TW202506830A - Resin composition, cured product, laminate, method for producing cured product, method for producing laminate, method for producing semiconductor element, and semiconductor element - Google Patents

Abstract

A resin composition, a cured product obtained by curing the composition, a laminate containing the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device including the method for producing the cured product, and a semiconductor device containing the cured product. The resin composition comprises: a resin A which is a polyimide and contains a structure represented by the following formula (A-1) in an amount of 0.20 to 5 mmol/g relative to the mass of the resin A; a polymerization initiator; and a polymerizable compound, wherein in the formula (A-1), L ^A1 represents a single bond or an m+1 valent linking group, R ^R1 each independently represents a hydrogen atom or an organic group, two R ^R1s may be linked, m represents an integer greater than 1, and * represents a bonding site with other atoms.

Description

Resin composition, cured product, laminate, method for producing cured product, method for producing laminate, method for producing semiconductor element, and semiconductor element

The present invention relates to a resin composition, a cured product, a laminate, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor element, and a semiconductor element.

Nowadays, the technology of resin materials made of resin compositions containing resins is being used in various fields. For example, the use of the above-mentioned resin materials is not particularly limited. If semiconductor components for mounting are taken as an example, it can be listed as an insulating film, a sealing material, or a protective film. In addition, it can also be used as a base film or a cover film of a flexible substrate, etc.

The resin composition can be applied by a known coating method, and therefore, it can be said that the resin composition has excellent manufacturing adaptability, such as high degree of design freedom in terms of shape, size, and application position when applied. In terms of such excellent manufacturing adaptability, the application expansion of the resin composition in the industry is increasingly expected.

For example, Patent Document 1 discloses a photosensitive resin composition comprising: a bis(cis-butylene)imide compound (I) obtained by reacting a diamine (A) derived from a dimer acid, a tetracarboxylic dianhydride (C) having an alicyclic structure, and maleic anhydride, and having a cyclic imide bond; and a photopolymerization initiator (II), wherein the photopolymerization initiator (II) is a compound having an oxime structure or a 9-thioxanthone structure.

[Patent Document 1] Japanese Patent Application Publication No. 2022-115907

Regarding a cured product obtained by curing a resin composition, it is required to reduce the dielectric loss tangent of the cured product in terms of suppressing transmission loss and the like.

The object of the present invention is to provide a resin composition capable of obtaining a cured product having a low dielectric loss tangent, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for manufacturing the cured product, a method for manufacturing the laminate, a method for manufacturing a semiconductor device including the method for manufacturing the cured product, and a semiconductor device including the cured product.

