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

Abstract

Provided are: a photosensitive resin composition that comprises a photopolymerization initiator and a resin having at least one selected from the group consisting of polyimide precursors having a group containing an ethylenically unsaturated bond and polyimides having a group containing an ethylenically unsaturated bond, wherein the in-plane orientation coefficient of a cured film obtained by heating the composition at 230 °C for 3 hours is -0.50 to -0.10; a cured product that is obtained by curing the composition; a method for producing the cured product; a laminate containing the cured product; a method for producing the laminate; a semiconductor device; and a method for producing the semiconductor device.

Description

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

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

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

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

[0004] For example, Patent Document 1 describes a photosensitive resin composition containing the following components: (A) a polyimide precursor having an i-line absorbance of 0.1 to 0.6 in a 0.1 wt % N-methylpyrrolidone solution; and (B) a photopolymerization initiator having a carbazole structure. Patent Document 2 describes a photosensitive resin composition containing 100 parts by mass of a polyimide precursor having a specific structure, (B) a photopolymerization initiator in an amount of 1 to 20 parts by mass based on 100 parts by mass of the (A) polyimide precursor, (C) an organic solvent having a boiling point of 180°C or higher at atmospheric pressure, and (D) an organic solvent having a boiling point of 130°C or higher and 160°C or lower at atmospheric pressure, the total amount of the organic solvent being 185 to 600 parts by mass based on 100 parts by mass of the (A) polyimide precursor, and having a viscosity at 23°C of 0.5 to 40 P.

[0005] JP 2022-109277 A JP 2017-021113 A

[0006] As wiring patterns become finer, there is a demand for using resin-containing components that are less likely to expand, thereby suppressing the occurrence of defects. Therefore, there is a demand for photosensitive resin compositions containing polyimide or its precursors to produce cured products with a small thermal expansion coefficient.

[0007] An object of the present invention is to provide a photosensitive resin composition that can give a cured product having a small thermal expansion coefficient, a cured product obtained by curing the photosensitive resin composition, a laminate including the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device that includes the method for producing the cured product, and a semiconductor device that includes the cured product.

[0008] Representative embodiments of the present invention are shown below. <1> A photosensitive resin composition comprising: a resin having at least one selected from the group consisting of a polyimide precursor having a group containing an ethylenically unsaturated bond and a polyimide having a group containing an ethylenically unsaturated bond; and a photopolymerization initiator, wherein the in-plane orientation coefficient of a cured film obtained by heating at 230°C for 3 hours is -0.50 to -0.10. <2> The photosensitive resin composition according to <1>, wherein the in-plane orientation coefficient is -0.50 to -0.20. <3> The photosensitive resin composition according to <1> or <2>, wherein the resin contains at least one of a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2): In formula (1), X １ represents an organic group having a valence of 4+m, and Y １ represents a 2+n-valent organic group, and R １ each independently represents a group containing a polymerizable group, n and m each independently represents an integer of 0 to 4, n+m is 1 or more, and at least one of the following conditions a and b is satisfied. Condition a: X １ has a group represented by any one of the following formulas (X-1) to (X-4). １ has a group represented by the following formula (Y-1) or formula (Y-2). In formula (2), X ２ represents a tetravalent organic group, Y ２ represents a divalent organic group, R ２１ and R ２２ are each independently a hydrogen atom or a monovalent organic group, and R ２１ and R ２２ At least one of the above is a monovalent organic group having an ethylenically unsaturated bond, and satisfies at least one of the following conditions c and d. Condition c: X ２ has a group represented by any one of the following formulas (X-1) to (X-4). ２ has a group represented by the following formula (Y-1) or formula (Y-2). In formula (X-1), each R independently represents a bonding site with a substituent or another structure, each n independently represents an integer of 0 to 3, and * represents a bonding site with a carbonyl group. In formula (X-2), each R independently represents a bonding site with a substituent or another structure, n independently represents an integer of 0 to 2, and * represents a bonding site with a carbonyl group. In formula (X-3), * represents a bonding site with a carbonyl group. In formula (X-4), each R independently represents a bonding site with a substituent or another structure, n independently represents an integer of 0 to 2, and * represents a bonding site with a carbonyl group. In formula (Y-1), each R independently represents a bonding site with a substituent or another structure, each n independently represents an integer of 0 to 2, and m independently represents an integer of 1 or greater, and * represents a bonding site with a nitrogen atom. In formula (Y-2), each R independently represents a substituent or a bonding site to another structure, each n independently represents an integer of 0 to 2, m represents an integer of 1 or more, and * represents a bonding site to a nitrogen atom. <4> A photosensitive resin composition comprising: a resin containing at least one of a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2); and a photopolymerization initiator. In formula (1), X １ represents an organic group having a valence of 4+m, and Y １ represents a 2+n-valent organic group, and R １ each independently represents a group containing a polymerizable group, n and m each independently represents an integer of 0 to 4, n+m is 1 or more, and at least one of the following conditions a and b is satisfied. Condition a: X １ has a group represented by any one of the following formulas (X-1) to (X-4). １ has a group represented by the following formula (Y-1) or formula (Y-2). In formula (2), X ２ represents a tetravalent organic group, Y ２ represents a divalent organic group, R ２１ and R ２２ are each independently a hydrogen atom or a monovalent organic group, and R ２１ and R ２２ At least one of the above is a monovalent organic group having an ethylenically unsaturated bond, and satisfies at least one of the following conditions c and d. Condition c: X ２has a group represented by any one of the following formulas (X-1) to (X-4). ２ has a group represented by the following formula (Y-1) or formula (Y-2). In formula (X-1), each R independently represents a bonding site with a substituent or another structure, each n independently represents an integer of 0 to 3, and * represents a bonding site with a carbonyl group. In formula (X-2), each R independently represents a bonding site with a substituent or another structure, n independently represents an integer of 0 to 2, and * represents a bonding site with a carbonyl group. In formula (X-3), * represents a bonding site with a carbonyl group. In formula (X-4), each R independently represents a bonding site with a substituent or another structure, n independently represents an integer of 0 to 2, and * represents a bonding site with a carbonyl group. In formula (Y-1), each R independently represents a bonding site with a substituent or another structure, each n independently represents an integer of 0 to 2, and m independently represents an integer of 1 or greater, and * represents a bonding site with a nitrogen atom. In formula (Y-2), each R independently represents a substituent or a bonding site to another structure, each n independently represents an integer of 0 to 2, m represents an integer of 1 or more, and * represents a bonding site to a nitrogen atom. <5> The photosensitive resin composition according to any one of <1> to <4>, wherein the content of the photopolymerization initiator is 1 mass% or more based on the total solid content of the composition. <6> The photosensitive resin composition according to any one of <1> to <5>, further comprising a radical polymerization inhibitor. <7> The photosensitive resin composition according to any one of <1> to <6>, further comprising at least one compound selected from the group consisting of a nitroso compound, an N-oxide compound, an N-oxyl compound, and a phenothiazine compound. <8> The photosensitive resin composition according to any one of <1> to <7>, further comprising a light absorber. <9> The photosensitive resin composition according to any one of <1> to <8>, further comprising at least one compound selected from the group consisting of naphthoquinone diazide compounds, azomethine compounds, indole compounds, benzotriazole compounds, cyanoacrylate compounds, triazine compounds, and anthracene compounds. <10> The photosensitive resin composition according to <9>, in which the content of the radical polymerization inhibitor is 0.1 mass% or more based on the total solid content of the composition. <11> The photosensitive resin composition according to any one of <1> to <10>, further comprising a polymerizable compound. <12> The photosensitive resin composition according to <11>, in which the number of polymerizable groups in the polymerizable compound is 2 or more.<13> The photosensitive resin composition according to <11> or <12>, wherein the polymerizable compound has a polymerizable group value of 1.0 to 15 mmol / g. <14> The photosensitive resin composition according to any one of <1> to <13>, wherein a cured film obtained by heating at 230°C for 3 hours contains a resin having a repeating unit represented by formula (A-1). In formula (A-1), X １ represents an organic group having a valence of 4+m, and Y １ represents a 2+n-valent organic group, * represents a bonding site with another structure, n and m each independently represent an integer of 0 to 4, and n+m is 0 to 4, and at least one of the following conditions a and b is satisfied. Condition a: X １ has a group represented by any one of the following formulas (X-1) to (X-4). １ has a group represented by the following formula (Y-1) or formula (Y-2). In formula (X-1), each R independently represents a bonding site with a substituent or another structure, each n independently represents an integer of 0 to 3, and * represents a bonding site with a carbonyl group. In formula (X-2), each R independently represents a bonding site with a substituent or another structure, n independently represents an integer of 0 to 2, and * represents a bonding site with a carbonyl group. In formula (X-3), * represents a bonding site with a carbonyl group. In formula (X-4), each R independently represents a bonding site with a substituent or another structure, n independently represents an integer of 0 to 2, and * represents a bonding site with a carbonyl group. In formula (Y-1), each R independently represents a bonding site with a substituent or another structure, each n independently represents an integer of 0 to 2, and m independently represents an integer of 1 or greater, and * represents a bonding site with a nitrogen atom. In formula (Y-2), each R independently represents a substituent or a bonding site with another structure, each n independently represents an integer of 0 to 2, m represents an integer of 1 or greater, and * represents a bonding site with a nitrogen atom. <15> The photosensitive resin composition according to any one of <1> to <14>, used for forming an interlayer insulating film for a redistribution layer. <16> A cured product obtained by curing the photosensitive resin composition according to any one of <1> to <15>. <17> A laminate comprising two or more layers made of the cured product according to <16>, and a metal layer between any two adjacent layers made of the cured products. <18> A method for producing a cured product, comprising a film-forming step of applying the photosensitive resin composition according to any one of <1> to <15> onto a substrate to form a film. <19> A method for producing a cured product according to <18>, comprising an exposure step of selectively exposing the film to light and a development step of developing the film with a developer to form a pattern. <20> A method for producing the cured product according to <18> or <19>, comprising a heating step of heating the film at 50 to 450°C. <21> A method for producing a laminate, comprising the method for producing a cured product according to any one of <18> to <20>. <22> A method for producing a semiconductor device, comprising the method for producing a cured product according to any one of <18> to <20>. <23> A semiconductor device, comprising the cured product according to <16>.

[0009] According to the present invention, there are provided a photosensitive resin composition that can give a cured product having a small thermal expansion coefficient, a cured product obtained by curing the photosensitive resin composition, a laminate including the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device that includes the method for producing the cured product, and a semiconductor device that includes the cured product.

[0010] Orientation state and in-plane orientation coefficient f ｚｘ 1 is a schematic cross-sectional view showing the relationship between the absorption spectrum measured by a polarized ATR-IR method.

[0011] The following describes the main embodiments of the present invention. However, the present invention is not limited to the explicitly described embodiments. In this specification, a numerical range expressed using the symbol "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits, respectively. In this specification, the term "process" refers not only to an independent process but also to a process that cannot be clearly distinguished from other processes as long as the process achieves its intended effect. In the description of a group (atomic group), a notation that does not specify whether it is substituted or unsubstituted encompasses both unsubstituted groups (atomic groups) and substituted groups (atomic groups). For example, the term "alkyl group" encompasses not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. In addition, examples of light used for exposure include actinic rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and electron beams. As used herein, "(meth)acrylate" refers to either or both of "acrylate" and "methacrylate," "(meth)acrylic" refers to either or both of "acrylic" and "methacrylic," and "(meth)acryloyl" refers to either or both of "acryloyl" and "methacryloyl." In the structural formulae herein, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. As used herein, the term "total solid content" refers to the total mass of all components of the composition excluding the solvent. Furthermore, as used herein, the term "solid content concentration" refers to the mass percentage of the components other than the solvent relative to the total mass of the composition. As used herein, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values ​​measured using gel permeation chromatography (GPC) and are defined as polystyrene equivalent values, unless otherwise specified.In this specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, by using an HLC-8220GPC (manufactured by Tosoh Corporation) and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) connected in series. Unless otherwise specified, these molecular weights are measured using NMP (N-methyl-2-pyrrolidone) as the eluent. However, when NMP is not suitable as the eluent, for example, due to low solubility, THF (tetrahydrofuran) can also be used. Furthermore, unless otherwise specified, detection in GPC measurement is assumed to be performed using a UV (ultraviolet) detector at a wavelength of 254 nm. In this specification, when the positional relationship of each layer constituting a laminate is described as "above" or "below," it is sufficient that another layer is above or below the reference layer among the multiple layers being considered. In other words, a third layer or element may be interposed between the reference layer and the other layer, and the reference layer and the other layer do not need to be in contact with each other. Unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "above." Alternatively, if a resin composition layer is present, the direction from the substrate to the resin composition layer is referred to as "above," and the opposite direction is referred to as "below." Note that such vertical directions are defined for convenience in this specification, and in actual embodiments, the "above" direction in this specification may differ from the vertically upward direction. In this specification, unless otherwise specified, the composition may contain two or more compounds corresponding to each component contained in the composition. Furthermore, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component. In this specification, unless otherwise specified, the temperature is 23° C., the atmospheric pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, a combination of preferred embodiments is a more preferred embodiment.

[0012] (Photosensitive Resin Composition) A photosensitive resin composition according to a first aspect of the present invention (hereinafter also referred to as the "first resin composition") comprises a resin having at least one selected from the group consisting of a polyimide precursor having a group containing an ethylenically unsaturated bond and a polyimide having a group containing an ethylenically unsaturated bond, and a photopolymerization initiator. The cured film obtained by heating at 230°C for 3 hours has an in-plane orientation coefficient of -0.50 to -0.10. A photosensitive resin composition according to a second aspect of the present invention (hereinafter also referred to as the "second resin composition") comprises a resin containing at least one of a repeating unit represented by formula (1) and a repeating unit represented by formula (2), and a photopolymerization initiator. In this specification, the first resin composition and the second resin composition are collectively referred to simply as the "resin composition". In this specification, the resin contained in the first resin composition is also referred to as the "first specific resin," and the resin contained in the second resin composition is also referred to as the "second specific resin," and the first specific resin and the second specific resin together are also simply referred to as the "specific resins."

[0013] The resin composition of the present invention is preferably used to form a photosensitive film that is subjected to exposure and development, and is preferably used to form a film that is 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 an insulating film for a semiconductor device, an interlayer insulating film for a redistribution layer, a stress buffer film, etc., and is more preferably used to form an interlayer insulating film for a redistribution layer. Furthermore, the resin composition of the present invention is preferably used to form a photosensitive film that is subjected to negative development. In the present invention, negative development refers to development in which non-exposed areas are removed by development in exposure and development, and positive development refers to development in which exposed areas are removed by development. As the exposure method, the developer, and the development method, for example, the exposure method described in the exposure step and the developer and development method described in the development step in the description of the method for producing a cured product described below can be used.

[0014] The resin composition of the present invention produces a cured product with a low coefficient of thermal expansion. The mechanism by which this effect is achieved is unclear, but is speculated as follows. The first resin composition has an in-plane orientation coefficient of -0.50 to -0.10 in the cured film obtained by heating at 230°C for 3 hours. It is known that the linear expansion coefficient of a polyimide film is closely related to the degree of orientation of the polyimide molecular chain (M. Hasegawa and T. Matano, Macromolecules, 29, 7897 (1996)). When the in-plane orientation coefficient is within the above range, interactions between resins are likely to occur, facilitating polymerization of groups containing ethylenically unsaturated bonds in the resin. It is believed that this interaction and polymerization effect results in a film with a low coefficient of thermal expansion (CTE), while also achieving high resolution through efficient polymerization. Furthermore, it is believed that when the in-plane orientation coefficient is within the above range, polymerization of groups containing ethylenically unsaturated bonds by a photopolymerization initiator is likely to occur, resulting in excellent resolution.

[0015] The second resin composition contains a resin containing at least one of a repeating unit represented by formula (1) and a repeating unit represented by formula (2). Such a resin has a rigid and linear structure, which is thought to result in a high in-plane orientation coefficient in the resulting cured product. As a result, for the same reasons as in the first resin composition described above, it is thought that a cured product with a low thermal expansion coefficient can be obtained. Furthermore, since the in-plane orientation coefficient is within the above range, it is thought that groups containing ethylenically unsaturated bonds can be easily polymerized by the photopolymerization initiator, resulting in excellent resolution.

[0016] In addition, in order to facilitate the polymerization of a resin composition and improve resolution, one method is to increase the content of a photopolymerization initiator. However, when the photopolymerization initiator is increased, the reaction gradually progresses even in unexposed areas due to leakage light (exposure light leaking into areas that should not be exposed), which may result in the generation of residues. Here, by using a polymerization inhibitor, a light absorber, or the like in combination, it is possible to achieve both a low CTE and high resolution while suppressing the generation of the residues.

[0017] Here, Patent Documents 1 and 2 do not describe a resin composition containing the first specific resin or the second specific resin.

[0018] The properties of the resin composition of the present invention and the components contained therein will be described in detail below.

[0019] <In-plane orientation coefficient> The first photosensitive resin composition has an in-plane orientation coefficient of -0.50 to -0.10, preferably -0.50 to -0.20, more preferably -0.50 to -0.30, and even more preferably -0.50 to -0.40, of a cured film obtained by heating for 3 hours at 230 ° C. The second photosensitive resin composition has an in-plane orientation coefficient of -0.50 to -0.10, more preferably -0.50 to -0.20, even more preferably -0.50 to -0.30, and particularly preferably -0.50 to -0.40, of a cured film obtained by heating for 3 hours at 230 ° C.

