the film obtained from such a comparative composition has a narrow focus margin.

[0275] <Example 201> 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 5 minutes to form a photosensitive film 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 the above exposure, it was developed with cyclopentanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain the layer pattern. Next, under a nitrogen atmosphere, the temperature was raised at a rate of 10°C / min until it reached 230°C, and then maintained at 230°C for 180 minutes to form an interlayer insulating film for redistribution layers. This interlayer insulating film for redistribution layers has excellent insulating properties. Furthermore, when a semiconductor device was manufactured using this interlayer insulating film for redistribution layers, it was confirmed that it operated without problems.

Claims

1. A resin composition comprising a polyimide containing a repeating unit represented by the following formula (A-1) and having a radically polymerizable group. In formula (A-1), X Ｙ２ , ８ , ７ , Ｙ１ , Ｙ２ , ７ , Ｙ２ represents a tetravalent organic group, and Y １ represents a group represented by any one of the following formulas (Y-1) to (Y-11). In formulas (Y-1) to (Y-4), R １ each independently represents a hydrogen atom or a substituent, and at least one of R １ is an electron-withdrawing group, and * represents a bonding site with a nitrogen atom. In formulas (Y-5) to (Y-7), R ２ each independently represents a hydrogen atom or a substituent having no radically polymerizable group, and A １ is -C(=O)-, -S(=O) ２ -, -S(=O)-, -C(R ３ ) ２ -, and R ３ is a hydrogen atom or a substituent, and * represents a bonding site with a nitrogen atom. In formula (Y-8), R ２ each independently represents a hydrogen atom or a substituent, R ４ each independently represents a substituent, R ５ each independently represents a substituent, L １ is a single bond or a divalent linking group, and * represents a bonding site with a nitrogen atom. In formula (Y-9), R ６ each independently represents a hydroxy group, an alkoxy group, a cyano group, a formyl group, -C(=O)NR Ｙ１ ２ , -C(=O)OR Ｙ２ , -C(=O)R Ｙ２ , an alkenyl group, an alkynyl group or an alkyl group having 2 or more carbon atoms which may have a substituent, R Ｙ１ is a hydrogen atom or a substituent, R Ｙ２ represents an organic group, R ７ each independently represents a hydrogen atom or a substituent, and any one of R ７ represents a bonding position with the nitrogen atom in formula (A-1), and R ８ Each is independently a hydrogen atom or a substituent, and R ８ One of these represents the bond position with the nitrogen atom in formula (A-1). In formula (Y-10), R ７ Each is independently a hydrogen atom or a substituent, and R ７ One of these represents the bonding position with the nitrogen atom in formula (A-1), and R ８ Each is independently a hydrogen atom or a substituent, and R ８ One of these represents the bonding position with the nitrogen atom in formula (A-1), and R ９ Each of these is independently an alkyl group which may have substituents. In formula (Y-11), R １０ Each of these is independently an alkyl group which may have substituents, and R １１ Each is independently a hydrogen atom or a substituent, and R １１ One of them is an organic group, R １１ One of these represents the bonding position with the nitrogen atom in formula (A-1), and R １２ Each is independently a hydrogen atom or a substituent, and R １２ One of them is an organic group, R １２ One of these represents the bonding position with the nitrogen atom in formula (A-1).

2. Y in formula (A-1) １ The resin composition according to claim 1, wherein is either formula (Y-12) or (Y-13) below. In formula (Y-12), R １３ Each is independently a hydrogen atom or a substituent, and R １４ Each of these is independently an alkyl group, an alkoxy group, or an aryl group, L ２ is a divalent linking group, and * represents the bond site with the nitrogen atom. In formula (Y-13), R １５ Each of these is independently an alkyl group which may have substituents, and R １６ Each of these is independently a hydrogen atom or a substituent.

3. The resin composition according to claim 1, wherein the absorbance of a 0.10 g / L NMP solution of the polyimide at a wavelength of 365 nm is 0.070 or less.

4. The resin composition according to any one of claims 1 to 3, wherein the radical polymerizable group in the polyimide is an aromatic vinyl group.

5. X in equation (A-1) １ The resin composition according to any one of claims 1 to 3, wherein the group is represented by the following formula (AA-1). In formula (AA-1), * represents a bonding site with a carbonyl group.