Representative embodiments of the present invention are shown below. <1> A resin composition comprising: a resin A which is a polyimide and contains a structure represented by the following formula (A-1) in an amount of 0.20 to 5 mmol/g relative to the mass of the resin A; a polymerization initiator; and a polymerizable compound. [Chemical Formula 1] In the formula (A-1), L ^A1 represents a single bond or an m+1 valent linking group, R ^R1 each independently represents a hydrogen atom or an organic group, two R ^R1s may be linked, m represents an integer greater than 1, and * represents a bonding site with other atoms. <2> The resin composition as described in <1>, wherein the structure represented by the above formula (A-1) is contained in a side chain in the resin A. <3> The resin composition as described in <1> or <2>, wherein the free radical polymerizable group value of the above resin A is 0.20 to 5 mmol/g. <4> The resin composition as described in any one of <1> to <3>, wherein L ^A1 in the formula (A-1) contains an aromatic group or an aliphatic saturated hydrocarbon group having 4 or more carbon atoms. <5> The resin composition as described in any one of <1> to <4>, further comprising a resin A2 as a polyimide precursor. <6> The resin composition as described in any one of <1> to <3>, wherein the resin A comprises a repeating unit represented by the following formula (1-1). [Chemical Formula 2] In formula (1-1), ^X1 represents an organic group having 4 or more carbon atoms, ^Y1 represents an organic group having 4 or more carbon atoms, ^R1 each independently represents a structure represented by the following formula (R-1), m represents an integer of 0 to 4, and n represents an integer of 1 or more. [Chemical Formula 3] In formula (R-1), ^L1 represents an a2+1 valent linking group, ^Z1 represents an aromatic group, a cyclic aliphatic group or a linear or branched aliphatic saturated hydrocarbon group, R ^R1 each independently represents a hydrogen atom or an organic group, two R ^R1s may be linked, a1 represents an integer greater than 1 and less than the maximum number of substituents of ^Z1 , a2 represents an integer greater than 1, and * represents a bonding site with ^X1 or ^Y1 in formula (1-1). <7> The resin composition as described in <6>, wherein ^X1 and ^Y1 in formula (1-1) each contain a structure obtained by removing two or more hydrogen atoms from a structure represented by any one of the following formulas (V-1) to (V-4). [Chemical Formula 4] In formula (V-2), ^RX1 is independently a hydrogen atom, an alkyl group or a halogenated alkyl group. In formula (V-3), ^RX2 and ^RX3 are independently a hydrogen atom or a substituent, and ^RX2 and ^RX3 may be bonded to form a ring structure. <8> The resin composition described in <6>, which contains a repeating unit represented by formula (1-1) and has at least one group selected from the group consisting of a linear or branched monovalent aliphatic hydrocarbon group having 6 or more carbon atoms, and a cyclic aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted by a linear aliphatic hydrocarbon group having 4 or more carbon atoms. <9> A resin composition comprising: a resin B comprising a repeating unit represented by the following formula (1-1); a resin C comprising at least one of the repeating units represented by the following formula (2-1) and the following formula (3-1); a polymerization initiator; and a polymerizable compound. [Chemical Formula 5] In formula (1-1), ^X1 represents an organic group having 4 or more carbon atoms, ^Y1 represents an organic group having 4 or more carbon atoms, ^Y1 is not bonded to the nitrogen atom via a linking group outside the repeating unit, ^R1 each independently represents a structure represented by the following formula (R-1), m represents an integer of 0 to 4, and n represents an integer of 1 or more. [Chemical Formula 6] In formula (R-1), ^L1 represents an a2+1 valent linking group, ^Z1 represents an aromatic group, a cyclic aliphatic group, or a linear or branched aliphatic saturated hydrocarbon group, R ^R1 each independently represents a hydrogen atom or an organic group, two R ^R1s may be linked, a1 represents an integer greater than 1 and less than the maximum number of substituents of ^Z1 , a2 represents an integer greater than 1, and * represents a bonding site with ^X1 or ^Y1 in formula (1-1). [Chemical Formula 7] In formula (2-1), ^X2 represents an organic group having 4 or more carbon atoms, ^Y2 represents an organic group having 4 or more carbon atoms, ^R2 each independently represents a group represented by the following formula (R-2), and n represents an integer greater than 1. In formula (3-1), ^X3 represents an organic group having 4 or more carbon atoms, ^Y3 represents an organic group having 4 or more carbon atoms, ^A3 and ^A4 each independently represent an oxygen atom or -NR ^N -, ^RN represents a hydrogen atom or a monovalent organic group, ^R3 and ^R4 each independently represent a hydrogen atom or a monovalent organic group, ^R2 each independently represents a group represented by the following formula (R-2), and n represents an integer greater than 0. [Chemical formula 8] In the formula (R-2), ^L2 represents a b2+1 valent linking group, ^Z2 represents a b1+1 valent organic group, ^A2 represents a methacryloyloxy group, an acryloxy group, a methacrylamide group, an acrylamide group, a vinyl group, a styryl group, an allyl group or a vinyl ether group, b1 represents an integer greater than 1 and less than the maximum number of substituents of ^Z2 , b2 represents an integer greater than 1, and * represents a bonding site with ^Y2 in the formula (2-1) or ^Y3 in the formula (3-1). <10> The resin composition according to <9>, wherein in the formula (3-1), ^R3 and ^R4 are groups having an ethylenically unsaturated bond, and ^X3 has a structure obtained by removing two or more hydrogen atoms from a structure represented by any one of the formulas (V-1) to (V-4). <11> The resin composition as described in <9> or <10>, wherein ^X1 and Y1 in formula (1-1) ^each contain a structure obtained by removing two or more hydrogen atoms from a structure represented by any one of the following formulas (V-1) to (V-4). [Chemical Formula 9] In formula (V-2), ^RX1 is independently a hydrogen atom, an alkyl group or a halogenated alkyl group. In formula (V-3), ^RX2 and ^RX3 are independently a hydrogen atom or a substituent, and ^RX2 and ^RX3 may be bonded to form a ring structure. <12> The resin composition as described in any one of <9> to <11>, wherein the resin B has at least one group selected from the group consisting of a linear or branched monovalent aliphatic hydrocarbon group having 6 or more carbon atoms, and a cyclic aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted by a linear aliphatic hydrocarbon group having 4 or more carbon atoms. <13> The resin composition according to any one of <1> to <12>, wherein when the resin composition is used to form a cured film having a film thickness of 10 μm, the cured film has a light transmittance of 15% or more at a wavelength of 365 nm. <14> The resin composition according to any one of <1> to <13>, wherein the melting point of the polymerizable compound is 25° C. or less. <15> The resin composition according to any one of <1> to <14>, wherein the ClogP of the polymerizable compound is 3 or more. <16> The resin composition according to any one of <1> to <15>, comprising an azole compound and a silane coupling agent. <17> A resin composition as described in any one of <1> to <16>, which is used to form an interlayer insulating film for a redistribution layer. <18> A cured product obtained by curing the resin composition as described in any one of <1> to <17>. <19> A laminate comprising two or more layers composed of the cured product as described in <18>, and a metal layer between any of the layers composed of the cured product. <20> A method for producing a cured product, comprising a film forming step of applying the resin composition as described in any one of <1> to <12> to a substrate to form a film. ＜21＞A method for producing a hardened material as described in ＜20＞, comprising: an exposure step of selectively exposing the above-mentioned film; and a developing step of developing the above-mentioned film using a developer to form a pattern. ＜22＞A method for producing a hardened material as described in ＜20＞ or ＜21＞, comprising a heating step of heating the above-mentioned film at 50 to 450°C. ＜23＞A method for producing a laminate, comprising the method for producing a hardened material as described in ＜20＞. ＜24＞A method for producing a semiconductor element, comprising the method for producing a hardened material as described in ＜20＞. ＜25＞A semiconductor element comprising the hardened material as described in ＜18＞. [Effect of the invention]

According to the present invention, there can be provided a resin composition capable of obtaining a cured product having a low dielectric loss tangent, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for manufacturing the cured product, a method for manufacturing the laminate, a method for manufacturing a semiconductor device including the method for manufacturing the cured product, and a semiconductor device including the cured product.

The main embodiments of the present invention are described below. However, the present invention is not limited to the embodiments explicitly described. In this specification, the numerical range represented by the symbol "～" means a range including the numerical values recorded before and after "～" as the lower limit and the upper limit, respectively. In this specification, the term "step" means not only independent steps, but also steps that cannot be clearly distinguished from other steps as long as the expected effect of the step can be achieved. In the marking of the base (atomic group) in this specification, the marking without substitution and unsubstituted includes the base (atomic group) without substitution and also includes the base (atomic group) with substitution. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (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, as light used for exposure, there can be listed active light or radiation such as the bright line spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV rays), X-rays, and electron beams. In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", "(meth)acrylic acid" means both or either of "acrylic acid" and "methacrylic acid", and "(meth)acryl" means both or either of "acryl" and "methacryl". In this specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the total solid content refers to the total mass of the components excluding the solvent from all the components of the composition. In addition, in this specification, the solid content concentration refers to the mass percentage of the components other than the solvent relative to the total mass of the composition. In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC) and are defined as polystyrene conversion values. In this specification, for example, HLC-8220GPC (manufactured by TOSOH CORPORATION) is used to connect guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) in series as columns to determine weight average molecular weight (Mw) and number average molecular weight (Mn). Unless otherwise specified, these molecular weights are measured using THF (tetrahydrofuran) as an eluent. However, in the case of low solubility, when THF is not suitable as an eluent, NMP (N-methyl-2-pyrrolidone) can also be used. In addition, unless otherwise specified, a UV ray (ultraviolet) detector with a wavelength of 254nm is used for detection in GPC measurement. In this manual, when the positional relationship of each layer constituting the laminate is recorded as "upper" or "lower", it is sufficient as long as other layers exist on the upper side or lower side of the layer serving as the reference among the multiple layers concerned. In other words, a third layer or element may be further interposed between the layer serving as the reference and the other layers mentioned above, and the layer serving as the reference and the other layers mentioned above do not need to be in contact. Unless otherwise specified, the direction of the stacked layers to the substrate is referred to as "upper", or in the case of the presence of a resin component layer, the direction from the substrate toward the resin component layer is referred to as "upper", and the opposite direction is referred to as "lower". Furthermore, this setting of the up and down direction is for the convenience of explaining this specification. In actual forms, the "up" direction in this specification may also be different from the vertical direction. In this specification, unless otherwise specified, the composition may contain two or more compounds corresponding to the component as each component contained in the composition. In addition, unless otherwise specified, the content of each component in the composition refers to the total content of all compounds corresponding to the component. In this specification, unless otherwise specified, the temperature is 23°C, the air pressure is 101,325Pa (1 atmosphere), and the relative humidity is 50%RH. In this specification, the combination of the best form is the best form.