[0020] The cured film can be obtained by applying a photosensitive resin composition to a silicon wafer, exposing the formed resin composition film to a thickness of 15 μm, heating the film at 230° C. for 3 hours, and then immersing the cured resin layer (cured product) in a 4.9 mass % aqueous solution of hydrofluoric acid, and peeling the cured film from the silicon wafer.

[0021] Here, the method of applying the resin composition is not particularly limited, and any method can be used as long as the distance from the substrate to the film surface is 15 μm. Spin coating can be used. If it is difficult to form a film with a distance of 15 μm by a single spin coating, the spin coating can be performed multiple times. If it is still difficult to form a film with a distance of 15 μm by the spin coating, the application method can be appropriately selected from known methods such as dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, slit coating, and inkjet coating.

[0022] If the resin composition contains a solvent, it is preferable to dry it after the application. In this case, the distance from the substrate to the surface of the dried film corresponds to the thickness. Drying is preferably performed until the amount of solvent in the film is 0.5% by mass or less. Drying conditions are not particularly limited, but drying by heating is possible. Furthermore, if sufficient drying is difficult to achieve by heating alone, further reduction in pressure may be performed. Drying can be performed in the atmosphere. However, if the resin composition contains components that are easily denatured by oxygen, drying can also be performed under inert gas replacement such as nitrogen or under vacuum. Drying means are not particularly limited, but examples include a hot plate. However, if the above-mentioned reduction in pressure or inert gas replacement is required, an oven with a reduction in pressure function or an oven with a gas replacement function can also be used. When drying by heating, the heating temperature (drying temperature) can be, for example, 110°C. However, if drying at 110°C is difficult, the drying temperature may be appropriately changed between 70°C and 130°C, preferably between 90°C and 120°C, depending on the type of solvent contained in the resin composition. When drying by heating, the drying time (the time exposed to the above heating temperature) can be, for example, 5 minutes. However, if drying within 5 minutes is difficult, the drying time may be appropriately changed between 30 seconds and 20 minutes, preferably between 1 minute and 10 minutes, depending on the type of solvent contained in the resin composition. When drying by heating, the temperature rise rate during heating to dry the film is not particularly limited and can be, for example, 5°C / min. If drying at the above temperature rise rate is difficult, the temperature rise rate may be appropriately changed between 1 to 12°C / min or 2 to 10°C / min, depending on the type of solvent contained in the resin composition.

[0023] The film of the resin composition obtained by the application is exposed to light, and after the exposure, is heated at 230° C. for 3 hours to form a cured product. The exposure method may be determined according to the type of photopolymerization initiator contained in the resin composition, etc., so as to ensure that the photopolymerization initiator is sufficiently exposed to light. For example, an ultra-high pressure mercury lamp is used to expose the resin composition to light at 400 mJ / cm ２The heating can be performed with an exposure energy of 1000 kJ / min. The heating can be performed in an oven under a nitrogen atmosphere. The pressure during the heating is 1 atmosphere (101,325 Pa). The temperature rise rate during the heating can be, for example, 10°C / min. The heating time (time exposed to 230°C) during the heating is 3 hours.

[0024] For the above cured film, the in-plane orientation coefficient can be calculated using polarized ATR-IR as described in the reference (JP Patent Publication No. 2004-126109). Polarized ATR-IR Measurement Polarized ATR-IR measurement is performed under the following conditions. A general macro ATR-IR device can be used as the measurement device, but it is preferable to use an MCT detector to obtain sufficient detection sensitivity. Prism: Germanium Pressure between prism and sample: 20 cN m Incident angle: 45° Number of reflections: 1 Resolution: 4 cm -1 Measurements are performed after confirming that the sample is in close contact with the entire surface of the prism. The FTIR-ATR spectrum is measured by irradiating perpendicularly polarized light (s-polarized light; transverse electric, TE) and horizontally polarized light (transverse magnetic, TM) onto the incident surface, which is made up of light incident on the sample surface and light reflected from it, using a wire grid polarizer. The absorption spectrum when perpendicularly polarized light is incident is called the S ＴＥ , the absorption spectrum when horizontally polarized light is incident is S ＴＭ In the obtained spectrum, atmospheric correction is performed so that the signal derived from water vapor is below the noise level.

[0025] Calculation of absorbance (peak area) S ＴＥ , S ＴＭ In each spectrum, 1765 to 1790 cm －１ The area A enclosed by the spectrum and the baseline for the imide C=O group symmetric stretching peak having a maximum absorption point in the range ＴＥ , A ＴＭ At this time, the endpoints on the low wavenumber side and the high wavenumber side of the baseline are calculated by dividing the endpoint on the low wavenumber side by 1750 to 1775 cm －１ Between the high wavenumber end points, 1780 and 1815 cm－１ The spectrum is set on the spectrum between the points 1 and 2 so that the baseline does not intersect with the spectrum and the area enclosed by the spectrum and the baseline is maximized.

[0026] Calculation of in-plane orientation coefficient fzx In this sample, the absorption coefficients in the x and y directions can be considered to be equal (k x =k y ) A mentioned in the previous paragraph TE , A TM Using the above, k is calculated according to the formulas 1, 2 and 3 described in the reference document (JP 2004-126109 A). x and k z The infrared dichroic ratio D ｚｘ = k ｚ / k ｘ As the in-plane orientation coefficient f ｚｘ is calculated using the following formula: Here, D ０ =cot ２ δ is the angle between the transition moment vector formed by molecular vibration and the molecular axis. The imide C=O group symmetric stretching mode used here is a vibration mode parallel to the molecular axis, and can be calculated with δ set to 0°. The in-plane orientation coefficient f ｚｘ is based on the film thickness direction (axis perpendicular to the film surface), and is 1 when the molecular chains are perfectly oriented parallel, 0 when they are randomly oriented, and -0.5 when they are perfectly oriented perpendicular.

[0027] Fig. 1 shows the relationship between the orientation state and the in-plane orientation coefficient f ｚｘ 1A, when the resin 1 in the cured film 10 is completely oriented parallel to the film thickness direction (Z axis), f ｚｘ is 1. In addition, as shown in FIG. 1B, when the orientation state of the resin 1 is completely random in the film thickness direction (Z axis), f ｚｘ is 0, and when the resin 1 is completely oriented perpendicular to the film thickness direction (Z axis) as shown in FIG. 1C, f ｚｘ becomes -0.5.

[0028] Figure 2 shows the absorption spectrum (S ＴＥ), and the absorption spectrum when horizontally polarized light is incident (S ＴＭ ) is a schematic diagram showing the measurement results of the area A enclosed by the spectrum and the baseline for each peak, which is obtained by creating a baseline by the above-mentioned method. ＴＥ , A ＴＭ Calculate the in-plane orientation coefficient f ｚｘ Calculate.

[0029] Furthermore, the cured film obtained by heating at 230° C. for 3 hours preferably contains a resin having a repeating unit represented by formula (A-1). In formula (A-1), X １ represents an organic group having a valence of 4+m, and Y １ represents a 2+n-valent organic group, * represents a bonding site with another structure, n and m each independently represent an integer of 0 to 4, and n+m is 0 to 4, and at least one of the following conditions a and b is satisfied. Condition a: X １ has a group represented by any one of formulas (X-1) to (X-4) described below. １ has a group represented by formula (Y-1) or formula (Y-2) described below.

[0030] The repeating unit represented by formula (A-1) is preferably a repeating unit formed by a polymerization reaction of an ethylenically unsaturated bond contained in a repeating unit represented by formula (1) described below, or by imidization of a repeating unit represented by formula (2) described below.

[0031] In formula (A-1), X １ , Y １ A preferred embodiment of the formula (1) is X １ , Y １In another preferred embodiment of the present invention, n+m is 0 in formula (A-1). Such a repeating unit is formed, for example, as a repeating unit formed by imidizing a repeating unit represented by formula (2) described below. In another preferred embodiment of the present invention, the preferred aspects of n, m, and n+m in formula (A-1) are the same as the preferred aspects of n, m, and n+m in formula (1) described below. Such a repeating unit is formed, for example, as a repeating unit formed by imidizing a repeating unit represented by formula (1) described below. In another preferred embodiment of the present invention, the repeating unit represented by formula (A-1) satisfies conditions a and b.

[0032] <Specific Resin> [First Specific Resin] The first specific resin is a resin having at least one selected from the group consisting of a polyimide precursor having a group containing an ethylenically unsaturated bond and a polyimide having a group containing an ethylenically unsaturated bond.

[0033] In the present invention, the term "polyimide precursor" refers to a resin whose chemical structure changes upon external stimulation to become a polyimide. A resin whose chemical structure changes upon heating to become a polyimide is preferred, and a resin whose ring structure is formed upon heating to become a polyimide is more preferred. In the present invention, the term "polyimide" refers to a resin having a repeating unit containing an imide group in the molecular chain, and preferably a resin having a repeating unit containing an imide ring structure in the molecular chain. Furthermore, when the polyimide is a linear resin, the polyimide is preferably a resin having a repeating unit containing an imide group in the main chain, and more preferably a resin having a repeating unit containing an imide ring structure in the main chain. In this specification, the term "main chain" refers to the relatively longest bonding chain in the resin molecule, and the term "side chain" refers to any other bonding chain. In this specification, the term "imide group" refers to a structure represented by *-C(═O)N(-*)C(═O)-*, where * represents a bonding site to another structure, preferably a bonding site to a carbon atom, and more preferably a bonding site to a quaternary carbon atom. In this specification, the imide ring structure refers to a ring structure containing two carbon atoms and all of the nitrogen atoms in the imide as ring members. The imide ring structure is preferably a five-membered ring. The polyimide may be a so-called polyamideimide, which has an amide group in the molecular chain in addition to the imide group. In this specification, the amide group refers to a structure represented by *-C(=O)N(-#)-*, where * represents a bonding site to another structure, preferably a bonding site to a carbon atom, and more preferably a bonding site to a quaternary carbon atom. Furthermore, # represents a bonding site to another structure, preferably a bonding site to a hydrogen atom or a bonding site to a carbon atom, and more preferably a bonding site to a hydrogen atom.

[0034] In the present invention, the polyimide precursor preferably has an imidization rate of less than 70%, more preferably 50% or less, and even more preferably 30% or less. The lower limit of the imidization rate is not limited, as long as it is 0% or more. In the present invention, the polyimide preferably has an imidization rate of 70% or more, more preferably 80% or more, and even more preferably 90% or more. The upper limit of the imidization rate is not limited, as long as it is 100% or less.

[0035] In the present invention, the imidization rate is a value calculated by the following method. The resin is dissolved in γ-butyrolactone, diluted to a viscosity of 2,000 mPa·s, and applied to a silicon wafer by spin coating to form a resin layer. If a resin layer cannot be formed due to reasons such as low solubility of the resin in γ-butyrolactone, the solvent may be changed to another solvent. Examples of such solvents include solvents contained in the resin composition, such as NMP. The viscosity may also be adjusted as appropriate within an adjustable range. The silicon wafer to which the resulting resin layer is applied is dried on a hot plate at 110°C for 5 minutes to obtain a resin layer on the silicon wafer with a uniform thickness of approximately 15 μm after film formation. Here, if only a resin solution with a low viscosity is obtained and it is difficult to obtain a resin layer with a thickness of 15 μm, the film thickness may be adjusted as appropriate. For example, if the film thickness is 5 μm or greater, a similar imidization rate value can be obtained. The resin layer was measured by the ATR method using NicoletiS20 (manufactured by Thermofisher) in the measurement range of 4000 to 700 cm －１ , the measurement is performed 50 times. －１ Around (1350-1450 cm －１ (If there are multiple peaks, the peak with the greatest intensity) and 1500 cm －１ Around (1460-1550 cm －１The imidization index B is calculated in the same manner for a film that has been heated at a heating rate of 10°C / min in a nitrogen atmosphere and heated at 350°C for 1 hour, and the imidization rate of the resin is calculated by dividing the imidization index A by the imidization index B. The imidization rate of the resin is calculated by dividing the imidization index A by the imidization index B.

[0036] The first specific resin has a group containing an ethylenically unsaturated bond. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (such as a vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a maleimide group, with a vinylphenyl group, a (meth)acryloyloxy group, or a maleimide group being preferred.

[0037] The first specific resin preferably contains at least one of a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2): The second specific resin is a resin containing at least one of a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2): In formula (1), X １ represents an organic group having a valence of 4+m, and Y １ represents a 2+n-valent organic group, and R １ each independently represents a group containing a polymerizable group, n and m each independently represents an integer of 0 to 4, n+m is 1 or more, and at least one of the following conditions a and b is satisfied. Condition a: X １ has a group represented by any one of the following formulas (X-1) to (X-4). １ has a group represented by the following formula (Y-1) or formula (Y-2). In formula (2), X ２ represents a tetravalent organic group, Y １ represents a divalent organic group, R ２１ and R ２２ are each independently a hydrogen atom or a monovalent organic group, and R ２１ and R ２２At least one of the above is a monovalent organic group having an ethylenically unsaturated bond, and satisfies at least one of the following conditions c and d. Condition c: X ２ has a group represented by any one of the following formulas (X-1) to (X-4). ２ has a group represented by the following formula (Y-1) or formula (Y-2). In formula (X-1), each R independently represents a bonding site with a substituent or another structure, each n independently represents an integer of 0 to 3, and * represents a bonding site with a carbonyl group. In formula (X-2), each R independently represents a bonding site with a substituent or another structure, n independently represents an integer of 0 to 2, and * represents a bonding site with a carbonyl group. In formula (X-3), * represents a bonding site with a carbonyl group. In formula (X-4), each R independently represents a bonding site with a substituent or another structure, n independently represents an integer of 0 to 2, and * represents a bonding site with a carbonyl group. In formula (Y-1), each R independently represents a bonding site with a substituent or another structure, each n independently represents an integer of 0 to 2, and m independently represents an integer of 1 or greater, and * represents a bonding site with a nitrogen atom. In formula (Y-2), each R independently represents a substituent or a bonding site to another structure, each n independently represents an integer of 0 to 2, m represents an integer of 1 or more, and * represents a bonding site to a nitrogen atom.

[0038] [Repeating unit represented by formula (1)] -X １ - In formula (1), X １ preferably has a group represented by any one of formulas (X-1) to (X-4).

[0039] In formula (X-1), R preferably represents a substituent. The substituent 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. When R in formula (X-1) represents a bonding site with another structure, R is preferably the same as R in formula (1). １ In formula (X-1), n ​​is preferably 0 or 1, and more preferably 0.

[0040] In formula (X-2), the preferred embodiments of R and n are the same as the preferred embodiments of R and n in formula (X-1).

[0041] In formula (X-4), the preferred embodiments of R and n are the same as the preferred embodiments of R and n in formula (X-1).

[0042] Other, X １ may be a tetracarboxylic acid residue remaining after removal of the anhydride group from a tetracarboxylic acid dianhydride described in paragraphs 0055 to 0057 of JP-A No. 2023-003421.

[0043] -Y １ - In formula (1), Y １ preferably has a group represented by formula (Y-1) or formula (Y-2).

[0044] In formula (Y-1), R preferably represents a substituent. The substituent 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. When R in formula (Y-1) represents a bonding site with another structure, R is preferably the same as R in formula (1). １ In formula (Y-1), n ​​is preferably 0 or 1, and more preferably 1. In addition, when n is 1 and R is R in formula (1), １ In formula (Y-1), m is preferably an integer of 1 to 3, and more preferably 1 or 2.

[0045] In formula (Y-2), the preferred embodiments of R, n, and m are the same as the preferred embodiments of R, n, and m in formula (Y-1).

[0046] In formula (1), R １ Each of R independently represents a group containing a polymerizable group. As the polymerizable group, the above-mentioned group having an ethylenically unsaturated bond is preferred. １ is preferably a group represented by the following formula (R-1). In formula (R-1), L１ represents a 1+1-valent linking group, A １ represents a group having an ethylenically unsaturated bond, a1 represents an integer of 1 or more, * represents X in formula (1). １ or Y １ In formula (R-1), L １ is preferably a group represented by the following formula (L-2). In formula (L-2), Z ２ -O-, -NR Ｎ -, -C(=O)O- or -C(=O)NR Ｎ represents -, and R Ｎ represents a hydrogen atom or a monovalent organic group; when a1 is 1, L ｘ represents a single bond or a divalent linking group, and when a1 is 2 or more, L ｘ represents an a1+1-valent linking group, a1 represents an integer of 1 or more, * represents X in formula (1). １ or Y １ represents a bonding site with another structure in formula (R-1), and # represents a bonding site with another structure in formula (R-1). １ represents the binding site with

[0047] In formula (L-2), Z ２ is preferably —O— or —C(═O)O—. ２ Ga-NR Ｎ -, then R Ｎ is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or a phenyl group, and even more preferably a hydrogen atom. ２ is -C(=O)O- or -C(=O)NR Ｎ -, the direction of the bond is not particularly limited, but the carbon atom in these structures is Ｘ It is preferable that Z is oriented in a direction that bonds with Z. ２ -C(=O)NR Ｎ -, then R Ｎ In formula (L-2), when a1 is 1, L ｘ is preferably an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. ｘis preferably a hydrocarbon group, a heterocyclic group, or a group represented by a combination thereof, more preferably a saturated aliphatic hydrocarbon group having 2 to 20 carbon atoms, and even more preferably a saturated aliphatic hydrocarbon group having 3 to 15 carbon atoms. In formula (L-2), a1 has the same meaning as a1 in formula (R-1).