6. The polyimide is Y １ The repeating unit represented by formula (A-1) is a structure that can be expressed by any of formulas (Y-3) to (Y-8), and Y １ A resin composition according to any one of claims 1 to 3, comprising a repeating unit represented by formula (A-1) having a structure represented by any one of formulas (Y-1) to (Y-2) and formulas (Y-9) to (Y-11).

7. The resin composition according to any one of claims 1 to 3, wherein the polyimide includes a polyimide having repeating units represented by the following formula (A-2) and repeating units represented by the following formula (A-3). In formula (A-2), X ２ represents a tetravalent organic group, Y ２ represents a group represented by any of the above formulas (Y-1) to (Y-11). In formula (A-3), X ３ represents a tetravalent organic group, Y ３ This group is a divalent group having radical polymerizability and does not correspond to any of the above formulas (Y-1) to (Y-11).

8. X in the polyimide ２ and X ３ The resin composition according to claim 7, wherein at least one of the groups is a group represented by the following formula (AA-1). In formula (AA-1), * represents a bonding site with a carbonyl group.

9. Y in the aforementioned polyimide ３ The resin composition according to claim 7, wherein the radical polymerizable group contained therein is an aromatic vinyl group.

10. The resin composition according to any one of claims 1 to 3, wherein the content of the group represented by any one of formulas (Y-1) to (Y-11) in the polyimide is 0.25 to 1.70 mmol / g.

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

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

13. A laminate comprising two or more layers made of the cured material described in claim 12, wherein a metal layer is included between any of the layers made of the cured material.

14. 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.

15. A method for producing a cured product according to claim 14, comprising an exposure step of selectively exposing the film and a developing step of developing the film using a developer to form a pattern.

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

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

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

19. A semiconductor device comprising the cured product described in claim 12.

20. A polyimide having repeating units represented by the following formula (A-2) and formula (A-3). In formula (A-2), X ２ represents a tetravalent organic group, Y ２ represents a group represented by any of the following formulas (Y-1) to (Y-11). In formula (A-3), X ３ represents a tetravalent organic group, Y ３ This group is a divalent group having radical polymerizability and does not fall under any of the following formulas (Y-1) to (Y-11). In equations (Y-1) to (Y-4), R １ Each of these independently represents a hydrogen atom or a substituent, R １ At least one of the groups is an electron-withdrawing group, and * represents the bonding site with the nitrogen atom. In equations (Y-5) to (Y-7), R ２ Each of these independently represents a substituent that does not have a hydrogen atom or a radical polymerizable group, R １ At least one of them is an electron-withdrawing group, A １ -C(=O)-, -S(=O) ２ -, -S(=O)-, -C(R ３ ) ２ - is one of the following, R ３ * represents a hydrogen atom or substituent, and * represents a bond site with a nitrogen atom. In formula (Y-8), R ２ Each is independently a hydrogen atom or a substituent, and R ４ Each of these independently represents a substituent, R ５ Each of these independently represents a substituent, L １ represents a single bond or a divalent linking group, and * represents the bond site with the nitrogen atom. In formula (Y-9), R ６ These are independently a hydroxyl group, an alkoxy group, a cyano group, a formyl group, and -C(=O)NR Ｙ１ ２ , -C (=O) OR Ｙ２ , -C(=O)R Ｙ２ R is an alkenyl group, an alkynyl group, or an alkyl group having 2 or more carbon atoms which may have substituents. Ｙ１ R is a hydrogen atom or substituent. Ｙ２ represents an organic group, and R ７ each independently represents a hydrogen atom or a substituent, and one of R ７ represents the bonding position with the nitrogen atom in formula (A-2), and R ８ each independently represents a hydrogen atom or a substituent, and one of R ８ represents the bonding position with the nitrogen atom in formula (A-2). In formula (Y-10), R ７ each independently represents a hydrogen atom or a substituent, and one of R ７ represents the bonding position with the nitrogen atom in formula (A-2), and R ８ each independently represents a hydrogen atom or a substituent, and one of R ８ represents the bonding position with the nitrogen atom in formula (A-2), and R ９ each independently represents an alkyl group which may have a substituent. In formula (Y-11), R １０ each independently represents an alkyl group which may have a substituent, and R １１ each independently represents a hydrogen atom or a substituent, and one of R １１ is an organic group, and one of R １１ represents the bonding position with the nitrogen atom in formula (A-2), and R １２ each independently represents a hydrogen atom or a substituent, and one of R １２ is an organic group, and one of R １２ represents the bonding position with the nitrogen atom in formula (A-2).

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