(Resin composition) The resin composition of the first aspect of the present invention (hereinafter, also referred to as the "first resin composition") contains: resin A, which is a polyimide and contains a structure represented by formula (A-1) in an amount of 0.20 to 5 mmol/g relative to the mass of resin A; a polymerization initiator; and a polymerizable compound. The resin composition of the second aspect of the present invention (hereinafter, also referred to as the "second resin composition") contains: resin B, which contains a repeating unit represented by formula (1-1); resin C, which contains at least one of the repeating units represented by formula (2-1) and formula (3-1); a polymerization initiator; and a polymerizable compound. Hereinafter, the above-mentioned resin A and resin B are also collectively referred to as "specific resins".

The resin composition of the present invention is preferably used to form a photosensitive film (for exposure and development), and is more preferably used to form a film (for 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 element, an interlayer insulating film for a redistribution layer, a stress buffer film, etc., and is preferably used to form an interlayer insulating film for a redistribution layer. In particular, the resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer, which is also one of the better embodiments of the present invention. In addition, the resin composition of the present invention is preferably used to form a photosensitive film for negative development. In the present invention, negative development refers to development in which the non-exposed portion is removed by development during exposure and development, and positive development refers to development in which the exposed portion is removed by development. As the above-mentioned exposure method, the above-mentioned developer, and the above-mentioned developing method, for example, the exposure method described in the exposure step in the description of the method for producing a hardened product described later, and the developer and developing method described in the developing step can be used.

According to the resin composition of the present invention, a hardened material with low dielectric loss tangent can be obtained. The mechanism for achieving the above effect is not yet clear, but it is speculated as follows.

In the first aspect of the resin composition of the present invention, the resin A as a polyimide contains a group represented by formula (A-1) containing a cis-butylene imide group in an amount of 0.20 to 5 mmol/g relative to the mass of the resin A. The resin A in the first aspect of the resin composition of the present invention contains a repeating unit represented by formula (1-1). Historically, as a resin composition containing polyimide, a cured product having excellent physical properties such as chemical resistance can be obtained by using a resin having a polymerizable group such as a (meth)acryloyloxy group, a composition containing a polymerizable compound and a polymerization initiator. Here, for example, since the carbonyl group contained in the (meth)acryloyloxy group can rotate freely, the degree of freedom of movement of the structure in the obtained cured product is sometimes high, resulting in an increase in the dielectric loss tangent. In contrast, it is believed that since the carbonyl group of the cis-butylene diimide group is fixed in the ring structure, it is not easy to rotate freely, and the structure is easy to be fixed, so the dielectric loss tangent is reduced. In addition, it is believed that the cis-butylene diimide group reacts with various structures in the composition, such as addition reaction with phenolic hydroxyl groups, in addition to free radical polymerization, so that in the obtained cured product, the resin and various components or various parts in the resin are cross-linked. That is, it is believed that a strong cross-linking network is formed in the cured product. As a result, it is believed that the hardening property and chemical resistance of the hardened material obtained by exposure can be improved. In addition, it is believed that the polymerization in the succinimidyl group is less likely to be depolymerized by heat, etc., compared with the polymerization in the (meth)acrylate, and therefore, for example, when exposed to high temperature conditions, high humidity conditions or after a long time, it is not easy to cause a decrease in the chemical resistance and adhesion of the hardened material. Furthermore, it is believed that when a film composed of the resin composition of the present invention is exposed and developed to form a pattern, since the resin has a succinimidyl group, the removability of the non-image part by the developer containing an organic solvent is improved, and the resolution is also improved.

Here, Patent Document 1 does not describe a resin composition containing a specific resin.

Hereinafter, the components contained in the resin composition of the present invention will be described in detail.

<Specific resin> [Resin A] The first resin composition of the present invention contains resin A, which is a polyimide and contains a structure represented by the following formula (A-1) in an amount of 0.20 to 5 mmol/g relative to the mass of the resin A. [Chemical formula 10] In formula (A-1), L ^A1 represents a single bond or an m+1 valent linking group, R ^R1 each independently represents a hydrogen atom or an organic group, two R ^R1 may be linked, m represents an integer greater than 1, and * represents a bonding site with other atoms.

In the present invention, a resin having an imidization rate of less than 70% as measured by the following method is referred to as a polyimide precursor, and a resin having an imide structure in a repeating unit and having an imidization rate of 70% or more as described below is referred to as a polyimide. In the present invention, an imide structure refers to a structure represented by *-C(=O)N(-*)C(=O)-*, where * represents a bonding site with other structures, preferably a bonding site with a carbon atom, and more preferably a bonding site with a quaternary carbon atom. In the present invention, a polyimide is preferably a resin having a repeating unit containing an imide ring structure in a molecular chain. Furthermore, when the polyimide is a linear resin, it is preferred that the polyimide is a resin having a repeating unit containing an imide structure in the main chain, and it is more preferred that the polyimide is a resin having a repeating unit containing an imide ring structure in the main chain. In the present invention, "main chain" refers to the longest bond chain in the resin molecule, and "side chain" refers to other bond chains.

The imidization rate of the resin is measured by the following method. The infrared absorption spectrum of the resin is measured, and the peak intensity P1 at around 1377 cm ^-1 , which is the absorption peak originating from the imide structure, is calculated. Then, after the specific resin is heat treated at 350°C for 1 hour, the infrared absorption spectrum is measured again, and the peak intensity P2 at around 1377 cm ^- 1 is calculated. The obtained peak intensities P1 and P2 can be used to calculate the imidization rate of the specific resin according to the following formula. Imidization rate (%) = (peak intensity P1/peak intensity P2) × 100

The imidization rate of the specific resin is preferably 75% or more, more preferably 80% or more, and even more preferably 90% or more in terms of the film strength, insulation, flatness, etc. of the obtained organic film. The upper limit of the above imidization rate is not particularly limited, and it can be 100% or less. In addition, in terms of reducing the dielectric loss tangent, the content of the imide structure in the specific resin is preferably 3mmol/g or less, and more preferably 2.5mmol/g or less. The lower limit of the above content is not particularly limited, but can be set to 0.5mmol/g or more, for example.