[0048] In formula (R-1), A １ is preferably a (meth)acryloxy group, a maleimide group, or a vinylphenyl group, and more preferably a maleimide group or a vinylphenyl group from the viewpoint of reducing the dielectric loss tangent of the cured product, etc. Furthermore, a (meth)acryloxy group is more preferred from the viewpoint of reactivity, etc.

[0049] Among these, A in formula (R-1) １ is a vinylphenyl group, and L １ is preferably a group represented by formula (L-2-1). In formula (L-2-1), L Ｘ２ represents a hydrocarbon group, and a1 represents an integer of 1 or more. Ｘ２ is preferably an aliphatic saturated hydrocarbon group. Ｘ２ is preferably an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, still more preferably an alkylene group having 1 to 4 carbon atoms, and particularly preferably a methylene group. In formula (L-2-1), a1 has the same meaning as a1 in formula (R-1).

[0050] In addition, A in formula (R-1) １ is a maleimide group, and L １ is a group represented by formula (L-2), and L Ｘis preferably an aromatic group or an aliphatic saturated hydrocarbon group having 4 or more carbon atoms. The aromatic group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, but is preferably an aromatic hydrocarbon group. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, more preferably an aromatic hydrocarbon group having 6 carbon atoms. Examples of heteroatoms in the aromatic heterocyclic group include an oxygen atom, a nitrogen atom, and a sulfur atom. The number of heteroatoms in the aromatic heterocyclic group is preferably 1 or 2. Furthermore, the aromatic heterocyclic group is preferably a 5- or 6-membered ring containing the above heteroatom. Furthermore, the aromatic heterocyclic group may be condensed with another aromatic heterocyclic group or another aromatic hydrocarbon ring group. The aliphatic saturated hydrocarbon group having 4 or more carbon atoms may be linear, branched, cyclic, or have a structure represented by a combination thereof. The number of carbon atoms in the aliphatic saturated hydrocarbon group having 4 or more carbon atoms is preferably 4 to 20, more preferably 5 to 10.

[0051] In formula (R-1), a1 is preferably an integer of 1 to 4, and more preferably an integer of 1 or 2. An embodiment in which a1 is 1 is also one of the preferred embodiments of the present invention.

[0052] The number of ester bonds contained in formula (R-1) is preferably 1 or 0.

[0053] Others, Y １ may be a group described in paragraphs 0042 to 0053 of JP-A No. 2023-003421.

[0054] -n and m- In formula (1), m is preferably an integer of 0 to 2, and more preferably 0 or 1. An embodiment in which m is 0 is also one of the preferred embodiments of the present invention. In formula (1), n ​​is preferably 1 or 2, and more preferably 2.

[0055] -Condition a, Condition b- In formula (1), satisfying conditions a and b is also one of the preferred embodiments of the present invention.

[0056] The specific resin may contain one type of repeating unit represented by formula (1), or may contain two or more types of repeating units represented by formula (1). In addition, the specific resin may contain a structural isomer of the repeating unit represented by formula (1).

[0057] [Repeating unit represented by formula (2)] In formula (2), X ２ and Y ２ A preferred embodiment of the formula (1) is １ and Y １ This is the same as the preferred embodiment of the above.

[0058] In formula (2), R ２１ and R ２２ each independently represents a hydrogen atom or a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. ２１ and R ２２ Preferably, at least one of R contains a polymerizable group, and more preferably, both of R ２１ and R ２２ It is also preferable that at least one of the groups contains two or more polymerizable groups. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, radicals, or the like, and a radically polymerizable group is preferred. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. The radically polymerizable group possessed by the polyimide precursor is preferably a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., a vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III), with a group represented by the following formula (III) being preferred.

[0059]

[0060] In formula (III), R ２００represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, and is preferably a hydrogen atom or a methyl group. In formula (III), * represents a bonding site with another structure. In formula (III), R ２０１ represents an alkylene group having 2 to 12 carbon atoms, —CH ２ CH(OH)CH ２ -, a cycloalkylene group or a polyalkyleneoxy group. ２０１ Examples of the alkylene group include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, and a dodecamethylene group; a 1,2-butanediyl group, a 1,3-butanediyl group; a —CH ２ CH(OH)CH ２ alkylene groups such as ethylene and propylene; ２ CH(OH)CH ２More preferred are alkylene groups such as ethylene and propylene, or polyalkyleneoxy groups. In the present invention, a polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the multiple alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different. When a polyalkyleneoxy group contains multiple alkyleneoxy groups with different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, a block arrangement, or an arrangement having an alternating pattern. The number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent if the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 6, even more preferably 2 to 5, even more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2. The alkylene group may also have a substituent. Preferred substituents include alkyl groups, aryl groups, and halogen atoms. The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoint of solvent solubility and solvent resistance, the polyalkyleneoxy group is preferably a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, more preferably a polyethyleneoxy group or a polypropyleneoxy group, and even more preferably a polyethyleneoxy group. In the group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, the ethyleneoxy groups and propyleneoxy groups may be arranged randomly, in blocks, or in an alternating pattern. The preferred embodiments of the number of repeating ethyleneoxy groups and the like in these groups are as described above.

[0061] In formula (2), R ２１is a hydrogen atom, or R ２２ When is a hydrogen atom, the polyimide precursor may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

[0062] -Conditions c and d- In formula (2), satisfying conditions c and d is also one of the preferred embodiments of the present invention.

[0063] The specific resin may contain one type of repeating unit represented by formula (2), or may contain two or more types of repeating units represented by formula (2). In addition, the specific resin may contain a structural isomer of the repeating unit represented by formula (2).

[0064] [Other Repeating Units] The specific resin may contain other types of repeating units in addition to the repeating unit represented by formula (1) and the repeating unit represented by formula (2).

[0065] Other types of repeating units include repeating units in formula (1) that do not satisfy either condition a or condition b, repeating units in formula (1) where n and m are 0, repeating units in formula (2) that do not satisfy either condition c or condition d, and repeating units in formula (2) where R ２１ and R ２２ However, none of the repeating units is a monovalent organic group having an ethylenically unsaturated bond.

[0066] [Content] In one embodiment of the specific resin of the present invention, the total content of the repeating units represented by formula (1) and the repeating units represented by formula (2) is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all of the repeating units in the polyimide precursor except for the terminal repeating units may be the repeating units represented by formula (1) or the repeating units represented by formula (2).

[0067] The weight average molecular weight (Mw) of the specific resin is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 40,000 or less. Furthermore, the Mw is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 15,000 or more. The number average molecular weight (Mn) of the specific resin is preferably 40,000 or less, more preferably 30,000 or less, and even more preferably 20,000 or less. Furthermore, the Mn is preferably 2,000 or more, more preferably 3,000 or more, and even more preferably 4,000 or more. The molecular weight dispersity of the specific resin is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the specific resin is not particularly specified, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. In this specification, the molecular weight dispersity is a value calculated by dividing the weight average molecular weight by the number average molecular weight.

[0068] [Method for producing specific resin] The method for synthesizing the specific resin is not particularly limited and a known method can be used, for example, the method described in paragraphs 0134 to 0136 of WO 2022 / 145355. Alternatively, the specific resin may be synthesized by referring to the method described in the examples below.

[0069] [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 may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0070] <Other Resins> The resin composition of the present invention may contain the specific resin described above and another resin (hereinafter simply referred to as "other resin") different from the specific resin. Examples of other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins. For example, by further adding a (meth)acrylic resin, a resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained. For example, instead of or in addition to the polymerizable compound described below, a resin having a high polymerizable group value and a weight average molecular weight of 20,000 or less (for example, a polymerizable group content of 1×10 per 1 g of resin) can be used. －３ By adding a (meth)acrylic resin (having a molecular weight of 1000 to 1000 mol / g or more) to the resin composition, it is possible to improve the coatability of the resin composition and the solvent resistance of the pattern (cured product).

[0071] When the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, 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. When 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. A preferred embodiment of the resin composition of the present invention may also be an embodiment in which the content of the other resin is low. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the resin composition. The lower limit of the content is not particularly limited, as long as it is 0% by mass or more. The resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0072] <Polymerizable Compound> The resin composition of the present invention preferably contains a polymerizable compound. Examples of the polymerizable compound include a polymerizable compound having a radical polymerizable group (radical crosslinking agent) and other crosslinking agents.

[0073] The number of polymerizable groups in the polymerizable compound is preferably 2 or more, more preferably 2 to 10, and even more preferably 2 to 6. The polymerizable group value in the polymerizable compound (the molar amount of polymerizable groups per 1 g of polymerizable compound) is preferably 1.0 to 15 mmol / g, preferably 2.0 to 12 mmol / g, and more preferably 3.0 to 12 mmol / g.

[0074] [Radical Crosslinking Agent] The resin composition of the present invention preferably contains a radical crosslinking agent. The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group containing an ethylenically unsaturated bond. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group. Among these, a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferred, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferred. In particular, the resin composition of the present invention preferably contains a compound containing a (meth)acryloyl group as a polymerizable compound.

[0075] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds. The radical crosslinking agent may have three or more ethylenically unsaturated bonds. The compound having two or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and even more preferably a compound having 2 to 6 ethylenically unsaturated bonds. From the viewpoint of the film strength of the obtained pattern (cured product), it is also preferable that the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and the compound having three or more ethylenically unsaturated bonds.

[0076] 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.

[0077] Specific examples of radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, and amides. Preferred are esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. Also suitable are addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxyl group, amino group, or sulfanyl group with monofunctional or polyfunctional isocyanates or epoxies, and dehydration condensation reaction products of monofunctional or polyfunctional carboxylic acids. Also suitable are addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as a halogeno group or a tosyloxy group with monofunctional or polyfunctional alcohols, amines, or thiols. As another example, it is also possible to use a group of compounds in which the above-mentioned unsaturated carboxylic acids are replaced with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc. Specific examples can be found in paragraphs 0113 to 0122 of JP 2016-027357 A, the contents of which are incorporated herein by reference.

[0078] The radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples of compounds having a boiling point of 100°C or higher under normal pressure include the compounds described in paragraph 0203 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0079] Other preferred radical crosslinking agents include the radical polymerizable compounds described in paragraphs 0204 to 0208 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0080] Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available products include KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available products include KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available products include KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), and dipentaerythritol hexa(meth)acrylate (commercially available products include KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)), and structures in which the (meth)acryloyl group is bonded via an ethylene glycol residue or a propylene glycol residue. Oligomers of these agents can also be used.

[0081] Commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, SR-209, 231, and 239, which are difunctional methacrylates having four ethyleneoxy chains (all manufactured by Sartomer Corporation), DPCA-60, a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, a trifunctional acrylate having three isobutyleneoxy chains (all manufactured by Nippon Kayaku Co., Ltd.), and urethane oligomers such as Examples of such an ester include UAS-10 and UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, and UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), and Blenmar PME400 (manufactured by NOF Corporation).

[0082] Suitable radical crosslinking agents include urethane acrylates such as those described in JP-B No. 48-041708, JP-A No. 51-037193, JP-B No. 02-032293, and JP-B No. 02-016765, and urethane compounds having an ethylene oxide skeleton such as those described in JP-B No. 58-049860, JP-B No. 56-017654, JP-B No. 62-039417, and JP-B No. 62-039418. Compounds having an amino structure or a sulfide structure in the molecule, such as those described in JP-A Nos. 63-277653, 63-260909, and JP-A No. 01-105238, can also be used as radical crosslinking agents.

[0083] The radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphate group. The radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent obtained by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound to provide an acid group. Particularly preferred is a radical crosslinking agent obtained by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound to provide an acid group, in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include polybasic acid-modified acrylic oligomers M-510 and M-520 manufactured by Toagosei Co., Ltd.

[0084] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH / g, more preferably 1 to 100 mgKOH / g. When the acid value of the radical crosslinking agent is within the above range, the agent has excellent handleability in production and developability. Furthermore, the agent has good polymerizability. The acid value is measured in accordance with the description of JIS K 0070:1992.

[0085] As the radical crosslinking agent, a radical crosslinking agent having at least one selected from the group consisting of a urea bond and a urethane bond (hereinafter also referred to as "crosslinking agent U") is also preferred. In the present invention, the urea bond is a radical crosslinking agent having at least one selected from the group consisting of *-NR Ｎ —C(═O)—NR Ｎ- is a bond represented by *, and R Ｎ Each of the *'s independently represents a hydrogen atom or a monovalent organic group, and each * represents a bonding site with a carbon atom. In the present invention, the urethane bond is *—O—C(═O)—NR Ｎ - is a bond represented by *, and R Ｎ represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom. The inclusion of crosslinker U in a resin composition may improve chemical resistance, resolution, and the like. While the mechanism by which this effect is achieved is unclear, it is thought that, for example, a portion of crosslinker U thermally decomposes during curing by heating, generating amines, etc., which then promote the cyclization of precursors of cyclized resins such as polyimide precursors. Crosslinker U may have only one urea bond or urethane bond, one or more urea bonds and one or more urethane bonds, no urethane bonds and two or more urea bonds, or no urea bonds and two or more urethane bonds. The total number of urea bonds and urethane bonds in crosslinker U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2. When crosslinker U does not have a urethane bond, the number of urea bonds in crosslinker U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2. When the crosslinking agent U does not have a urea bond, the number of urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0086] The radical polymerizable group in the crosslinking agent U is not particularly limited, but examples thereof include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, and a maleimide group. A (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group is preferred, and a (meth)acryloxy group is more preferred. When the crosslinking agent U has two or more radical polymerizable groups, the structures of the respective radical polymerizable groups may be the same or different. The number of radical polymerizable groups in the crosslinking agent U may be only one or may be two or more, preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4. The radical polymerizable group value (mass of the compound per mole of radical polymerizable group) in the crosslinking agent U is preferably 150 to 400 g / mol. From the viewpoint of chemical resistance of the cured product, the lower limit of the radical polymerizable group value is more preferably 200 g / mol or more, even more preferably 210 g / mol or more, even more preferably 220 g / mol or more, even more preferably 230 g / mol or more, still more preferably 240 g / mol or more, and particularly preferably 250 g / mol or more. From the viewpoint of developability, the upper limit of the radical polymerizable group value is more preferably 350 g / mol or less, even more preferably 330 g / mol or less, and particularly preferably 300 g / mol or less. In particular, the polymerizable group value of crosslinking agent U is preferably 210 to 400 g / mol, and more preferably 220 to 400 g / mol.

[0087] The crosslinking agent U preferably has a structure represented by the following formula (U-1): In formula (U-1), R Ｕ１ represents a hydrogen atom or a monovalent organic group, and A represents —O— or —NR Ｎ - and R Ｎ is a hydrogen atom or a monovalent organic group, Z Ｕ１ is an m-valent organic group, and Z Ｕ２ is an (n+1)-valent organic group, X is a radical polymerizable group, n is an integer of 1 or more, and m is an integer of 1 or more.

[0088] R Ｕ１ R is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and more preferably a hydrogen atom. Ｎ is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, more preferably a hydrogen atom. Ｕ１ represents a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O) ２ -, -NR Ｎ - or a group in which two or more of these are bonded is preferred, and a hydrocarbon group, or a hydrocarbon group and -O-, -C(=O)-, -S-, -S(=O) ２ - and -NR Ｎ - is more preferred. The hydrocarbon group is preferably a hydrocarbon group having 20 or less carbon atoms, more preferably a hydrocarbon group having 18 or less carbon atoms, and even more preferably a hydrocarbon group having 16 or less carbon atoms. Examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by a combination of these. R Ｎ represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom or a methyl group. Ｕ２ represents a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O) ２ -, -NR Ｎ - or a group in which two or more of these are bonded is preferred, and a hydrocarbon group, or a hydrocarbon group and -O-, -C(=O)-, -S-, -S(=O) ２ - and -NR Ｎ A group bonded to at least one group selected from the group consisting of - is more preferred. Ｕ１Examples of the groups include those listed in 1. and preferred embodiments are also the same. X is not particularly limited, but examples include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, and a maleimide group, with a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group being preferred, and a (meth)acryloxy group being more preferred. n is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, even more preferably 1 or 2, and particularly preferably 1. m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and even more preferably 1 or 2.

[0089] It is also preferable that the crosslinking agent U has at least one of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group. From the viewpoint of the chemical resistance of the resulting cured film, the hydroxy group may be an alcoholic hydroxy group or a phenolic hydroxy group, but an alcoholic hydroxy group is preferred. From the viewpoint of the chemical resistance of the resulting cured film, the alkyleneoxy group is preferably an alkyleneoxy group having 2 to 20 carbon atoms, more preferably an alkyleneoxy group having 2 to 10 carbon atoms, even more preferably an alkyleneoxy group having 2 to 4 carbon atoms, even more preferably an ethylene group or a propylene group, and particularly preferably an ethylene group. The alkyleneoxy group may be contained in the crosslinking agent U as a polyalkyleneoxy group. In this case, the number of repeating alkyleneoxy groups is preferably 2 to 10, more preferably 2 to 6. The amide group is a -C(=O)-NR Ｎ - refers to a bond represented by R Ｎ When the crosslinking agent U has an amide group, the crosslinking agent U may be, for example, R—C(═O)—NR Ｎ - a group represented by *, or *-C(=O)-NR ＮIt can be contained as a group represented by -R. R represents a hydrogen atom or a monovalent substituent, and is preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group. Crosslinking agent U may have two or more structures selected from the group consisting of a hydroxy group, an alkyleneoxy group (however, when a polyalkyleneoxy group is formed, a polyalkyleneoxy group), an amide group, and a cyano group in the molecule, but an embodiment in which only one structure is present in the molecule is also preferred. The hydroxy group, alkyleneoxy group, amide group, and cyano group may be present at any position in crosslinking agent U, but from the viewpoint of chemical resistance, it is also preferred that at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group is linked to at least one radically polymerizable group contained in crosslinking agent U via a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-1"). In particular, when crosslinking agent U contains only one radically polymerizable group, it is preferred that the radically polymerizable group contained in crosslinking agent U and at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group are linked via a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-2"). When crosslinking agent U contains an alkyleneoxy group (however, when it constitutes a polyalkyleneoxy group, it is a polyalkyleneoxy group) and has the linking group L2-1 or the linking group L2-2, the structure bonded to the side of the alkyleneoxy group (however, when it constitutes a polyalkyleneoxy group, it is a polyalkyleneoxy group) opposite to the linking group L2-1 or the linking group L2-2 is not particularly limited, but is preferably a hydrocarbon group, a radically polymerizable group, or a group represented by a combination thereof. As the hydrocarbon group, a hydrocarbon group having 20 or fewer carbon atoms is preferred, a hydrocarbon group having 18 or fewer carbon atoms is more preferred, and a hydrocarbon group having 16 or fewer carbon atoms is even more preferred. Examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by a combination thereof. Preferred embodiments of the radical polymerizable group are the same as those of the radical polymerizable group in the crosslinking agent U.When crosslinking agent U contains an amide group and has the linking group L2-1 or L2-2, the structure bonded to the side of the amide group opposite the linking group L2-1 or L2-2 is not particularly limited, but is preferably a hydrocarbon group, a radically polymerizable group, or a group represented by a combination thereof. The hydrocarbon group is preferably a hydrocarbon group having 20 or fewer carbon atoms, more preferably a hydrocarbon group having 18 or fewer carbon atoms, and even more preferably a hydrocarbon group having 16 or fewer carbon atoms. Examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by a combination thereof. Preferred aspects of the radically polymerizable group are the same as those of the radically polymerizable group in crosslinking agent U described above. In the above aspect, the carbon atom side of the amide group may be bonded to the linking group L2-1 or L2-2, or the nitrogen atom side of the amide group may be bonded to the linking group L2-1 or L2-2. Among these, from the viewpoints of adhesion to the substrate, chemical resistance, and suppression of Cu voids, it is preferable that crosslinking agent U have a hydroxy group.

[0090] From the viewpoint of compatibility with the specific resin, etc., the crosslinking agent U preferably contains an aromatic group. The aromatic group is preferably directly bonded to a urea bond or urethane bond contained in the crosslinking agent U. When the crosslinking agent U contains two or more urea bonds or urethane bonds, it is preferable that one of the urea bonds or urethane bonds is directly bonded to the aromatic group. The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, or may have a structure in which these form a condensed ring, but is preferably an aromatic hydrocarbon group. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and even more preferably a group in which two or more hydrogen atoms have been removed from a benzene ring structure. The aromatic heterocyclic group is preferably a 5- or 6-membered aromatic heterocyclic group. Examples of the aromatic heterocycle in such an aromatic heterocyclic group include pyrrole, imidazole, triazole, tetrazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, etc. These rings may be condensed with other rings, for example, indole or benzimidazole. The heteroatom contained in the aromatic heterocyclic group is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. The aromatic group is preferably contained in a linking group that links two or more radical polymerizable groups and contains a urea bond or a urethane bond, or a linking group that links at least one selected from the group consisting of the above-mentioned hydroxy group, alkyleneoxy group, amide group, and cyano group to at least one radical polymerizable group contained in the crosslinking agent U.

[0091] The number of atoms (linking chain length) between the urea bond or urethane bond and the radical polymerizable group in crosslinking agent U is not particularly limited, but is preferably 30 or less, more preferably 2 to 20, and even more preferably 2 to 10. When crosslinking agent U contains a total of two or more urea bonds or urethane bonds, when it contains two or more radical polymerizable groups, or when it contains two or more urea bonds or urethane bonds and two or more radical polymerizable groups, the minimum number of atoms (linking chain length) between the urea bond or urethane bond and the radical polymerizable group may be within the above range. In this specification, the "number of atoms (linking chain length) between the urea bond or urethane bond and the polymerizable group" refers to the atomic chain on the path connecting the two atoms or atomic groups to be linked that connects these objects via the shortest distance (minimum number of atoms). For example, in the structure represented by the following formula, the number of atoms (linking chain length) between the urea bond and the radical polymerizable group (methacryloyloxy group) is 2.

[0092] [Axis of symmetry] It is also preferable that the crosslinking agent U is a compound having a structure that does not have an axis of symmetry. The fact that the crosslinking agent U does not have an axis of symmetry means that the crosslinking agent U is a bilaterally asymmetric compound that does not have an axis that would produce a molecule identical to the original molecule by rotating the entire compound. Furthermore, when the structural formula of the crosslinking agent U is written on paper, the fact that the crosslinking agent U does not have an axis of symmetry means that the structural formula of the crosslinking agent U cannot be written in a form that has an axis of symmetry. It is believed that the fact that the crosslinking agent U does not have an axis of symmetry suppresses aggregation of the crosslinking agent U molecules in the composition film.

[0093] [Molecular Weight] The molecular weight of the crosslinking agent U is preferably 100 to 2,000, more preferably 150 to 1,500, and even more preferably 200 to 900.

[0094] The method for producing the crosslinking agent U is not particularly limited, but for example, the crosslinking agent U can be obtained by reacting a radical polymerizable compound and a compound having an isocyanate group with a compound having at least one of a hydroxy group and an amino group.

[0095] Specific examples of the crosslinking agent U are shown below, but the crosslinking agent U is not limited to these.

[0096] From the viewpoints of pattern resolution and film elasticity, it is preferable to use a bifunctional methacrylate or acrylate for 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, 1,6-hexyl ... Examples of usable radical crosslinkers include xanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, ethylene oxide (EO) adduct diacrylate of bisphenol A, propylene oxide (PO) adduct dimethacrylate of bisphenol A, propylene oxide (PO) adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, EO-modified isocyanuric acid diacrylate, EO-modified isocyanuric acid dimethacrylate, and other bifunctional acrylates and bifunctional methacrylates having urethane bonds. Two or more of these may be mixed and used as needed. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a formula weight of approximately 200 for the polyethylene glycol chain. From the viewpoint of suppressing warpage of the pattern (cured product), the resin composition of the present invention preferably uses a monofunctional radical crosslinker as the radical crosslinker.Preferred examples of monofunctional radical crosslinking agents include (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate; N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam; and allyl glycidyl ether. Preferred monofunctional radical crosslinking agents include compounds having a boiling point of 100°C or higher under normal pressure in order to suppress volatilization before exposure. Other examples of bifunctional or higher radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0097] When a radical crosslinking agent is contained, the content of the radical crosslinking agent is preferably more than 0% by mass and not more than 60% by mass, based on the total solid content of the resin composition. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0098] The radical crosslinking agent may be used alone or in combination of two or more. When two or more types are used in combination, the total amount thereof is preferably within the above range.

[0099] [Other Crosslinking Agents] The resin composition of the present invention preferably contains another crosslinking agent different from the radical crosslinking agent described above. The other crosslinking agent refers to a crosslinking agent other than the radical crosslinking agent described above. Preferably, the other crosslinking agent is a compound having a plurality of groups in the molecule that promote the reaction of forming a covalent bond with other compounds in the composition or their reaction products upon exposure to light by a photoacid generator or a photobase generator. Preferably, the other crosslinking agent is a compound having a plurality of groups in the molecule that promote the reaction of forming a covalent bond with other compounds in the composition or their reaction products under the action of an acid or base. Examples of other crosslinking agents include the compounds described in paragraphs 0179 to 0207 of WO 2022 / 145355. The above descriptions are incorporated herein by reference.

[0100] The content of the other crosslinking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass, based on the total solid content of the resin composition. Only one type of other crosslinking agent may be contained, or two or more types may be contained. When two or more types of other crosslinking agents are contained, the total amount thereof is preferably within the above range.

[0101] [Polymerization initiator] The resin composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular limitations on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible range is preferred. Alternatively, it may be an activator that reacts with a photoexcited sensitizer to generate active radicals.

[0102] The photoradical polymerization initiator has a capacity of at least about 50 L·mol within a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). －１ ・cm －１The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to measure the molar absorption coefficient using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g / L using ethyl acetate as a solvent.

[0103] Any known compound can be used as the photoradical polymerization initiator. Examples include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organic boron compounds, and iron arene complexes. For details of these compounds, please refer to paragraphs

[0165] to

[0182] of JP 2016-027357 A and paragraphs

[0138] to

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

[0104] Examples of ketone compounds include the compounds described in paragraph 0087 of JP 2015-087611 A, the contents of which are incorporated herein by reference. As a commercially available product, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

[0105] In one embodiment of the present invention, a hydroxyacetophenone compound, an aminoacetophenone compound, or an acylphosphine compound can be suitably used as the photoradical polymerization initiator. More specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 or an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, the contents of which are incorporated herein by reference.

[0106] Examples of α-hydroxyketone initiators that can be used include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF).

[0107] Examples of α-aminoketone initiators that can be used include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins B.V.), and IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF).

[0108] As the aminoacetophenone initiator, acylphosphine oxide initiator, and metallocene compound, for example, compounds described in paragraphs 0161 to 0163 of WO 2021 / 112189 can also be suitably used. The contents of this specification are incorporated herein by reference.

[0109] As the photoradical polymerization initiator, an oxime compound is more preferably used. By using an oxime compound, it is possible to more effectively improve the exposure latitude. An oxime compound is particularly preferred because it has a wide exposure latitude (exposure margin) and also functions as a photocuring accelerator.

[0110] Specific examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), compounds described in J. C. S. Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232) described compounds, compounds described in JP-A-2000-066385, compounds described in JP-T-2004-534797, compounds described in JP-A-2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in WO 2015 / 152153, compounds described in WO 2017 / 051680, compounds described in JP-A-2017-198865, compounds described in paragraphs 0025 to 0038 of WO 2017 / 164127, compounds described in WO 2013 / 167515 and the like, the contents of which are incorporated herein.

[0111] Preferred oxime compounds include, for example, compounds having the following structure: 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one. In the resin composition, it is particularly preferable to use an oxime compound as a photoradical polymerization initiator. The oxime compound as a photoradical polymerization initiator has a linking group of >C=N-O-C(=O)- in the molecule.

[0112]

[0113] Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (manufactured by BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in JP 2012-014052 A), TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA ARCLES NCI-730, NCI-831, and ADEKA ARCLES NCI-930 (manufactured by ADEKA Corporation), DFI-091 (manufactured by Daito ChemiX Co., Ltd.), and SpeedCure PDO (SARTOMER Also, an oxime compound having the following structure can be used.

[0114] Examples of photoradical polymerization initiators include oxime compounds having a fluorene ring, oxime compounds having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring, and oxime compounds having a fluorine atom, as described in paragraphs 0169 to 0171 of WO 2021 / 112189. Also usable are oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds in which a substituent having a hydroxy group is bonded to a carbazole skeleton, as described in paragraphs 0208 to 0210 of WO 2021 / 020359. The contents of these compounds are incorporated herein by reference.

[0115] In addition, compounds described in paragraphs 0113 to 0117 of JP-A No. 2023-058585 can also be used as the photopolymerization initiator, the disclosure of which is incorporated herein by reference.

[0116] The content of the photopolymerization initiator is preferably 0.1% by mass or more, preferably 0.5% by mass or more, and more preferably 1% by mass or more, relative to the total solid content of the resin composition. The upper limit of the content is preferably 30% by mass or less, preferably 15% by mass or less, and more preferably 10% by mass or less. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more types of photopolymerization initiators are contained, it is preferable that the total amount is within the above range. Note that the photopolymerization initiator may also function as a thermal polymerization initiator, and therefore crosslinking by the photopolymerization initiator may be further promoted by heating in an oven, hot plate, or the like.

[0117] [Sensitizer] The resin composition may contain a sensitizer. The sensitizer absorbs specific actinic radiation and becomes electronically excited. The electronically excited sensitizer comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and undergoes electron transfer, energy transfer, heat generation, and other actions. This causes the thermal radical polymerization initiator or the photoradical polymerization initiator to undergo a chemical change and decompose, generating a radical, acid, or base. Usable sensitizers include benzophenone-based, Michler's ketone-based, coumarin-based, pyrazole azo-based, anilino azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, and indigo-based compounds.Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylideneindanone, p-dimethylaminobenzylideneindanone, and Non, 2-(p-dimethylaminophenylbiphenylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin Phosphorus, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (ethyl 7-(diethylamino)coumarin-3-carboxylate), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate Examples of sensitizing dyes include soamyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, and 3',4'-dimethylacetanilide. Other sensitizing dyes may also be used. For details of sensitizing dyes, please refer to the descriptions in paragraphs 0161 to 0163 of JP-A-2016-027357, the contents of which are incorporated herein by reference.

[0118] When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20 mass %, more preferably 0.1 to 15 mass %, and still more preferably 0.5 to 10 mass %, based on the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more types.

[0119] [Chain Transfer Agent] The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pages 683-684. Examples of chain transfer agents include those having -S-S-, -SO ２ Examples of compounds that can be used include compounds having -S-, -N-O-, SH, PH, SiH, and GeH, and dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthate compounds having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These compounds can donate hydrogen to low-activity radicals to generate radicals, or can be oxidized and then deprotonated to generate radicals. Thiol compounds are particularly preferred.

[0120] In addition, the chain transfer agent may be a compound described in paragraphs 0152 to 0153 of WO 2015 / 199219, the contents of which are incorporated herein by reference.

[0121] When the resin composition contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the total solid content of the resin composition. Only one type of chain transfer agent may be used, or two or more types may be used. When two or more types of chain transfer agents are used, the total content thereof is preferably within the above range.

[0122] In another preferred embodiment of the present invention, the resin composition of the present invention contains two or more polymerization initiators. Specifically, the resin composition of the present invention may contain a photopolymerization initiator and a thermal polymerization initiator described below.

[0123] By including a photopolymerization initiator and a thermal polymerization initiator described below, pattern formation by exposure becomes possible, and radical polymerization also proceeds more easily during curing by a heating step described below, which may improve performance such as chemical resistance. When a photopolymerization initiator and a thermal polymerization initiator described below are included, the content of the thermal polymerization initiator is preferably 20 to 70% by mass, and more preferably 30 to 60% by mass, relative to the total content of the photopolymerization initiator and the thermal polymerization initiator.

[0124] Inclusion of a photoradical polymerization initiator and a photoacid generator may improve performance such as resolution. When a photopolymerization initiator and a photoacid generator are included, the content ratio of the photoacid generator relative to the total content of the photopolymerization initiator and the photoacid generator is preferably 20 to 70 mass %, more preferably 30 to 60 mass %.

[0125] [Thermal Polymerization Initiator] Examples of the thermal polymerization initiator include a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or promotes the polymerization reaction of a polymerizable compound. Addition of a thermal radical polymerization initiator can also promote the polymerization reaction of the resin and the polymerizable compound, thereby further improving solvent resistance.

[0126] Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated herein by reference.

[0127] When a thermal polymerization initiator is contained, the content thereof is preferably 0.1 to 30 mass% relative to the total solid content of the resin composition, more preferably 0.1 to 20 mass%, and even more preferably 0.5 to 15 mass%. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more types of thermal polymerization initiators are contained, it is preferable that the total amount is in the above range.

[0128] <Components that inhibit polymerization> The resin composition of the present invention preferably contains a component that inhibits polymerization. Examples of the component that inhibits polymerization include at least one compound selected from the group consisting of a radical polymerization inhibitor, a nitroso compound, an N-oxide compound, an N-oxyl compound, and a phenothiazine compound, a light absorber, a naphthoquinone diazide compound, an azomethine compound, an indole compound, a benzotriazole compound, a cyanoacrylate compound, a triazine compound, and an anthracene compound.

[0129] [Radical Polymerization Inhibitor] The resin composition of the present invention preferably contains a radical polymerization inhibitor. Examples of the radical polymerization inhibitor include nitroso compounds, N-oxide compounds, N-oxyl compounds, phenothiazine compounds, phenolic compounds, quinone compounds, amino compounds, nitro compounds, heteroaromatic ring compounds, and metal compounds, and the resin composition preferably contains at least one compound selected from the group consisting of nitroso compounds, N-oxide compounds, N-oxyl compounds, and phenothiazine compounds.

[0130] Specific examples of the polymerization inhibitor include the compounds described in paragraph 0310 of WO 2021 / 112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenoxazine, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N-dioxide, and the like, the contents of which are incorporated herein by reference.

[0131] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, and particularly preferably 0.2% by mass or more, based on the total solid content of the resin composition. The content is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 10% by mass or less.

[0132] The polymerization inhibitor may be one kind or two or more kinds. When two or more kinds of polymerization inhibitors are used, the total amount thereof is preferably within the above range.