-Formula (A-1)- The structure represented by formula (A-1) is preferably contained in the side chain of resin A. In addition, * in formula (A-1) is preferably a bonding site with an atom contained in the main chain of resin A. In addition, at least one of R and ^R1 in formula (A-1) may be a structure contained in the main chain of the resin.

In formula (A-1), L ^A1 preferably contains an aromatic group or an aliphatic saturated alkyl group having 4 or more carbon atoms. It is preferred that the aromatic group or the aliphatic saturated alkyl group having 4 or more carbon atoms is bonded to the cis-butenediimide group (i.e., the nitrogen atom in formula A-1) by a single bond without a linking group. The aromatic group may be any of an aromatic alkyl group and an aromatic heterocyclic group, but an aromatic alkyl group is preferred. As the aromatic alkyl group, an aromatic alkyl group having 6 to 10 carbon atoms is preferred, and an aromatic alkyl group having 6 carbon atoms is more preferred. As heteroatoms in the aromatic heterocyclic group, oxygen atoms, nitrogen atoms, sulfur atoms, etc. may be listed. The number of heteroatoms in the aromatic heterocyclic group is preferably 1 or 2. In addition, as the aromatic heterocyclic group, a 5-membered or 6-membered ring containing the above-mentioned heteroatoms is preferred. In addition, the aromatic heterocyclic group may be condensed with other aromatic heterocyclic groups or other aromatic alkyl ring groups. As the aliphatic saturated alkyl group having 4 or more carbon atoms, it may be any of a linear, branched, cyclic or a combination thereof. The aliphatic saturated alkyl group having 4 or more carbon atoms preferably has 4 to 20 carbon atoms, and more preferably 5 to 10 carbon atoms.

Furthermore, L ^A1 is preferably the following formula (A-1-1) or formula (A-2-2). [Chemical formula 11] In formula (A-1-1), ^Z1 represents -O- or -NR ^N -, ^RN represents a hydrogen atom or a monovalent organic group, ^RA1 represents an aromatic group or an aliphatic saturated hydrocarbon group having 4 or more carbon atoms, m represents an integer of 1 or more, * has the same meaning as that of * in formula (A-1), and # represents a bonding site with the nitrogen atom in formula (A-1). In formula (A-1-2), ^Z2 represents -O- or -NR ^N -, ^RN represents a hydrogen atom or a monovalent organic group, ^RA2 represents an aromatic group or an aliphatic saturated hydrocarbon group having 4 or more carbon atoms, m represents an integer of 1 or more, * has the same meaning as that of * in formula (A-1), and # represents a bonding site with the nitrogen atom in formula (A-1).

In formula (A-1-1), ^Z1 is preferably -O-. ^RN is preferably a hydrogen atom or a alkyl group, more preferably a hydrogen atom or an alkyl group, and still more preferably a hydrogen atom. In formula (A-1-1), ^RA1 represents an aromatic group or an aliphatic saturated alkyl group having 4 or more carbon atoms, and preferred embodiments of such groups are as described above. In formula (A-1-1), m has the same meaning as m in formula (A-1), and preferred embodiments are also the same.

In formula (A-1-2), ^Z2 is preferably -O-. Preferred embodiments of ^RN are as described above. Preferred embodiments of ^RA2 in formula (A-1-2) are the same as preferred embodiments of ^RA1 in formula (A-1-1). In formula (A-1-2), m has the same meaning as m in formula (A-1), and preferred embodiments are also the same.

Preferred embodiments of ^RA1 and ^RA2 are shown below, but the present invention is not limited thereto. In the following formula, n independently represents an integer greater than 0, * has the same meaning as * in formula (A-1), and # represents a bonding site with the nitrogen atom in formula (A-1). In the following formula, n is preferably an integer of 0 to 20, and more preferably an integer of 0 to 6. [Chemical Formula 12]

In formula (A-1), R ^R1 are each independently preferably a hydrogen atom or a alkyl group, more preferably a hydrogen atom or an alkyl group, further preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom. In formula (A-1), examples of the ring structure formed by two R ^R1s linked together include cyclohexene ring and the like.

In formula (A-1), m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, further preferably an integer of 1 to 3, and particularly preferably 1 or 2. In addition, the aspect in which m is 1 is also one of the preferred aspects of the present invention.

Resin A contains the structure represented by formula (A-1) in an amount of 0.20 to 5 mmol/g, preferably 0.30 to 4 mmol/g, and more preferably 0.50 to 3 mmol/g relative to the mass of resin A. The content of the structure represented by formula (A-1) in resin A can be confirmed by ¹ H-NMR. Specifically, the content of the structure represented by formula (A-1) in resin A can be calculated from the amount of phenol residue and the amount of phenol used for polymerization by dissolving the polymer in deuterated DMSO and performing ¹ H-NMR (accumulated 128 times). In addition, the radical polymerizable group value (the molar amount of the radical polymerizable group relative to the mass of the resin A) in the resin A is preferably 0.20 to 5 mmol/g, more preferably 0.30 to 4 mmol/g, and even more preferably 0.50 to 3 mmol/g. The radical polymerizable group value in the resin A can be confirmed by ¹ H-NMR. The content of the structure represented by the formula (A-1) in the resin A is preferably 50% or more, more preferably 70% or more, and even more preferably 90% or more relative to the radical polymerizable group value in the resin A. The upper limit of the above ratio is not particularly limited, and it can be 100% or less.

The resin A preferably contains a repeating unit represented by the following formula (1-1). [Chemical formula 13] In formula (1-1), ^X1 represents an organic group having 4 or more carbon atoms, ^Y1 represents an organic group having 4 or more carbon atoms, ^Y1 is not bonded to the nitrogen atom via a linking group outside the repeating unit, ^R1 each independently represents a structure represented by the following formula (R-1), m represents an integer of 0 to 4, and n represents an integer of 1 or more. [Chemical Formula 14] In the formula (R-1), ^L1 represents an a2+1 valent linking group, ^Z1 represents an aromatic group, a cyclic aliphatic group or a linear or branched aliphatic saturated hydrocarbon group, R ^R1 each independently represents a hydrogen atom or an organic group, two R ^R1s may be linked, a1 represents an integer greater than 1 and less than the maximum number of substituents of ^Z1 , a2 represents an integer greater than 1, and * represents a bonding site with ^X1 or ^Y1 in the formula (1-1).