[0133] [Nitroso Compound, N-Oxide Compound, N-Oxyl Compound, and Phenothiazine Compound] The resin composition of the present invention preferably contains at least one compound (also referred to as "compound A") selected from the group consisting of nitroso compounds, N-oxide compounds, N-oxyl compounds, and phenothiazine compounds.

[0134] Examples of nitroso compounds include nitrosobenzene, 2-nitrosotoluene, 1,2,4,5-tetramethyl-3-nitrosobenzene, 4-nitrosophenol, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 4-nitrosodiphenylamine, 3,5-dibromo-4-nitrosobenzenesulfonic acid, N-nitrosopyrrolidine, N-t-butyl-N-nitrosoaniline, N-nitrosodimethylamine, N-nitrosodiethylamine, 1-nitrosopiperidine, 4-nitrosomorpholine, N-nitroso-N-methylbutylamine, N-nitroso-N-ethylurea, N-nitrosohexamethyleneimine, N-nitrosophenylhydroxyamine cerous salt and N-nitrosophenylhydroxyamine aluminum salt, 2,4,6-Tris-t-butyl-nitrosobenzene, and N-nitrosodiphenylamine.

[0135] Examples of N-oxide compounds include phenyl-t-butylnitrone, 3,3,5,5-tetramethyl-1-pyrroline-N-oxide, 5,5-dimethyl-1-pyrroline N-oxide, 4-methylmorpholine N-oxide, pyridine N-oxide, 4-nitropyridine N-oxide, 3-hydroxypyridine N-oxide, picolinic acid N-oxide, nicotinic acid N-oxide, and isonicotinic acid N-oxide.

[0136] Examples of N-oxyl compounds include 2,2,6,6-tetramethylpiperidine 1-oxyl, 4-cyano-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-carboxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine 1-oxyl, and piperidine 1-oxyl free radicals. Examples include alkane, 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acetamido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-maleimido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, and 4-phosphonoxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, pyrrolidine 1-oxyl free radical compounds, and 3-carboxyproxyl free radical (3-carboxy-2,2,5,5-tetramethylpyrrolidine 1-oxyl free radical).

[0137] Examples of the phenothiazine compound include phenothiazine, 10-methylphenothiazine, 2-methylthiophenothiazine, 2-chlorophenothiazine, 2-ethylthiophenothiazine, 2-(trifluoromethyl)phenothiazine, and 2-methoxyphenothiazine.

[0138] When the resin composition of the present invention contains Compound A, the content of Compound A is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, and particularly preferably 0.2% by mass or more, based on the total solid content of the resin composition. Also, the content is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 10% by mass or less.

[0139] There may be only one type or two or more types of compound A. When there are two or more types of compound A, the total amount thereof is preferably within the above range.

[0140] [Light Absorber] The resin composition of the present invention preferably contains 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 WO 2022 / 202647 and the compounds described in paragraphs 0088 to 0108 of JP 2019-206689 A. The contents of these compounds are incorporated herein by reference. The light absorber is preferably at least one compound selected from the group consisting of naphthoquinone diazide compounds, azomethine compounds, indole compounds, benzotriazole compounds, cyanoacrylate compounds, triazine compounds, and anthracene compounds. Specific embodiments of these compounds are as described in Compound B below.

[0141] 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 mass%, more preferably 0.5 to 10 mass%, and even more preferably 1 to 5 mass%.

[0142] The light absorbing agent may be one kind or two or more kinds. When two or more kinds of light absorbing agents are used, the total amount thereof is preferably within the above range.

[0143] [Naphthoquinone diazide compounds, azomethine compounds, indole compounds, benzotriazole compounds, cyanoacrylate compounds, triazine compounds, anthracene compounds] The resin composition of the present invention preferably contains at least one compound (also referred to as "compound B") selected from the group consisting of naphthoquinone diazide compounds, azomethine compounds, indole compounds, benzotriazole compounds, cyanoacrylate compounds, triazine compounds, and anthracene compounds. Examples of naphthoquinone diazide compounds include the compounds described in paragraphs

[0159] to

[0183] of WO 2022 / 202647 and the compounds described in paragraphs

[0088] to

[0108] of JP 2019-206689 A, the contents of which are incorporated herein by reference. Examples of azomethine compounds include the compounds described in paragraph

[0109] of JP 2020 / 105707 A, the contents of which are incorporated herein by reference. Examples of indole-based compounds include the compounds described in paragraph 0110 of Republished Patent Publication No. 2020 / 105707. The contents of these compounds are incorporated herein by reference. Examples of benzotriazole-based compounds include the compounds described in paragraph 0104 of Republished Patent Publication No. 2020 / 105707. The contents of these compounds are incorporated herein by reference. Examples of cyanoacrylate-based compounds include the compounds described in paragraph 0108 of Republished Patent Publication No. 2020 / 105707. The contents of these compounds are incorporated herein by reference. Examples of triazine-based compounds include the compounds described in paragraph 0106 of Republished Patent Publication No. 2020 / 105707. The contents of these compounds are incorporated herein by reference. Examples of anthracene-based compounds include the compounds described in paragraph 0064 of JP 2023-149537 A. The contents of these compounds are incorporated herein by reference.

[0144] The content of compound B 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 mass%, more preferably 0.5 to 10 mass%, and even more preferably 1 to 5 mass%.

[0145] There may be only one type or two or more types of compound B. When there are two or more types of compound B, the total amount thereof is preferably within the above range.

[0146] <Base Generator> The resin composition of the present invention may contain a base generator. Here, the base generator is a compound capable of generating a base by physical or chemical action. Preferred base generators include thermal base generators and photobase generators. In particular, when the resin composition contains a precursor of a cyclized resin, the resin composition preferably contains a base generator. By containing a thermal base generator in the resin composition, the cyclization reaction of the precursor can be promoted, for example, by heating, and the mechanical properties and chemical resistance of the cured product can be improved, resulting in excellent performance as an interlayer insulating film for a rewiring layer included in a semiconductor package. The base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines. The base generator is not particularly limited, and known base generators can be used. Examples of known base generators include carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, α-lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, and acyloxyimino compounds. Specific examples of non-ionic base generators include the compounds described in paragraphs 0249 to 0275 of WO 2022 / 145355. The above descriptions are incorporated herein by reference.

[0147] Examples of the base generator include, but are not limited to, the following compounds:

[0148]

[0149] 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.

[0150] Specific preferred compounds for the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of WO 2018 / 038002.

[0151] Specific examples of ammonium salts include, but are not limited to, the following compounds:

[0152] Specific examples of iminium salts include, but are not limited to, the following compounds:

[0153] The base generator is preferably an amine in which the amino group is protected with a t-butoxycarbonyl group, from the viewpoints of storage stability and generating a base by deprotection during curing.

[0154] Examples of amine compounds protected by a t-butoxycarbonyl group include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, and 2-amino-1,3-propanediol. alcohol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzyl alcohol, diethanolamine diamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidyl)-2-propanol, 1,4-butanolbis(3-aminopropyl)ethanol ter, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybis(ethylamine), 1,14-diamino-3,6,9,12-tetraoxatetradecane, 1-aza-15-crown-5-ether, diethylene glycol bis(3-aminopropyl)ether, 1,11-diamino-3,6,9-trioxaundecane, or compounds in which the amino group of an amino acid or a derivative thereof is protected with a t-butoxycarbonyl group, but are not limited to these.

[0155] When the resin composition contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass per 100 parts by mass of the resin in the resin composition. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less. One or more types of base generators can be used. When two or more types are used, the total amount is preferably within the above range.

[0156] <Solvent> The resin composition of the present invention preferably contains a solvent. Any known solvent can be used as the solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0157] Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, γ-valerolactone, alkyl alkyloxyacetates (for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionic acid alkyl esters (for example, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters ...alkyloxypropionate, ethyl 3-alkyloxypropionate, 2-alkyloxypropionic acid alkyl esters (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (for example, methyl 3-alkyloxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (for example, methyl 3- Preferred examples thereof include alkyl esters of alkyloxypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, and diethyl malonate.

[0158] Suitable examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0159] Suitable examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0160] Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0161] A preferred example of the sulfoxides is dimethyl sulfoxide.

[0162] Preferred examples of the amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0163] Preferred examples of ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0164] Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.

[0165] From the viewpoint of improving the properties of the coated surface, it is also preferable to mix two or more kinds of solvents.

[0166] In the present invention, one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, levoglucosenone, and dihydrolevoglucosenone, or a mixed solvent composed of two or more solvents, is preferred. Particularly preferred are a combination of dimethyl sulfoxide and γ-butyrolactone, a combination of dimethyl sulfoxide and γ-valerolactone, a combination of 3-methoxy-N,N-dimethylpropionamide and γ-butyrolactone, a combination of 3-methoxy-N,N-dimethylpropionamide, γ-butyrolactone and dimethyl sulfoxide, or a combination of N-methyl-2-pyrrolidone and ethyl lactate. An embodiment in which toluene is further added to these combined solvents in an amount of approximately 1 to 10% by mass, based on the total mass of the solvent, is also a preferred embodiment of the present invention. In particular, from the viewpoint of the storage stability of the resin composition, an embodiment in which γ-valerolactone is included as a solvent is also a preferred embodiment of the present invention. In such an embodiment, the content of γ-valerolactone relative to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. The upper limit of the above content is not particularly limited and may be 100% by mass. The above content may be determined taking into consideration the solubility of components such as the specific resin contained in the resin composition, etc. Furthermore, when dimethyl sulfoxide and γ-valerolactone are used in combination, the solvent preferably contains 60 to 90 mass% of γ-valerolactone and 10 to 40 mass% of dimethyl sulfoxide, more preferably 70 to 90 mass% of γ-valerolactone and 10 to 30 mass% of dimethyl sulfoxide, and even more preferably 75 to 85 mass% of γ-valerolactone and 15 to 25 mass% of dimethyl sulfoxide, relative to the total mass of the solvent.

[0167] From the viewpoint of coatability, the content of the solvent is preferably an amount such that the total solids concentration of the resin composition of the present invention is 5 to 80 mass %, more preferably an amount such that the total solids concentration is 5 to 75 mass %, even more preferably an amount such that the total solids concentration is 10 to 70 mass %, and even more preferably an amount such that the total solids concentration is 20 to 70 mass %. The solvent content may be adjusted depending on the desired thickness of the coating film and the coating method. When two or more solvents are contained, the total amount of the solvents is preferably within the above range.

[0168] <Metal Adhesion Improver> The resin composition of the present invention preferably contains a metal adhesion improver from the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc. Examples of metal adhesion improvers include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure, compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, and amino compounds.

[0169] [Silane Coupling Agent] Examples of silane coupling agents include the compounds described in paragraph 0316 of WO 2021 / 112189 and the compounds described in paragraphs 0067 to 0078 of JP 2018-173573 A, the contents of which are incorporated herein by reference. It is also preferable to use two or more different silane coupling agents, as described in paragraphs 0050 to 0058 of JP 2011-128358 A. It is also preferable to use the following compounds as the silane coupling agent. In the formula below, Me represents a methyl group, and Et represents an ethyl group. Furthermore, the following R represents a structure derived from a blocking agent in a blocked isocyanate group. The blocking agent may be selected depending on the desorption temperature, and examples include alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, and active methylene compounds. For example, caprolactam is preferred from the viewpoint of achieving a desorption temperature of 160 to 180°C. Commercially available products of such compounds include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0170]

[0171] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- Examples of suitable silane coupling agents include (aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride. These may be used alone or in combination of two or more. Furthermore, oligomeric compounds having multiple alkoxysilyl groups may also be used as silane coupling agents. Examples of such oligomeric compounds include compounds containing a repeating unit represented by the following formula (S-1): In formula (S-1), R Ｓ１ represents a monovalent organic group, R Ｓ２ represents a hydrogen atom, a hydroxy group or an alkoxy group, and n represents an integer of 0 to 2. Ｓ１is preferably a structure containing a polymerizable group. Examples of the polymerizable group include a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group), a (meth)acrylamide group, and a (meth)acryloyloxy group. A vinylphenyl group, a (meth)acrylamide group, or a (meth)acryloyloxy group is preferred, a vinylphenyl group or a (meth)acryloyloxy group is more preferred, and a (meth)acryloyloxy group is even more preferred. R Ｓ２ is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. n represents an integer of 0 to 2, preferably 1. Here, the structures of the multiple repeating units represented by formula (S-1) contained in the oligomer-type compound may be the same. Here, of the multiple repeating units represented by formula (S-1) contained in the oligomer-type compound, it is preferable that n is 1 or 2 in at least one, more preferably that n is 1 or 2 in at least two, and even more preferably that n is 1 in at least two. Such oligomer-type compounds can be commercially available products, and an example of a commercially available product is KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0172] [Aluminum-Based Adhesion Aid] Examples of aluminum-based adhesion aids include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0173] Other metal adhesion improvers that can be used include the compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP-A-2013-072935, the contents of which are incorporated herein by reference.

[0174] The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the specific resin. By ensuring that the content is equal to or greater than the above lower limit, the adhesion between the pattern and the metal layer is improved, and by ensuring that the content is equal to or less than the above upper limit, the heat resistance and mechanical properties of the pattern are improved. Only one type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above range.

[0175] <Migration Inhibitor> The resin composition of the present invention preferably further contains a migration inhibitor. By including a migration inhibitor, for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, migration of metal ions derived from the metal layer (or metal wiring) into the film can be effectively inhibited.

[0176] The migration inhibitor is not particularly limited, but examples thereof include compounds having a heterocycle (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring), thioureas and compounds having a sulfanyl group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole are preferably used.

[0177] As the migration inhibitor, an ion trapping agent that traps anions such as halogen ions can also be used.

[0178] Other migration inhibitors include the rust inhibitors described in paragraph 0094 of JP-A-2013-015701, the compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, the compounds described in paragraph 0052 of JP-A-2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of JP-A-2012-194520, and the compounds described in paragraph 0166 of WO 2015 / 199219. The contents of this specification are incorporated herein by reference.

[0179] Specific examples of the migration inhibitor include the following compounds.

[0180]

[0181] When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass%, more preferably 0.05 to 2.0 mass%, and even more preferably 0.1 to 1.0 mass%, based on the total solid content of the resin composition.

[0182] The migration inhibitor may be one kind or two or more kinds. When two or more kinds of migration inhibitors are used, the total amount thereof is preferably within the above range.

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

[0184] [Surfactant] Various surfactants can be used as the surfactant, such as a fluorine-based surfactant, a silicone-based surfactant, a hydrocarbon-based surfactant, etc. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0185] By adding a surfactant to the resin composition of the present invention, the liquid properties (particularly fluidity) of the coating liquid composition when prepared are further improved, and the uniformity of the coating thickness and the liquid saving can be further improved. That is, when a film is formed using a coating liquid containing a surfactant, the interfacial tension between the surface to be coated and the coating liquid is reduced, improving the wettability of the surface to be coated and the coatability of the surface to be coated. Therefore, it is possible to more suitably form a uniform film with small thickness unevenness.

[0186] Examples of fluorine-based surfactants include the compounds described in paragraph 0328 of WO 2021 / 112189, the contents of which are incorporated herein by reference. As the fluorine-based surfactant, fluorine-containing polymer compounds containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups) can also be preferably used, and examples thereof include the following compounds.

[0187] The weight-average molecular weight of the above compound is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. As the fluorosurfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP 2010-164965 A, the contents of which are incorporated herein by reference. Commercially available products include Megafac RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

[0188] The fluorine content in the fluorine-containing surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-containing surfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and liquid saving, and also has good solubility in the composition.

[0189] Examples of silicone surfactants, hydrocarbon surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants include the compounds described in paragraphs 0329 to 0334 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0190] The surfactant may be used alone or in combination of two or more. The content of the surfactant is preferably 0.001 to 2.0 mass %, more preferably 0.005 to 1.0 mass %, based on the total solid content of the composition.

[0191] [Inorganic Particles] Specific examples of inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.

[0192] The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, even more preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. The above average particle size of the inorganic particles is the primary particle size and also the volume average particle size. The volume average particle size can be measured, for example, by dynamic light scattering using a Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurement is difficult, it can also be measured by centrifugal sedimentation light transmission method, X-ray transmission method, or laser diffraction / scattering method.

[0193] [Organotitanium Compound] When the resin composition contains an organotitanium compound, a resin layer having excellent chemical resistance can be formed even when cured at low temperatures.

[0194] Usable organic titanium compounds include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of organic titanium compounds are shown below in I) to VII): I) Titanium chelate compounds: Titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability to the resin composition and a good curing pattern. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), and titanium diisopropoxide bis(ethylacetoacetate). II) Tetraalkoxytitanium compounds: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], etc. III) Titanocene compounds: for example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc. IV) Monoalkoxytitanium compounds: for example, titanium tris(dioctylphosphate)isopropoxide, titanium tris(dodecylbenzenesulfonate)isopropoxide, etc. V) Titanium oxide compounds: for example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc.VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate, etc. VII) Titanate coupling agents: For example, isopropyl tridodecylbenzenesulfonyl titanate, etc.

[0195] Among these, from the viewpoint of better chemical resistance, the organic titanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

[0196] It is also preferable to contain a compound represented by the following formula (T-1) as the organotitanium compound or in place of the organotitanium compound. In formula (T-1), M is titanium, zirconium, or hafnium, l1 is an integer of 0 to 2, l2 is 0 or 1, l1 + l2 × 2 is an integer of 0 to 2, m is an integer of 0 to 4, n is an integer of 0 to 2, l1 + l2 + m + n × 2 = 4, and R １１ are each independently a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenoxy group; R １２ is a substituted or unsubstituted hydrocarbon group, R ２ are each independently a group containing a structure represented by the following formula (T-2), and R ３ are each independently a group containing a structure represented by the following formula (T-2), Ａ are each independently an oxygen atom or a sulfur atom. In formula (T-2), X １ ~X ３ each independently represents -C(-*)= or -N=, * represents a bonding site to another structure, and # represents a bonding site to a metal atom.

[0197] In formula (T-1), from the viewpoint of storage stability of the composition, M is preferably titanium. In formula (T-1), an embodiment in which l1 and l2 are 0 is also one of the preferred embodiments of the present invention. In formula (T-1), m is preferably 2 or 4, and more preferably 2. In formula (T-1), n ​​is preferably 1 or 2, and more preferably 1. Here, it is also preferable that in formula (T-1), l1 and l2 are 0, and m is 0, 2, or 4.

[0198] In formula (T-1), from the viewpoint of the stability of the specific metal complex, R １１ is preferably a substituted or unsubstituted cyclopentadienyl ligand. １１ The cyclopentadienyl group, alkoxy group and phenoxy group in the formula (I) may be substituted, but an embodiment in which they are unsubstituted is also one of the preferred embodiments of the present invention.

[0199] In formula (T-1), R １２ is preferably a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrocarbon group having 2 to 10 carbon atoms. １２ The hydrocarbon group in may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but an aromatic hydrocarbon group is preferred. The aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, but a saturated aliphatic hydrocarbon group is preferred. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and even more preferably a phenylene group. R １２ The substituent in R is preferably a monovalent substituent, such as a halogen atom. １２ When R is an aromatic hydrocarbon group, it may have an alkyl group as a substituent. １２ is preferably an unsubstituted phenylene group. １２ The phenylene group in is preferably a 1,2-phenylene group.

[0200] In formula (T-1), m is 2 or more, and R ２ If two or more are included,２ In formula (T-1), n ​​is 2 or more, and R ３ If two or more are included, ３ The structures may be the same or different.

[0201] In formula (T-2), X １ ~X ３ each independently represents -C(-*)= or -N=, and it is preferable that at least one represents -C(-*)=, and it is more preferable that at least two represent -C(-*)=.

[0202] Specific examples of the compound represented by formula (T-1) include, but are not limited to, the compound represented by formula H-1 in the examples.

[0203] When an organotitanium compound is contained, its content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the specific resin. When the content is 0.05 part by mass or more, the heat resistance and chemical resistance of the obtained cured pattern are improved, and when it is 10 parts by mass or less, the storage stability of the composition is improved.

[0204] When an organotitanium compound is contained, its content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the specific resin. When the content is 0.05 part by mass or more, the heat resistance and chemical resistance of the obtained cured pattern are improved, and when it is 10 parts by mass or less, the storage stability of the composition is superior.

[0205] Other additives include compounds described in paragraphs 0249 to 0282 and 0316 to 0358 of WO 2022 / 145355, the disclosures of which are incorporated herein by reference.

[0206] <Characteristics of Resin Composition> The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. ２ / s~12,000mm ２ / s is preferred, and 2,000 mm ２ / s~10,000mm ２ / s is more preferable, and 2,500 mm ２ / s~8,000mm ２ Within the above range, it is easy to obtain a highly uniform coating film. ２ If the thickness is more than 12,000 mm / s, it is easy to apply the coating to a thickness required for an insulating film for rewiring, for example. ２ If the viscosity is less than 1 / s, a coating film with excellent surface condition can be obtained.

[0207] <Restrictions on substances contained in the resin composition> The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.

[0208] From the viewpoint of insulating properties, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but metals contained as complexes of organic compounds and metals are excluded. When multiple metals are contained, the total amount of these metals is preferably within the above range.

[0209] Furthermore, examples of methods for reducing metal impurities unintentionally contained in the resin composition of the present invention include selecting raw materials with a low metal content as raw materials for constituting the resin composition of the present invention, filtering the raw materials for constituting the resin composition of the present invention, and lining the inside of the apparatus with polytetrafluoroethylene or the like to perform distillation under conditions that minimize contamination as much as possible.

[0210] Considering the use of the resin composition of the present invention as a semiconductor material, the content of halogen atoms is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass, from the viewpoint of wiring corrosion. In particular, those present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferable that the total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above-mentioned range. Preferred methods for adjusting the content of halogen atoms include ion exchange treatment.

[0211] A conventionally known container can be used as a container for storing the resin composition of the present invention. For the purpose of preventing impurities from being mixed into the raw materials or the resin composition of the present invention, it is also preferable to use a multi-layer bottle whose inner wall is made of six types of six resin layers, or a bottle with a seven-layer structure made of six types of resin. Examples of such containers include the container described in JP 2015-123351 A.

[0212] <Cured Product of Resin Composition> A cured product of the resin composition can be obtained by curing the resin composition of the present invention. The cured product of the present invention is a cured product obtained by curing the resin composition. The resin composition is preferably cured by heating, with a heating temperature of 120°C to 400°C being more preferred, 140°C to 380°C being even more preferred, 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 depending on the application, such as a film, rod, sphere, or pellet. In the present invention, the cured product is preferably in the form of a film. By patterning the resin composition, the shape of the cured product can be selected depending on the application, such as forming a protective film on a wall surface, forming via holes for electrical conductivity, adjusting impedance, capacitance, or internal stress, or imparting heat dissipation functionality. The film thickness of the cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less. The shrinkage rate 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 of change in volume of the resin composition before and after curing, and can be calculated by the following formula: Shrinkage rate [%] = 100 - (volume after curing / volume before curing) x 100

[0213] <Characteristics of cured product of resin composition> The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, the cured product may have excellent mechanical properties. The elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more. The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180°C or more, more preferably 210°C or more, and even more preferably 230°C or more.

[0214] <Preparation of Resin Composition> The resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and can be carried out by a conventionally known method. Examples of the mixing method include mixing with a stirring blade, mixing with a ball mill, and mixing by rotating a tank. The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.

[0215] Filtration using a filter is preferably performed to remove foreign matter such as dust and fine particles from the resin composition of the present invention. The filter pore size is, for example, preferably 5 μm or less, more preferably 1 μm or less, even more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. When the filter material is polyethylene, HDPE (high-density polyethylene) is more preferable. The filter may be pre-washed with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or parallel. When multiple types of filters are used, filters with different pore sizes or materials may be combined. An example of a connection mode is a mode in which an HDPE filter with a pore size of 1 μm is connected in series as the first stage and an HDPE filter with a pore size of 0.2 μm is connected in series as the second stage. Various materials may also be filtered multiple times. When filtration is performed multiple times, circulating filtration may be used. Filtration may also be performed under pressure. When filtering under pressure, the pressure to be applied is preferably 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, even more preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less. In addition to filtering using a filter, a process of removing impurities using an adsorbent may be performed. Filter filtration and a process of removing impurities using an adsorbent may be combined. Known adsorbents can be used as the adsorbent. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. After filtering using a filter, the resin composition filled in a bottle may be subjected to a degassing process by placing it under reduced pressure.

[0216] (Method for producing a cured product) The method for producing a cured product of the present invention preferably includes a film-forming step in which a resin composition is applied to a substrate to form a film. The method for producing a cured product more preferably includes the film-forming step, an exposure step in which the film formed in the film-forming step is selectively exposed to light, and a development step in which the film exposed in the exposure step is developed using a developer to form a pattern. The method for producing a cured product particularly preferably includes the film-forming step, the exposure step, the development step, and at least one of a heating step in which the pattern obtained in the development step is heated and a post-development exposure step in which the pattern obtained in the development step is exposed to light. The method for producing a cured product also preferably includes the film-forming step and a step of heating the film. Details of each step are described below.

[0217] <Film Forming Step> The resin composition of the present invention can be used in a film forming step of applying the resin composition to a substrate to form a film. The method for producing a cured product of the present invention preferably includes a film forming step of applying the resin composition to a substrate to form a film.

[0218] [Substrate] The type of substrate can be appropriately determined depending on the application and is not particularly limited. Examples of substrates include semiconductor production substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metal and substrates on which a metal layer is formed by, for example, plating or vapor deposition), paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, mold substrates, and plasma display panel (PDP) electrode plates. Substrates are particularly preferably semiconductor production substrates, with silicon substrates, Cu substrates, and mold substrates being more preferred. These substrates may have a surface layer such as an adhesion layer or an oxide layer formed by hexamethyldisilazane (HMDS) or the like. The shape of the substrate is not particularly limited and may be circular or rectangular. The size of the substrate is preferably, for example, a diameter of 100 to 450 mm, more preferably 200 to 450 mm, if it is circular. If it is rectangular, the length of the short side is preferably, for example, 100 to 1000 mm, more preferably 200 to 700 mm. As the substrate, for example, a plate-shaped, preferably a panel-shaped substrate (substrate) is used.

[0219] When a film is formed by applying a resin composition to the surface of a resin layer (for example, a layer made of a cured product) or the surface of a metal layer, the resin layer or the metal layer serves as the substrate.

[0220] Coating is preferred as a means for applying the resin composition to a substrate. Specific application methods include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating, or inkjet coating is preferred, and from the viewpoint of uniformity of film thickness and productivity, spin coating and slit coating are more preferred. By adjusting the solid content concentration of the resin composition and coating conditions depending on the application method, a film of the desired thickness can be obtained. In addition, the coating method can be appropriately selected depending on the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, inkjet coating, etc. are preferred, and for rectangular substrates, slit coating, spray coating, inkjet coating, etc. are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. Alternatively, a method can be used in which a coating film formed by applying the coating composition to a temporary support in advance using the above-described application method is transferred onto the substrate. Regarding the transfer method, the preparation methods described in paragraphs 0023 and 0036 to 0051 of JP-A No. 2006-023696 and paragraphs 0096 to 0108 of JP-A No. 2006-047592 can be suitably used. A step of removing excess film from the edge of the substrate may also be performed. Examples of such a step include edge bead rinsing (EBR) and back rinsing. A pre-wetting step may also be employed in which the substrate is coated with various solvents before applying the resin composition to the substrate, improving the wettability of the substrate and then applying the resin composition.

[0221] <Drying Step> After the film-forming step (layer-forming step), the film may be subjected to a step (drying step) of drying the formed film (layer) to remove the solvent. That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film-forming step. The drying step is preferably carried out after the film-forming step and before the exposure step. The drying temperature of the film in the drying step is preferably 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. Drying may also be carried out under reduced pressure. The drying time is, for example, 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.

[0222] <Exposure Step> The film may be subjected to an exposure step in which the film is selectively exposed to light. The method for producing a cured product may include an exposure step in which the film formed in the film formation step is selectively exposed to light. Selective exposure means that a portion of the film is exposed to light. Furthermore, selective exposure forms exposed regions (exposed portions) and unexposed regions (unexposed portions) in the film. The exposure dose is not particularly limited as long as it can cure the resin composition of the present invention, but for example, it is 50 to 10,000 mJ / cm2 in terms of exposure energy at a wavelength of 365 nm. ２ is preferred, and 200 to 8,000 mJ / cm ２ is more preferred.

[0223] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

[0224] The exposure wavelengths, in relation to the light source, are: (1) semiconductor laser (wavelengths 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.); (2) metal halide lamp; (3) high-pressure mercury lamp, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, and i-line); (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ２Examples of such light include excimer laser (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron beam, and (7) YAG laser second harmonic 532 nm and third harmonic 355 nm. For the resin composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferred, and exposure with i-line is more preferred from the viewpoint of exposure sensitivity. The exposure method is not particularly limited as long as it is a method that exposes at least a portion of the film made of the resin composition of the present invention, and examples thereof include exposure using a photomask and exposure by laser direct imaging.

[0225] <Post-Exposure Bake Step> The film may be subjected to a heating step (post-exposure bake step) after exposure. That is, the method for producing a cured product of the present invention may include a post-exposure bake step in which the film exposed in the exposure step is heated. The post-exposure bake step can be carried out after the exposure step and before the development step. The heating temperature in the post-exposure bake step is preferably 50°C to 140°C, more preferably 60°C to 120°C. The heating time in the post-exposure bake step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes. The temperature rise rate in the post-exposure bake step from the temperature at the start of heating to the maximum heating temperature is preferably 1 to 12°C / min, more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. The temperature rise rate may also be changed as appropriate during heating. The heating means in the post-exposure bake step is not particularly limited, and known hot plates, ovens, infrared heaters, etc. may be used. It is also preferable to carry out the heating in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.

[0226] <Development step> The above-mentioned film after exposure may be subjected to a development step in which it is developed using a developer to form a pattern. That is, the method for producing a cured product of the present invention may include a development step in which the film exposed in the exposure step is developed using a developer to form a pattern. By carrying out development, one of the exposed and unexposed parts of the film is removed to form a pattern. Here, development in which the unexposed parts of the film are removed in the development step is called negative development, and development in which the exposed parts of the film are removed in the development step is called positive development.

[0227] [Developer] The developer used in the development step may be an aqueous alkaline solution or a developer containing an organic solvent.

[0228] When the developer is an alkaline aqueous solution, examples of the basic compound that can be contained in the alkaline aqueous solution include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferred are TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine, and more preferred is TMAH. The content of the basic compound in the developer is preferably from 0.01 to 10% by mass, more preferably from 0.1 to 5% by mass, and even more preferably from 0.3 to 3% by mass, based on the total mass of the developer.

[0229] When the developer contains an organic solvent, the organic solvent may be a compound described in paragraph

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

[0230] When the developer contains an organic solvent, the organic solvent may be used alone or in combination. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide is more preferred, and a developer containing cyclopentanone is particularly preferred.

[0231] When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Alternatively, the content may be 100% by mass.

[0232] The developer may further contain other components, such as known surfactants and known defoaming agents.

[0233] [Method of Supplying Developer] The method of supplying the developer is not particularly limited as long as it can form the desired pattern, and includes a method of immersing a substrate on which a film has been formed in the developer, puddle development in which the developer is supplied to the film formed on the substrate using a nozzle, and a method of continuously supplying the developer. The type of nozzle is not particularly limited, and examples include a straight nozzle, a shower nozzle, and a spray nozzle. From the viewpoints of the permeability of the developer, the removability of non-image areas, and production efficiency, a method of supplying the developer using a straight nozzle or a method of continuously supplying the developer using a spray nozzle is preferred, and from the viewpoint of the permeability of the developer to the image areas, a method of supplying using a spray nozzle is more preferred. In addition, a process may be adopted in which the developer is continuously supplied using a straight nozzle, the substrate is spun to remove the developer from the substrate, and after spin drying, the developer is continuously supplied again using a straight nozzle, and the substrate is spun to remove the developer from the substrate, or this process may be repeated multiple times. Methods of supplying the developer in the development process include a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept substantially stationary on the substrate, a process in which the developer is vibrated on the substrate using ultrasound or the like, and a combination thereof.

[0234] The development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

[0235] In the developing step, after the treatment with the developer, the pattern may be further washed (rinsed) with a rinse liquid. Alternatively, a method may be employed in which a rinse liquid is supplied before the developer in contact with the pattern is completely dried.

[0236] [Rinse Liquid] When the developer is an alkaline aqueous solution, for example, water can be used as the rinse liquid. When the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (for example, water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinse liquid.

[0237] When the rinse solution contains an organic solvent, examples of the organic solvent include the same organic solvents as those exemplified when the developer contains an organic solvent. The organic solvent contained in the rinse solution is preferably different from the organic solvent contained in the developer, and more preferably an organic solvent that has a lower solubility for the pattern than the organic solvent contained in the developer.

[0238] When the rinse solution contains an organic solvent, the organic solvent may be used alone or in combination of two or more. The organic solvent is preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, or PGME, more preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, or PGME, and even more preferably cyclohexanone or PGMEA.

[0239] When the rinse solution contains an organic solvent, the organic solvent preferably accounts for 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more of the total mass of the rinse solution, and may also account for 100% by mass of the total mass of the rinse solution.

[0240] The rinse liquid may further contain other components, such as known surfactants and known defoaming agents.

[0241] [Method of Supplying Rinse Liquid] The method of supplying the rinse liquid is not particularly limited as long as it can form a desired pattern, and examples thereof include a method of immersing the substrate in the rinse liquid, a method of supplying the rinse liquid to the substrate by puddling, a method of supplying the rinse liquid to the substrate by showering, and a method of continuously supplying the rinse liquid onto the substrate by means of a straight nozzle or the like. From the viewpoints of the permeability of the rinse liquid, the removability of non-image areas, and production efficiency, methods of supplying the rinse liquid using a shower nozzle, straight nozzle, spray nozzle, etc. are available, and a method of continuously supplying using a spray nozzle is preferred, and from the viewpoint of the permeability of the rinse liquid into the image areas, a method of supplying using a spray nozzle is more preferred. The type of nozzle is not particularly limited, and examples include a straight nozzle, shower nozzle, spray nozzle, etc. That is, the rinsing step is preferably a step of supplying or continuously supplying the rinse liquid to the exposed film using a straight nozzle, and more preferably a step of supplying the rinse liquid using a spray nozzle. The method of supplying the rinse liquid in the rinsing step may include a step of continuously supplying the rinse liquid to the substrate, a step of keeping the rinse liquid substantially stationary on the substrate, a step of vibrating the rinse liquid on the substrate by ultrasonic waves or the like, and a combination of these steps.