-R ¹ - R ¹ each independently represents a structure represented by the formula (R-1).

In formula (R-1), ^L1 is preferably a group represented by the following formula (L-1). [Chemical Formula 15] In the formula (L-1), Z ^L1 represents -O-, -NR ^N -, -C(=O)O- or -C(=O)NR ^N -, ^RN represents a hydrogen atom or a monovalent organic group, when a2 is 1, L ^X represents a single bond or a alkyl group, when a2 is 2 or more, L ^X represents a alkyl group, Z ^L2 represents a single bond or -O-, -NR ^N -, -C(=O)O- or -C(=O)NR ^N -, ^RN represents a hydrogen atom or a monovalent organic group, * represents a bonding site with X ¹ or Y ¹ in the formula (1-1), and # represents a bonding site with Z ¹ in the formula (R-1).

In the formula (L-1), Z ^L1 is preferably -O- or -C(=O)O-. The preferred embodiment of ^RN when ^{Z L1} is -NR ^N - or -C(=O)NR ^N - is as described above. In the formula (L-1), L ^x is preferably an aromatic alkyl group, an aliphatic saturated alkyl group, or a group represented by a combination thereof. As the aromatic alkyl group, a group obtained by removing two or more hydrogen atoms from a benzene ring is preferred. As the aliphatic saturated alkyl group, an aliphatic saturated alkyl group having 1 to 20 carbon atoms is preferred, and an aliphatic saturated alkyl group having 1 to 10 carbon atoms is more preferred. In the formula (L-1), Z ^L2 is preferably -O- or -C(=O)O-. When Z ^L2 is -NR ^N - or -C(=O)NR ^N -, the preferred embodiment of ^RN is as described above. The preferred embodiment of a2 in formula (L-1) is the same as the preferred embodiment of a2 in formula (R-1).

In the formula (R-1), ^Z1 is preferably an aromatic group or an aliphatic saturated hydrocarbon group having 4 or more carbon atoms. The preferred embodiments are the same as those of ^RA1 in the formula (A-1-1).

In the formula (R-1), preferred aspects of R ^R1 are the same as preferred aspects of R ^R1 in the above formula (A-1).

In formula (R-1), a1 is preferably an integer of 1 to 4, and an integer of 1 to 2 is more preferably. In addition, the embodiment in which a1 is 1 is also one of the preferred embodiments of the present invention. In formula (R-1), a2 represents an integer greater than 1, and 1 or 2 is preferably, and 1 is further preferably.

-X ¹ - The carbon number of X ¹ is 4 or more, preferably 4 to 50, and more preferably 4 to 40. In formula (1-1), X ¹ preferably represents an organic group having a structure formed by removing two or more hydrogen atoms from a structure represented by any one of the following formulas (V-1) to (V-4). Since it is an organic group having a structure formed by removing two or more hydrogen atoms from a structure represented by any one of the following formulas (V-1) to (V-4), the chemical resistance and flatness of the cured product are improved. Furthermore, since it is an organic group having a structure formed by removing two or more hydrogen atoms from a structure represented by any one of the following formulas (V-1) to (V-4), the generation of development residues, the dielectric constant of the cured product, and the thermal expansion coefficient can be suppressed. [Chemical Formula 16] In formula (V-2), ^RX1 is independently a hydrogen atom, an alkyl group or a halogenated alkyl group. In formula (V-3), ^RX2 and ^RX3 are independently a hydrogen atom or a substituent, and ^RX2 and ^RX3 may be bonded to form a ring structure.

In formula (V-2), ^RX1 is preferably independently 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 more preferably a methyl group or a trifluoromethyl group. Halogenated alkyl groups refer to groups in which at least one of the hydrogen atoms of an alkyl group is substituted with a halogen atom. As the halogen atom, F or Cl is preferred, and F is more preferred. In formula (V-3), ^RX2 and ^RX3 are preferably independently a hydrogen atom. When ^RX2 and ^RX3 are bonded to form a ring structure, the structure formed by the bond between ^RX2 and ^RX3 is preferably a single bond, -O- or -C(R) _2- , more preferably -O- or -C(R) _2- , and more preferably -O-. R represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom.

When ^X1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-1), ^X1 is preferably a group represented by the following formula (V-1-1). In the following formula, * represents the bonding site of the four carbonyl groups bonded to ^X1 in formula (1-1), and n1 represents an integer of 0 to 5, preferably an integer of 1 to 5. In addition, the hydrogen atoms in the following structure may be further substituted by a known substituent such as a hydroxyl group. [Chemical Formula 17]

When ^X1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-2), ^X1 is preferably a group represented by the following formula (V-2-1) or formula (V-2-2). In terms of reducing the amine value in the resin, the group represented by formula (V-2-2) is preferred. In the present specification, a bond intersecting the edge of a ring structure refers to a bond that replaces any one of the hydrogen atoms in the ring structure. In the following formula, ^LX1 represents a single bond or -O-, and * represents the bonding site of the four carbonyl groups bonded to ^X1 in formula (1-1). In addition, the definition and preferred embodiment of ^RX1 are as described above. In addition, the hydrogen atoms in these structures can be further substituted by known substituents such as alkyl groups. [Chemical Formula 18]

When ^X1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-3), ^X1 is preferably a group represented by the following formula (V-3-1) or formula (V-3-2). In terms of reducing the dielectric constant of the cured product, the group represented by formula (V-3-2) is more preferred. In the following formula, * represents the bonding site of the four carbonyl groups bonded to ^X1 in formula (1-1). In addition, the definitions and preferred embodiments of ^RX2 and ^RX3 are as described above. In addition, the hydrogen atoms in these structures may be further substituted by known substituents such as alkyl groups. [Chemical Formula 19]

When ^X1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-4), ^X1 is preferably a group represented by the following formula (V-4-1). In the following formula, * represents the bonding site of the four carbonyl groups bonded to ^X1 in formula (1-1), and n1 represents an integer from 0 to 5. In addition, the hydrogen atoms in the following structure may be further substituted by a known substituent such as a alkyl group. It is also preferred that the hydrogen atoms in the structure represented by (V-4-1) are not substituted. [Chemical Formula 20]

Furthermore, ^X1 may be a tetracarboxylic acid residual group remaining after removing anhydride groups from tetracarboxylic dianhydride as described in paragraphs 0055 to 0057 of JP-A-2023-003421.