[0242] The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinsing liquid during rinsing is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

[0243] <Heating Step> The pattern obtained by the development step (or the pattern after rinsing, if a rinsing step is performed) may be subjected to a heating step in which the pattern obtained by the development step is heated. That is, the method for producing a cured product of the present invention may include a heating step in which the pattern obtained by the development step is heated. Furthermore, the method for producing a cured product of the present invention may include a heating step in which a pattern obtained by another method without performing a development step, or a film obtained by a film formation step, is heated. In the heating step, a resin such as a polyimide precursor is cyclized to form a resin such as a polyimide. Furthermore, crosslinking of unreacted crosslinkable groups in the specific resin or in a crosslinking agent other than the specific resin also proceeds. The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, even more preferably 150 to 250°C, even more preferably 160 to 250°C, and particularly preferably 160 to 230°C.

[0244] The heating step is preferably a step in which the cyclization reaction of the polyimide precursor is promoted within the pattern by the action of a base or the like generated from the base generator due to heating.

[0245] The heating step is preferably carried out at a temperature increase rate of 1 to 12°C / min from the temperature at the start of heating to the maximum heating temperature. The temperature increase rate is more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. By setting the temperature increase rate to 1°C / min or more, it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity, and by setting the temperature increase rate to 12°C / min or less, it is possible to alleviate residual stress in the cured product. In addition, in the case of an oven capable of rapid heating, it is preferable to increase the temperature from the temperature at the start of heating to the maximum heating temperature at a temperature increase rate of 1 to 8°C / sec, more preferably 2 to 7°C / sec, and even more preferably 3 to 6°C / sec.

[0246] The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the process of heating up to the maximum heating temperature. For example, when the resin composition of the present invention is applied to a substrate and then dried, the temperature is the temperature of the film (layer) after this drying, and it is preferable to raise the temperature from, for example, a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition.

[0247] The heating time (heating time at the maximum heating temperature) is preferably from 5 to 360 minutes, more preferably from 10 to 300 minutes, and even more preferably from 15 to 240 minutes.

[0248] In particular, when forming a multilayer laminate, from the viewpoint of interlayer adhesion, the heating temperature is preferably 30° C. or higher, more preferably 80° C. or higher, even more preferably 100° C. or higher, and particularly preferably 120° C. or higher. The upper limit of the heating temperature is preferably 350° C. or lower, more preferably 250° C. or lower, and even more preferably 240° C. or lower.

[0249] Heating may be performed in stages. For example, the temperature may be increased from 25°C to 120°C at a rate of 3°C / min, held at 120°C for 60 minutes, increased from 120°C to 180°C at a rate of 2°C / min, and held at 180°C for 120 minutes. It is also preferable to treat the film while irradiating it with ultraviolet light, as described in U.S. Pat. No. 9,159,547. Such a pretreatment step can improve the film's properties. The pretreatment step may be performed for a short period of time, preferably from 10 seconds to 2 hours, more preferably from 15 seconds to 30 minutes. The pretreatment step may be performed in two or more steps. For example, a first pretreatment step may be performed in the range of 100 to 150°C, followed by a second pretreatment step in the range of 150 to 200°C. Furthermore, cooling may be performed after heating. In this case, the cooling rate is preferably from 1 to 5°C / min.

[0250] The heating step is preferably carried out in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, or by carrying out the heating step under reduced pressure, in order to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less. The heating means used in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, and an infrared oven.

[0251] <Post-development exposure step> The pattern obtained in the development step (if a rinsing step is performed, the pattern after rinsing) may be subjected to a post-development exposure step in which the pattern obtained in the development step is exposed to light, instead of or in addition to the heating step. That is, the method for producing a cured product of the present invention may include a post-development exposure step in which the pattern obtained in the development step is exposed to light. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step. The post-development exposure step can promote, for example, a reaction in which cyclization of a polyimide precursor or the like progresses due to exposure of a photobase generator, or a reaction in which elimination of an acid-decomposable group progresses due to exposure of a photoacid generator. In the post-development exposure step, it is sufficient that at least a portion of the pattern obtained in the development step is exposed, but it is preferable that the entire pattern is exposed. The exposure dose in the post-development exposure step is 50 to 20,000 mJ / cm in terms of exposure energy at a wavelength to which the photosensitive compound has sensitivity. ２ is preferred, and 100 to 15,000 mJ / cm ２ The post-development exposure step can be carried out using, for example, the light source used in the exposure step described above, and it is preferable to use broadband light.

[0252] <Metal Layer Forming Step> The pattern obtained by the developing step (preferably subjected to at least one of a heating step and a post-development exposure step) may be subjected to a metal layer forming step of forming a metal layer on the pattern. That is, the method for producing a cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on the pattern obtained by the developing step (preferably subjected to at least one of a heating step and a post-development exposure step).

[0253] The metal layer is not particularly limited, and existing metal species can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are more preferred, and copper is even more preferred.

[0254] The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in JP 2007-157879 A, ​​JP 2001-521288 A, JP 2004-214501 A, JP 2004-101850 A, U.S. Patent No. 7,888,181 B2, and U.S. Patent No. 9,177,926 B2 can be used. Examples of suitable methods include photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and combinations of these. More specifically, examples include patterning methods that combine sputtering, photolithography, and etching, and patterning methods that combine photolithography and electroplating. Preferred plating methods include electroplating using a copper sulfate or copper cyanide plating solution.

[0255] The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm, at the thickest part.

[0256] <Applications> Fields to which the method for producing a cured product of the present invention or the cured product can be applied include insulating films for electronic devices, interlayer insulating films for rewiring layers, stress buffer films, etc. Other examples include sealing films, substrate materials (base films, coverlays, and interlayer insulating films for flexible printed circuit boards), and the etching of insulating films for packaging applications such as those described above. For these applications, reference can be made to, for example, Science & Technology Co., Ltd.'s "High Performance Polyimide and Application Technology" (April 2008), edited by Masaaki Kakimoto, CMC Technical Library "Fundamentals and Development of Polyimide Materials" (November 2011), and Japan Polyimide and Aromatic Polymer Research Association's "Latest Polyimide Fundamentals and Applications" (NTS, August 2010).

[0257] The method for producing the cured product of the present invention, or the cured product of the present invention, can also be used for producing printing plates such as offset printing plates or screen printing plates, for etching molded parts, for producing protective lacquers and dielectric layers in electronics, especially microelectronics, etc.

[0258] (Laminate and method for manufacturing laminate) The laminate of the present invention refers to a structure having a plurality of layers each made of the cured product of the present invention. The laminate is a laminate including two or more layers each made of the cured product, and may be a laminate including three or more layers. At least one of the two or more layers each made of the cured product contained in the laminate is a layer made of the cured product of the present invention, and from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product associated with the shrinkage, it is also preferable that all of the layers made of the cured product contained in the laminate are layers made of the cured product of the present invention.

[0259] That is, the method for producing a laminate of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes repeating the method for producing a cured product of the present invention multiple times.

[0260] The laminate of the present invention preferably includes two or more layers made of a cured product and a metal layer between any of the layers made of the cured product. The metal layer is preferably formed by the metal layer-forming step. That is, the method for producing a laminate of the present invention preferably further includes a metal layer-forming step of forming a metal layer on a layer made of a cured product between multiple cured product production processes. A preferred embodiment of the metal layer-forming step is as described above. Examples of the laminate include a laminate having at least a layer structure in which three layers are stacked in this order: a layer made of a first cured product, a metal layer, and a layer made of a second cured product. It is preferred that both the layer made of the first cured product and the layer made of the second cured product are layers made of the cured product of the present invention. The resin composition of the present invention used to form the layer made of the first cured product and the resin composition of the present invention used to form the layer made of the second cured product may have the same composition or different compositions. The metal layer in the laminate of the present invention is preferably used as metal wiring, such as a rewiring layer.

[0261] <Lamination Step> The method for producing a laminate of the present invention preferably includes a lamination step. The lamination step is a series of steps including performing at least one of (a) a film formation step (layer formation step), (b) an exposure step, (c) a development step, and (d) a heating step and a post-development exposure step again on the surface of the pattern (resin layer) or the metal layer in this order. However, at least one of (a) the film formation step and (d) the heating step and the post-development exposure step may be repeated. Furthermore, after at least one of (d) the heating step and the post-development exposure step, (e) a metal layer formation step may be included. It goes without saying that the lamination step may further include the above-mentioned drying step or the like as appropriate.

[0262] When a further lamination step is performed after the lamination step, a surface activation treatment step may be further performed after the exposure step, the heating step, or the metal layer forming step. An example of the surface activation treatment is a plasma treatment. Details of the surface activation treatment will be described later.

[0263] The lamination step is preferably performed 2 to 20 times, more preferably 2 to 9 times. For example, a structure having 2 to 20 resin layers, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferred, and a structure having 2 to 9 resin layers is even more preferred. Each of the layers may be the same or different in composition, shape, film thickness, etc.

[0264] In the present invention, a particularly preferred embodiment is one in which, after providing a metal layer, a cured product (resin layer) of the resin composition of the present invention is further formed so as to cover the metal layer.Specific examples include an embodiment in which the steps of (a) film formation step, (b) exposure step, (c) development step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step are repeated in this order, or an embodiment in which the steps of (a) film formation step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step are repeated in this order.By alternately performing the lamination step of laminating the resin composition layer (resin layer) of the present invention and the metal layer formation step, the resin composition layer (resin layer) of the present invention and the metal layer can be alternately laminated.

[0265] (Surface Activation Treatment Step) The method for producing a laminate of the present invention preferably includes a surface activation treatment step in which at least a portion of the metal layer and the resin composition layer are surface-activated. The surface activation treatment step is usually performed after the metal layer formation step, but after the development step (preferably after at least one of the heating step and the post-development exposure step), the resin composition layer may be surface-activated before the metal layer formation step. The surface activation treatment may be performed only on at least a portion of the metal layer, or only on at least a portion of the resin composition layer after exposure, or may be performed on at least a portion of both the metal layer and the resin composition layer after exposure. The surface activation treatment is preferably performed on at least a portion of the metal layer, and it is preferable to perform the surface activation treatment on part or all of the region of the metal layer on which the resin composition layer is to be formed. In this way, by performing the surface activation treatment on the surface of the metal layer, adhesion with the resin composition layer (film) provided on the surface can be improved. The surface activation treatment is also preferably performed on part or all of the resin composition layer (resin layer) after exposure. In this way, by performing the surface activation treatment on the surface of the resin composition layer, adhesion with the metal layer or resin layer provided on the surface that has been surface-activated can be improved. In particular, when negative development is performed, when the resin composition layer is cured, it is less susceptible to damage due to surface treatment and adhesion is likely to be improved. The surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of International Publication No. 2021 / 112189. The contents of this specification are incorporated herein.

[0266] (Semiconductor device and manufacturing method thereof) The present invention also discloses a semiconductor device comprising the cured product or laminate of the present invention. The present invention also discloses a manufacturing method for a semiconductor device comprising the manufacturing method for the cured product or the manufacturing method for the laminate of the present invention. Specific examples of semiconductor devices using the resin composition of the present invention to form an interlayer insulating film for a rewiring layer can be found in paragraphs 0213 to 0218 and FIG. 1 of JP 2016-027357 A, the contents of which are incorporated herein by reference.

[0267] The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

[0268] Synthesis Example 1 Synthesis of Polyimide Precursor (Resin A-1) 109.0 g of pyromellitic anhydride (PMDA) was placed in a 2 L separable flask, 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 mL of γ-butyrolactone were added, and 79.1 g of pyridine was added at room temperature while stirring to obtain a reaction mixture. After the reaction ceased to generate heat, the mixture was allowed to cool to room temperature and allowed to stand for an additional 16 hours. Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 mL of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by a suspension of 98.6 g of 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB) in 350 mL of γ-butyrolactone with stirring over 60 minutes. After further stirring at room temperature for 2 hours, 30 mL of ethyl alcohol was added and stirred for 1 hour, and then 400 mL of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution. The obtained reaction solution was added to 3 L of ethyl alcohol to produce a precipitate consisting of a crude resin. The produced crude resin was collected by filtration and dissolved in 1.5 L of tetrahydrofuran to obtain a crude resin solution. The obtained crude resin solution was added dropwise to 28 L of water to precipitate the resin, and the resulting precipitate was collected by filtration and dried in vacuum to obtain powdered Resin A-1. １ H-NMR confirmed that the structure of Resin A-1 was a structure represented by the following formula (A-1). The subscripts in parentheses represent the content (mol %) of the repeating unit. However, in the structure represented by formula (A-1), the imidizable moieties are imidized in accordance with the imidization rate described below. This also applies to Resins A-2 to A-10 below. The weight average molecular weight (Mw) and imidization rate (%) of Resin A-1 are shown in the table below.

[0269] [Method for Measuring Imidization Ratio] Resins A-1 to A-22 described below were each dissolved in γ-butyrolactone, diluted to 2,000 mPa s, and applied to a silicon wafer by spin coating to form a resin layer. The silicon wafer to which the obtained resin layer was applied was dried on a hot plate at 110°C for 5 minutes, yielding a resin layer with a uniform thickness of approximately 15 μm after film formation on the silicon wafer. The resin layer was measured by the ATR method using a NicoletiS20 (manufactured by Thermofisher) in a measurement range of 4,000 to 700 cm. －１ The measurement was carried out 50 times. －１ Around (1350-1450 cm －１ (If there are multiple peaks, the peak with the greatest intensity) and 1500 cm －１ Around (1460-1550 cm －１ The imidization index B was calculated in the same manner for a film that was heated at a heating rate of 10°C / min in a nitrogen atmosphere and heated at 350°C for 1 hour, and the imidization rate of the resin was calculated by dividing the imidization index A by the imidization index B.

[0270] Synthesis Examples 2 to 7, 10 Synthesis of Polyimide Precursors (Resins A-2 to A-7, and A-10) Resins A-2 to A-7 and A-10 were synthesized in the same manner as in Synthesis Example 1, except that the raw materials used were changed as appropriate. １ H-NMR confirmed that the structures of Resins A-2 to A-7 and Resin A-10 were represented by the following formulas (A-2) to (A-7) and (A-10), respectively. Furthermore, resins with different imidization rates were synthesized by adjusting the reaction time. The weight-average molecular weight (Mw), imidization rate (%), and C=C value (mmol / g) at an imidization rate of 0% of these resins are listed in the table below. In the structures below, the subscripts of the repeating units indicate the molar ratio of each repeating unit.

[0271] Synthesis Example 8 Synthesis of Polyimide (Resin A-8) 15.0 g (51.0 mmol) of 4,4'-biphthalic anhydride, 6.63 g (12.8 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 12.4 g (57.4 mmol) of 4,4'-diamino-3,3'-dihydroxybiphenyl, and 1.39 g (12.8 mmol) of 4-aminophenol were dissolved in 125 mL of NMP and stirred at 200°C for 3 hours under a nitrogen atmosphere to obtain a polyimide. Next, 0.1 g of TEMPO and 29.7 g (191.2 mmol) of MOI (2-isocyanatoethyl methacrylate) were added at room temperature, and the mixture was heated to 60°C. After that, 0.1 g of Neostan U-600 (Nitto Kasei Co., Ltd., inorganic bismuth) was added and stirred for 3 hours. To the resulting polyimide solution, 375 ml of THF was added, and the mixture was added dropwise to 1500 ml of methanol to precipitate the polymer. The polymer collected by filtration was dried under reduced pressure at 40°C for 1 day to obtain polyimide (A-8) as a powder. １ H-NMR confirmed that the structure of Resin A-8 was a structure represented by the following formula (A-8). The weight average molecular weight (Mw) and imidization rate (%) of Resin A-8 are shown in the table below. In the following structure, the subscripts of the repeating units indicate the molar ratio of each repeating unit. b and d form a repeating unit together with a or c, and a and c form a repeating unit together with b or d or are bonded to e.

[0272] Synthesis Example 9 Synthesis of Polyimide (Resin A-9) 20.0 g (38.4 mmol) of 4,4′-(4,4′-isopropylidenediphenoxy)diphthalic anhydride, 3.74 g (17.3 mmol) of 4,4′-diamino-3,3′-dihydroxybiphenyl, 1.87 g (17.3 mmol) of p-phenylenediamine, and 0.84 g (7.7 mmol) of 4-aminophenol were dissolved in 125 ml of NMP, and the solution was stirred at 200° C. for 3 hours under a nitrogen atmosphere to obtain a polyimide. The resulting polyimide-containing solution was brought to room temperature, and 0.42 g of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), 12.90 g (84.5 mmol) of 4-chloromethylstyrene, 12.85 g (93.0 mmol) of potassium carbonate, and 1.12 g (6.8 mmol) of potassium iodide were added, followed by stirring at 90°C for 14 hours. 375 ml of THF was added to the resulting polyimide solution, and the salt was removed by filtration. The resulting filtrate was added dropwise to 1500 ml of methanol to precipitate the polymer. The polymer collected by filtration was dried under reduced pressure at 40°C for 1 day, yielding polyimide (A-9) as a powder. １ H-NMR confirmed that the structure of Resin A-9 was a structure represented by the following formula (A-9). The weight-average molecular weight (Mw) and imidization rate (%) of Resin A-9 are shown in the table below. In the following structure, the subscripts of the repeating units indicate the molar ratio of each repeating unit. b and d form a repeating unit with a or c, and a and c form a repeating unit with b or d or are bonded to e.

[0273] <Examples and Comparative Examples> In each example, the components listed in the table below were mixed to obtain a photosensitive resin composition. In the comparative examples, the components listed in the table below were mixed to obtain a comparative composition. Specifically, the content of each component listed in the table was the amount (parts by mass) listed in the "parts by mass" column in each column of the table. The obtained photosensitive resin composition and comparative composition were pressure-filtered using a polytetrafluoroethylene filter with a pore width of 0.5 μm. In the tables, "-" indicates that the composition did not contain the corresponding component.

[0274]

[0275]

[0276] Details of each component listed in the table are as follows:

[0277] [Resins] A-1 to A-10: Resins A-1 to A-10 synthesized above

[0278] [Polymerizable compounds] B-1: Compound having the following structure (tetraethylene glycol dimethacrylate) B-2: DPHA: Dipentaerythritol (penta / hexa)acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: NK Ester A-DPH) B-3: Pentaerythritol tetraacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) B-4: Polyethylene glycol dimethacrylate (n = approximately 4) (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0279] [Photopolymerization initiator] C-1: Irgacure OXE01 (manufactured by BASF) C-2: Irgacure OXE02 (manufactured by BASF) C-3: SpeedCure PDO (manufactured by Arkema) C-4: Compound having the following structure

[0280] [Polymerization inhibitors] D-1: 4-hydroxy-TEMPO free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) D-2: phenothiazine (manufactured by Tokyo Chemical Industry Co., Ltd.) D-3: 2-nitroso-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.) D-4: compound having the following structure

[0281] [UV absorbers (light absorbers)] X-1: Compound having the following structure X-2: Adekastab LA-32 (triazole-based) (manufactured by ADEKA Corporation) X-3: Ester of 2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-1,1'-spirobi(1H-indene)-5,5',6,6',7,7'hexanol and 1,2-naphthoquinone-(2)-diazo-5-sulfonic acid (compound having the following structure; * indicates a bonding site.)

[0282] [Silane coupling agent] E-1: N-[3-(triethoxysilyl)propyl]phthalamic acid

[0283] [Migration inhibitor] F-1: 5-aminotetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0284] [Base generator] G-1: Compound having the following structure G-2: Compound having the following structure

[0285] [Metal Complex] H-1: Compound having the following structure H-2: Orgatix TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd.)

[0286] [Solvents] I-1: N-methylpyrrolidone I-2: Ethyl lactate I-3: γ-butyrolactone I-4: Dimethyl sulfoxide I-5: N,N-dimethylacetamide I-6: γ-valerolactone

[0287] [Surfactants] F-1: F-554 (manufactured by DIC) F-2: KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd.) F-3: TSF4445 (manufactured by Across Industries LLC)

[0288] [Other additives] M-1: N-phenyldiethanolamine (Tokyo Chemical Industry Co., Ltd.)

[0289] <Evaluation> [Evaluation of in-plane orientation coefficient] In each example and comparative example, a photosensitive resin composition or a comparative composition was applied to a silicon wafer by spin coating to form a resin composition layer. The silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 110°C for 5 minutes, to obtain a resin composition layer having a uniform thickness of about 15 µm after film formation on the silicon wafer. The obtained resin composition layer was exposed to a Ushio exposure machine (light source: 500 W / m ２ , ultra-high pressure mercury lamp) at 400 mJ / cm ２ The front surface was exposed to light with an exposure energy of 1000 W. The temperature was increased at a rate of 10°C / min under a nitrogen atmosphere, and the resin layer (cured product) was heated at 230°C for 3 hours. The cured resin layer (cured product) was then immersed in a 4.9% by mass aqueous solution of hydrofluoric acid, and the cured film was peeled off from the silicon wafer. The in-plane orientation coefficient f zx The obtained f zxThe evaluation was carried out according to the following evaluation criteria, and the evaluation results are shown in the column of "In-plane orientation coefficient" in the table. - Evaluation criteria - A: f zx was between -0.5 and -0.4. zx was greater than -0.4 and less than -0.3. zx was greater than -0.3 and less than -0.2. zx was greater than -0.2 and less than -0.1. zx exceeded -0.1.

[0290] [Evaluation of Thermal Expansion (CTE)] In each Example and Comparative Example, a photosensitive resin composition or a comparative composition was applied to a silicon wafer by spin coating to form a resin composition layer. The silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 110°C for 5 minutes to obtain a resin composition layer having a uniform thickness of about 15 µm after film formation on the silicon wafer. The obtained resin composition layer was then exposed to a Ushio exposure machine (light source: 500 W / m ２ , ultra-high pressure mercury lamp) at 400 mJ / cm ２The film was exposed using a dumbbell-shaped mask at an exposure energy of 100 uV. The dumbbell shape was a No. 7 dumbbell shape as described in JIS K 6251:2017. The exposed resin composition layer (resin layer) was developed with cyclopentanone until the unexposed areas were removed, and then rinsed with PGMEA for 30 seconds. The temperature was then increased at a rate of 10°C / min under a nitrogen atmosphere, and the film was heated to 230°C for 3 hours. The cured resin layer (cured product) was immersed in a 4.9% by mass aqueous solution of hydrofluoric acid, and a dumbbell-shaped cured product (test specimen) was peeled off from the silicon wafer (sample width: 2 mm, sample length: 35 mm). The CTE of the test specimen prepared above was measured at 25°C to 125°C using a TMA450 (TA Instruments). The heating and cooling conditions during evaluation were as follows (1) to (4). (1) The temperature was increased from room temperature to 130°C at a temperature increase rate of 5°C / min. (2) The temperature was decreased from 130°C to 10°C at a temperature decrease rate of 5°C / min. (3) The temperature was increased from 10°C to 300°C at a temperature increase rate of 5°C / min. (4) The sample was allowed to cool naturally to room temperature. The elongation (displacement) of the sample was measured during the temperature increase and decrease processes of (1) to (4) above, and the elongation (displacement) of the sample at 25°C and 125°C in process (3) was divided by the temperature to calculate the thermal expansion coefficient. (For example, if the length of the sample at 25°C was 50 mm and the length of the sample at 125°C was 50.2 mm, the displacement was calculated to be 0.4% = 4000 ppm, and the thermal expansion coefficient was 4000 / (125-25) = 40 ppm / °C.) The obtained CTE was evaluated according to the following evaluation criteria, and the evaluation results are recorded in the "CTE" column of the table. -Evaluation criteria- A: CTE was less than 20 ppm / °C. B: CTE was 20 ppm / °C or more and less than 30 ppm / °C. C: CTE was 30 ppm / °C or more and less than 40 ppm / °C. D: CTE was 40 ppm / °C or more and less than 60 ppm / °C. E: CTE was 60 ppm / °C or more.

[0291] [Evaluation of Resolution] The photosensitive resin composition used in each Example and Comparative Example was applied in the form of a layer by spin coating onto the surface of a thin copper layer of a resin substrate having a thin copper layer formed on its surface, and dried at 110°C for 5 minutes to form a resin composition layer having a thickness of 7 μm after film formation. The obtained resin composition layer was then subjected to a spin coating of 100 to 800 mJ / cm using an i-line stepper (Canon: FPA-3000i5, NA=0.5, σ=0.7) using a square via mask having a pattern formed in 0.5 μm increments from 0.5 to 10 μm. ２ in the range of 50 mJ / cm ２ The film was exposed to each exposure dose in increments. Subsequently, the film was developed with cyclopentanone until the unexposed areas were removed, rinsed with PGMEA for 30 seconds, and then heated at a heating rate of 10°C / min under a nitrogen atmosphere and heated at 230°C for 3 hours. The minimum opening mask diameter of the obtained cured product was determined by cross-sectional observation of the opening pattern portion using a scanning microscope S-4800 (manufactured by Hitachi High-Technologies Corporation) and evaluated according to the following evaluation criteria. The minimum opening mask diameter was defined as the smallest mask diameter among those that formed an opening pattern with at least one of the above exposure doses. The evaluation results are shown in the "Resolution" column in the table. -Evaluation Criteria- A: The minimum opening mask diameter was 3 μm or less. B: The minimum opening mask diameter was greater than 3 μm and less than 4 μm. C: The minimum opening mask diameter was greater than 4 μm and less than 5 μm. D: The minimum opening mask diameter was greater than 5 μm and less than 7 μm. E: The minimum opening mask diameter exceeded 7 μm.

[0292] The above results show that the photosensitive resin composition according to the present invention can produce a cured product with a small thermal expansion coefficient and high resolution. In comparison, the cured product produced from the composition according to Comparative Example 1 has a large thermal expansion coefficient and low resolution.

[0293] Example 101 The photosensitive resin composition used in Example 1 was applied in the form of a layer by spin coating to the surface of a substrate on which copper wiring with 2 μm lines and spaces was formed, and dried at 110° C. for 5 minutes to form a resin composition layer with a thickness of 5 μm. Then, using an i-line stepper (Canon: FPA-3000i5), a wavelength of 365 nm and 300 mJ / cm２ The photosensitive resin composition of Example 1 was exposed to light at 1000 W. The resulting film was then developed with cyclopentanone for 15 seconds and rinsed with PGMEA for 30 seconds to obtain a pattern. The photosensitive resin composition of Example 1 exhibited excellent resolution in forming an interlayer insulating film for a rewiring layer. The temperature was then increased at a rate of 10°C / min under a nitrogen atmosphere until it reached 230°C, at which point it was maintained at 230°C for 3 hours to form an interlayer insulating film for a rewiring layer. This interlayer insulating film for a rewiring layer exhibited excellent insulating properties. Furthermore, when semiconductor devices were manufactured using these interlayer insulating films for a rewiring layer, it was confirmed that they operated without any problems.

Claims

1. A photosensitive resin composition comprising a resin having at least one member selected from the group consisting of a polyimide precursor having a group containing an ethylenically unsaturated bond and a polyimide having a group containing an ethylenically unsaturated bond, and a photopolymerization initiator, the composition providing a cured film obtained by heating the composition at 230°C for 3 hours having an in-plane orientation coefficient of -0.50 to -0.

10.

2. The photosensitive resin composition according to claim 1, wherein the in-plane orientation coefficient is -0.50 to -0.

20.

3. The photosensitive resin composition according to claim 1, wherein the resin contains at least one of a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2): In formula (1), X １ represents an organic group having a valence of 4+m; Y １ represents an organic group having a valence of 2+n; R １ Each of n and m independently represents an integer of 0 to 4, n+m is 1 or more, and at least one of the following conditions a and b is satisfied. Condition a: X １ has a group represented by any one of the following formulas (X-1) to (X-4). １ has a group represented by the following formula (Y-1) or formula (Y-2). In formula (2), X ２ represents a tetravalent organic group; Y ２ represents a divalent organic group; R ２１ and R ２２ are each independently a hydrogen atom or a monovalent organic group; R ２１ and R ２２ At least one of the above is a monovalent organic group having an ethylenically unsaturated bond, and satisfies at least one of the following conditions c and d. Condition c: X ２ has a group represented by any one of the following formulas (X-1) to (X-4). ２ has a group represented by the following formula (Y-1) or formula (Y-2). In formula (X-1), R each independently represents a bonding site with a substituent or other structure, n each independently represents an integer of 0 to 3, and * represents a bonding site with a carbonyl group. In formula (X-2), R each independently represents a bonding site with a substituent or other structure, n represents an integer of 0 to 2, and * represents a bonding site with a carbonyl group. In formula (X-3), * represents a bonding site with a carbonyl group. In formula (X-4), R each independently represents a bonding site with a substituent or other structure, n represents an integer of 0 to 2, and * represents a bonding site with a carbonyl group. In formula (Y-1), R each independently represents a bonding site with a substituent or other structure, n each independently represents an integer of 0 to 2, m represents an integer of 1 or more, and * represents a bonding site with a nitrogen atom. In formula (Y-2), R each independently represents a substituent or a bonding site to another structure, n each independently represents an integer of 0 to 2, m represents an integer of 1 or more, and * represents a bonding site to a nitrogen atom.

4. A photosensitive resin composition comprising a resin containing at least one of a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), and a photopolymerization initiator. In formula (1), X １ represents an organic group having a valence of 4+m; Y １ represents an organic group having a valence of 2+n; R １ Each of n and m independently represents an integer of 0 to 4, n+m is 1 or more, and at least one of the following conditions a and b is satisfied. Condition a: X １ has a group represented by any one of the following formulas (X-1) to (X-4). １ has a group represented by the following formula (Y-1) or formula (Y-2). In formula (2), X ２ represents a tetravalent organic group; Y ２ represents a divalent organic group; R ２１ and R ２２ are each independently a hydrogen atom or a monovalent organic group; R ２１ and R ２２ At least one of the above is a monovalent organic group having an ethylenically unsaturated bond, and satisfies at least one of the following conditions c and d. Condition c: X ２ has a group represented by any one of the following formulas (X-1) to (X-4). ２ has a group represented by the following formula (Y-1) or formula (Y-2). In formula (X-1), R each independently represents a bonding site with a substituent or other structure, n each independently represents an integer of 0 to 3, and * represents a bonding site with a carbonyl group. In formula (X-2), R each independently represents a bonding site with a substituent or other structure, n represents an integer of 0 to 2, and * represents a bonding site with a carbonyl group. In formula (X-3), * represents a bonding site with a carbonyl group. In formula (X-4), R each independently represents a bonding site with a substituent or other structure, n represents an integer of 0 to 2, and * represents a bonding site with a carbonyl group. In formula (Y-1), R each independently represents a bonding site with a substituent or other structure, n each independently represents an integer of 0 to 2, m represents an integer of 1 or more, and * represents a bonding site with a nitrogen atom. In formula (Y-2), R each independently represents a substituent or a bonding site to another structure, n each independently represents an integer of 0 to 2, m represents an integer of 1 or more, and * represents a bonding site to a nitrogen atom.

5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the content of the photopolymerization initiator is 1 mass % or more based on the total solid content of the composition.

6. The photosensitive resin composition according to any one of claims 1 to 4, further comprising a radical polymerization inhibitor.

7. The photosensitive resin composition according to any one of claims 1 to 4, further comprising at least one compound selected from the group consisting of nitroso compounds, N-oxide compounds, N-oxyl compounds and phenothiazine compounds.

8. The photosensitive resin composition according to any one of claims 1 to 4, further comprising a light absorbing agent.

9. The photosensitive resin composition according to any one of claims 1 to 4, further comprising at least one compound selected from the group consisting of naphthoquinone diazide compounds, azomethine compounds, indole compounds, benzotriazole compounds, cyanoacrylate compounds, triazine compounds, and anthracene compounds.

10. The photosensitive resin composition according to claim 6, wherein the content of the radical polymerization inhibitor is 0.1 mass % or more based on the total solid content of the composition.

11. The photosensitive resin composition according to any one of claims 1 to 4, further comprising a polymerizable compound.

12. The photosensitive resin composition according to claim 11, wherein the polymerizable compound has two or more polymerizable groups.

13. The photosensitive resin composition according to claim 11, wherein the polymerizable compound has a polymerizable group value of 1.0 to 15 mmol / g.

14. The photosensitive resin composition according to any one of claims 1 to 4, wherein a cured film obtained by heating at 230°C for 3 hours contains a resin having a repeating unit represented by formula (A-1). In formula (A-1), X １ represents an organic group having a valence of 4+m; Y １ represents an organic group having a valence of 2+n, * represents a bonding site with another structure, n and m each independently represent an integer of 0 to 4, n+m is 0 to 4, and at least one of the following conditions a and b is satisfied. Condition a: X １ has a group represented by any one of the following formulas (X-1) to (X-4). １ has a group represented by the following formula (Y-1) or formula (Y-2). In formula (X-1), R each independently represents a bonding site with a substituent or other structure, n each independently represents an integer of 0 to 3, and * represents a bonding site with a carbonyl group. In formula (X-2), R each independently represents a bonding site with a substituent or other structure, n represents an integer of 0 to 2, and * represents a bonding site with a carbonyl group. In formula (X-3), * represents a bonding site with a carbonyl group. In formula (X-4), R each independently represents a bonding site with a substituent or other structure, n represents an integer of 0 to 2, and * represents a bonding site with a carbonyl group. In formula (Y-1), R each independently represents a bonding site with a substituent or other structure, n each independently represents an integer of 0 to 2, m represents an integer of 1 or more, and * represents a bonding site with a nitrogen atom. In formula (Y-2), R each independently represents a substituent or a bonding site to another structure, n each independently represents an integer of 0 to 2, m represents an integer of 1 or more, and * represents a bonding site to a nitrogen atom.

15. The photosensitive resin composition according to any one of claims 1 to 4, which is used for forming an interlayer insulating film for a rewiring layer.

16. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 4.

17. A laminate comprising two or more layers of the cured product according to claim 16, and including a metal layer between any two of the layers of the cured product.

18. A method for producing a cured product, comprising a film-forming step of applying the photosensitive resin composition according to any one of claims 1 to 4 onto a substrate to form a film.

19. The method for producing a cured product according to claim 18, comprising an exposure step of selectively exposing the film to light, and a development step of developing the film with a developer to form a pattern.

20. A method for producing a cured product according to claim 18, comprising a heating step of heating the film at 50 to 450°C.

21. A method for producing a laminate, comprising the method for producing the cured product according to claim 18.

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

23. A semiconductor device comprising the cured product according to claim 16.

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