Furthermore, it is preferred that ^X1 does not contain an imide bond in its structure. Furthermore, it is preferred that ^X1 does not contain a carbamate bond, a urea bond, or an amide bond in its structure. In the present invention, a carbamate bond refers to a bond represented by *-OC(=O)-NR ^N -*, ^RN represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom. ^RN is preferably a hydrogen atom or a alkyl group, more preferably a hydrogen atom or an alkyl group, and further preferably a hydrogen atom. In the present invention, a urea bond refers to a bond represented by *-NR ^N -C(=O)-NR ^N -*, ^RN each independently represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom. Preferred aspects of ^RN are as described above. In addition, ^X1 preferably does not contain an ester bond in the structure. In the present invention, an ester bond refers to a bond represented by *-OC(=O)-*. Among them, ^X1 preferably does not contain an imide bond, a urethane bond, a urea bond, or an amide bond, and more preferably does not contain an imide bond, a urethane bond, a urea bond, an amide bond, or an ester bond.

Furthermore, ^X1 may be a structure represented by the following formula (X-2), or a structure in which a hydrogen atom of a group represented by ^X2 or a hydrogen atom of a group represented by L3 in the structure represented by (X- ²⁾ is substituted by a group represented by ^R1 in formula (1-1). [Chemical Formula 21] In formula (X-2), ^X2 each independently represents a trivalent linking group, ^L3 represents a divalent linking group, and * represents a bonding site with other structures.

In formula (X-2), ^X2 can be exemplified by a linear or branched aliphatic group, a cyclic aliphatic group and an aromatic group, or a group formed by linking two or more of these groups via a single bond or a linking group. Preferably, it is a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these groups via a single bond or a linking group. More preferably, it is an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group. The linking group is preferably -O-, -S-, -C(=O)-, -S(=O) _2- , an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these groups, and more preferably -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these groups. The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 4 carbon atoms. The halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and more preferably a halogenated alkylene group having 1 to 4 carbon atoms. In addition, as the halogen atom in the above-mentioned halogenated alkylene group, fluorine atom, chlorine atom, bromine atom, iodine atom, etc. can be listed, and fluorine atom is preferred. The above-mentioned halogenated alkylene group may have hydrogen atoms, and all hydrogen atoms may be substituted by halogen atoms, but all hydrogen atoms are preferably substituted by halogen atoms. As examples of preferred halogenated alkylene groups, (ditrifluoromethyl)methylene can be listed. As the above-mentioned arylene group, phenylene or naphthylene is preferred, phenylene is more preferred, and 1,3-phenylene or 1,4-phenylene is further preferred.

In addition, ^X2 is preferably derived from a tricarboxylic acid compound in which at least one carboxyl group can be halogenated. As the above-mentioned halogenation, chlorination is preferred. In the present invention, a compound having three carboxyl groups is referred to as a tricarboxylic acid compound. Two of the three carboxyl groups of the above-mentioned tricarboxylic acid compound can be anhydrided. As the tricarboxylic acid compound that can be halogenated, branched aliphatic, cyclic aliphatic or aromatic tricarboxylic acid compounds can be listed. Such tricarboxylic acid compounds can be used only one, or two or more.

It is preferred that ^X2 does not contain an imide structure in its structure. It is also preferred that ^X2 does not contain a urethane bond, a urea bond, or an amide bond in its structure. In addition, it is preferred that ^X2 does not contain an ester bond in its structure. Among these, it is preferred that ^X2 does not contain an imide structure, a urethane bond, a urea bond, or an amide bond, and it is more preferred that X2 does not contain an imide structure, a urethane bond, a urea bond, an amide bond, or an ester bond.

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

Specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, compounds in which phthalic acid (or phthalic anhydride) and benzoic acid are linked via a single bond, -O-, -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -SO ₂ - or phenylene groups, etc. These compounds may be compounds in which two carboxyl groups are anhydrified (e.g., trimellitic anhydride) or compounds in which at least one carboxyl group is halogenated (e.g., chlorotrimellityl anhydride).

In formula (X-2), ^L3 can be exemplified by a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, or a group formed by linking two or more of these groups via a single bond or a linking group. Preferably, it is a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these groups via a single bond or a linking group. More preferably, it is an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group. The linking group is preferably -O-, -S-, -C(=O)-, -S(=O) _2- , an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these groups, and more preferably -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these groups. The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 4 carbon atoms. The halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and more preferably a halogenated alkylene group having 1 to 4 carbon atoms. In addition, as the halogen atom in the above-mentioned halogenated alkylene group, fluorine atom, chlorine atom, bromine atom, iodine atom, etc. can be listed, and fluorine atom is preferred. The above-mentioned halogenated alkylene group may have hydrogen atoms, and all hydrogen atoms may be substituted by halogen atoms, but all hydrogen atoms are preferably substituted by halogen atoms. As examples of preferred halogenated alkylene groups, (ditrifluoromethyl)methylene can be listed. As the above-mentioned arylene group, phenylene or naphthylene is preferred, phenylene is more preferred, and 1,3-phenylene or 1,4-phenylene is further preferred.

Furthermore, ^X1 may be a structure represented by the following formula (X-3), or a structure in which a hydrogen atom of a group represented by ^X2 or a hydrogen atom of a group represented by L3 in the structure represented by (X- ³⁾ is substituted by a group represented by ^R1 in formula (1-1). [Chemical Formula 22] In formula (X-3), ^X2 independently represents a trivalent linking group, ^L3 represents a divalent linking group, and * represents a bonding site with other structures. In formula (X-3), preferred embodiments of ^X2 and ^L3 are the same as preferred embodiments of ^X2 and ^L3 in formula (X-2).

-Y ¹ - The carbon number of Y ¹ is 4 or more, preferably 4 to 50, and more preferably 4 to 40. In formula (1-1), Y ¹ may be a group containing a structure formed by removing two or more hydrogen atoms from a structure represented by any one of formulas (V-1) to (V-4). Since it is an organic group containing a structure formed by removing two or more hydrogen atoms from a structure represented by any one of formulas (V-1) to (V-4), the chemical resistance and flatness of the cured product are improved.

When ^Y1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-1), ^Y1 is preferably a group represented by the following formula (V-1-2). In the following formula, * represents the bonding site of the two nitrogen atoms to which ^Y1 in formula (1-1) is bonded, and n1 represents an integer of 1 to 5. In addition, the hydrogen atom in the following structure may be further substituted by a known substituent such as a hydroxyl group. [Chemical Formula 23]

When ^Y1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-2), ^Y1 is preferably a group represented by the following formula (V-2-3) or formula (V-2-4), and a group represented by formula (V-2-4) is preferably used in terms of lowering the dielectric constant of the cured product. In the following formula, ^LX1 represents a single bond or -O-, and * represents a bonding site to two nitrogen atoms bonded to ^Y1 in formula (1-1). In addition, the preferred embodiment of ^RX1 is as described above. In addition, the hydrogen atoms in these structures may be further substituted by known substituents such as alkyl groups. [Chemical Formula 24]

When ^Y1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-3), ^Y1 is preferably a group represented by the following formula (V-3-3) or formula (V-3-4). In terms of lowering the dielectric constant of the cured product, the group represented by formula (V-3-3) is more preferred. In the following formula, * represents the bonding site of the two nitrogen atoms bonded to ^Y1 in formula (1-1). In addition, the hydrogen atoms in these structures may be further substituted by known substituents such as alkyl groups. [Chemical Formula 25]

When ^Y1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-4), ^Y1 is preferably a group represented by the following formula (V-4-2) or formula (V-4-3). In the following formula, * represents the bonding site of the two nitrogen atoms bonded to ^Y1 in formula (1-1), and n1 represents an integer of 0 to 5. In addition, the embodiment in which n1 is 0 is also one of the preferred embodiments of the present invention. In addition, the hydrogen atom in the following structure may be further substituted by a known substituent such as a hydroxyl group. [Chemical Formula 26]

In addition, ^Y1 may be a group described in paragraphs 0042 to 0053 of Japanese Patent Publication No. 2023-003421. In addition, ^Y1 preferably does not contain an imide bond in the structure. In addition, ^Y1 preferably does not contain a carbamate bond, a urea bond, or an amide bond in the structure. In addition, ^Y1 preferably does not contain an ester bond in the structure. Among them, ^Y1 preferably does not contain an imide bond, a carbamate bond, a urea bond, or an amide bond, and more preferably does not contain an imide bond, a carbamate bond, a urea bond, an amide bond, or an ester bond.

Among them, ^X1 and ^Y1 in formula (1-1) are preferably organic groups each containing a structure obtained by removing two or more hydrogen atoms from a structure represented by any one of formulas (V-1) to (V-4). Preferred embodiments of these groups are as described above.

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

The second resin composition contains resin B, and the resin B contains a repeating unit represented by formula (1-1). The preferred embodiment of resin B is the same as the preferred embodiment of resin A except that it must contain a repeating unit represented by formula (1-1).

Resin A preferably contains a repeating unit represented by formula (1-1) and has at least one group selected from the group consisting of a linear or branched monovalent aliphatic hydrocarbon group having 6 or more carbon atoms, and a cyclic aliphatic hydrocarbon group in which one or more hydrogen atoms are replaced by a linear aliphatic hydrocarbon group having 4 or more carbon atoms. Resin B preferably has at least one group selected from the group consisting of a linear or branched monovalent aliphatic hydrocarbon group having 6 or more carbon atoms, and a cyclic aliphatic hydrocarbon group in which one or more hydrogen atoms are replaced by a linear aliphatic hydrocarbon group having 4 or more carbon atoms. Hereinafter, at least one group selected from the group consisting of a linear or branched monovalent aliphatic alkyl group having 6 or more carbon atoms and a cyclic aliphatic alkyl group in which one or more hydrogen atoms are replaced by a linear aliphatic alkyl group having 4 or more carbon atoms is also described as a "specific substituent", a linear or branched monovalent aliphatic alkyl group having 6 or more carbon atoms is also described as a specific substituent A, and a cyclic aliphatic alkyl group in which one or more hydrogen atoms are replaced by a linear aliphatic alkyl group having 4 or more carbon atoms is also described as a specific substituent B. Furthermore, for example, when the specific resin has a substituent X which is a cyclic aliphatic alkyl group in which one or more hydrogen atoms are replaced by a linear aliphatic alkyl group having 6 or more carbon atoms, it can be said that the linear aliphatic alkyl group having 6 or more carbon atoms of the substituent X corresponds to the specific substituent A, and it can also be said that the substituent X as a whole corresponds to the specific substituent B.

-Specific substituent A- In terms of resolution, the specific resin preferably has a group corresponding to the specific substituent A. The specific resin preferably has a linear or branched alkyl group with 6 or more carbon atoms as the specific substituent A. Furthermore, the specific resin preferably has a linear monovalent aliphatic hydrocarbon group with 6 or more carbon atoms as the specific substituent A, and more preferably has a linear alkyl group with 6 or more carbon atoms as the specific substituent A. The hydrogen atom in the specific substituent A is preferably unsubstituted or substituted with a halogen atom. As the halogen atom, a fluorine atom is preferably used. Furthermore, the embodiment in which the hydrogen atom in the specific substituent A is unsubstituted is also one of the preferred embodiments of the present invention. The carbon number of the specific substituent A is preferably 6 to 30, and more preferably 6 to 20.

-Specific substituent B- The cyclic aliphatic alkyl group in the specific substituent B is preferably a cyclic aliphatic saturated alkyl group. The cyclic aliphatic alkyl group in the specific substituent B is preferably a 5-10 membered ring, more preferably a 5-8 membered ring, and even more preferably a 6 membered ring. The cyclic aliphatic alkyl group in the specific substituent B may be condensed with other ring structures. As the other ring structure, a hydrocarbon ring structure is preferred, and an aliphatic hydrocarbon ring structure is more preferred. The linear aliphatic alkyl group having 4 or more carbon atoms in the specific substituent B is preferably a linear alkyl group having 4 or more carbon atoms. The carbon number of the linear aliphatic alkyl group having 4 or more carbon atoms in the specific substituent B is preferably 4 to 30, more preferably 4 to 10, and even more preferably 4 to 8.

-Content of specific substituent- The molar amount of the specific substituent relative to the number average molecular weight of the specific resin is preferably 0.01 to 10 mmol/g, more preferably 0.1 to 5 mmol/g, and even more preferably 0.1 to 2 mmol/g.

When the specific resin has a specific substituent, the resin may contain a group having the specific substituent as a substituent of the above-mentioned ^X1 or ^Y1 , but it may also be contained at the end of the specific resin. Specifically, the specific resin preferably has a structure represented by any one of the following formulas (TA-1) to (TA-3). [Chemical Formula 27] In the formula (TA-1), X ³¹ represents a tetravalent organic group, Y ³¹ represents a divalent organic group, R ³¹ represents a group having at least one group selected from the group consisting of a linear or branched monovalent aliphatic hydrocarbon group having 6 or more carbon atoms and a cyclic aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted by a linear aliphatic hydrocarbon group having 4 or more carbon atoms, R ³¹ is a group not containing an imide structure, and * represents a bonding site with other structures. In formula (TA-2), X ³¹ represents a tetravalent organic group, Y ³¹ represents a divalent organic group, R ³² represents a group having at least one group selected from the group consisting of a linear or branched monovalent aliphatic hydrocarbon group having 6 or more carbon atoms and a cyclic aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted by a linear aliphatic hydrocarbon group having 4 or more carbon atoms, R ³² is a group not containing an imide structure, and * represents a bonding site with other structures. In the formula (TA-3), X ³¹ represents a tetravalent organic group, Y ³¹ represents a divalent organic group, R ³³ and R ³⁴ each independently represent -OH or a monovalent organic group, at least one of R ³³ and R ³⁴ is a group having at least one group selected from the group consisting of a linear or branched monovalent aliphatic hydrocarbon group having 6 or more carbon atoms and a cyclic aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted by a linear aliphatic hydrocarbon group having 4 or more carbon atoms, R ³³ and R ³⁴ are groups not containing an imide structure, and * represents a bonding site with other structures.

The specific resin preferably has a structure represented by any one of formula (TA-1) to formula (TA-3) at the end of the main chain. In addition, the specific resin preferably has a structure represented by formula (TA-1).

In formula (TA-1) to formula (TA-3), preferred embodiments of X ³¹ and Y ³¹ are the same as preferred embodiments of the group consisting of X ¹ and m R ^1s and the group consisting of Y ¹ and n R ^1s in formula (1-1). In formula (TA-1), R ³¹ is preferably a group represented by the following formula (R-31). [Chemical Formula 28] In formula (R-31), when a31 is 1, L ³¹ represents a single bond or an a31+1 valent linking group, when a31 is 2 or more, L ³¹ represents an a31+1 valent linking group, Z ³¹ represents a single bond, -O- or -NR ^N -, ^RN represents a hydrogen atom or a monovalent organic group, A ¹ represents a group having at least one group selected from the group consisting of a linear or branched monovalent aliphatic hydrocarbon group having 6 or more carbon atoms, and a cyclic aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted by a linear aliphatic hydrocarbon group having 4 or more carbon atoms, and a31 represents an integer of 1 or more.

In formula (R-31), when a31 is 1, L ³¹ is preferably a single bond. In formula (R-31), when L ³¹ is an a31+1 valent linking group, L ³¹ is preferably a alkyl group or a group represented by a combination of a alkyl group and at least one selected from the group consisting of -O-, -C(=O)- and -NR ^N -. Preferred aspects of ^RN are as described above. In formula (R-31), Z ³¹ is preferably a single bond. In formula (R-31), preferred aspects of A ¹ are the same as preferred aspects of A ¹ in the above formula (R-1). In formula (R-31), a31 is preferably an integer of 1 to 4, and more preferably 1 or 2. Furthermore, the aspect in which a31 is 1 is also one of the better aspects of the present invention.

In the formula (TA-2), R ³² is preferably a group represented by the following formula (R-32). [Chemical Formula 29] In the formula (R-32), ^RN represents a hydrogen atom or a monovalent organic group, when a32 is 1, ^L32 represents a single bond or an a32+1 valent linking group, when a32 is 2 or more, ^L32 represents an a32+1 valent linking group, ^Z32 represents a single bond, -O- or ^-NRN- , ^RN represents a hydrogen atom or a monovalent organic group, ^A1 represents a group having at least one group selected from the group consisting of a linear or branched monovalent aliphatic hydrocarbon group having 6 or more carbon atoms and a cyclic aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted by a linear aliphatic hydrocarbon group having 4 or more carbon atoms, and a32 represents an integer of 1 or more.

In the formula (R-32), preferred aspects of ^RN are as described above. In the formula (R-32), preferred aspects of ^L32 , ^Z32 , ^A1 and a32 are the same as preferred aspects of ^L31 , ^Z31 , ^A1 and a31 in the above formula (R-31).

In formula (TA-3), at least one of R ³³ and R ³⁴ is preferably a group represented by the following formula (R-33). [Chemical formula 30] In the formula (R-33), Z ³³ represents -O- or -NR ^N -, when a33 is 1, L ³³ represents a single bond or an a33+1 valent linking group, when a33 is 2 or more, L ³³ represents an a33+1 valent linking group, Z ³⁴ represents a single bond, -O- or -NR ^N -, ^RN represents a hydrogen atom or a monovalent organic group, A ¹ represents a group having at least one group selected from the group consisting of a linear or branched monovalent aliphatic hydrocarbon group having 6 or more carbon atoms, and a cyclic aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted by a linear aliphatic hydrocarbon group having 4 or more carbon atoms, and a33 represents an integer greater than 1. In the formula (R-33), Z ³³ is preferably -NR ^N -. Preferred embodiments of ^RN are as described above. In the formula (R-33), preferred aspects of L ³³ , Z ³⁴ , A ¹ and a33 are the same as preferred aspects of L ³¹ , Z ³¹ , A ¹ and a31 in the above-mentioned formula (R-31).

In formula (TA-3), one of R ³³ and R ³⁴ may be -OH, or may be an alkoxy group having no specific substituent such as -OC ₂ H ₅ .

The specific resin may contain a repeating unit represented by formula (4). The repeating unit corresponding to the repeating unit represented by formula (1-1) is set to be non-corresponding to the repeating unit represented by formula (4). [Chemical formula 31] In formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group.

R ¹³¹ represents a divalent organic group. Examples of the divalent organic group include those described in paragraphs 0042 to 0053 of JP-A-2023-003421. These descriptions are incorporated into this specification.

R ¹³² represents a tetravalent organic group. Examples of R ¹³² include compounds described in paragraphs 0055 to 0057 of JP-A-2023-003421. These descriptions are incorporated into the present specification.

The content of the repeating unit represented by formula (1-1) relative to the total mass of the specific resin is preferably 30 mass% or more, more preferably 50 mass% or more, further preferably 70 mass% or more, and particularly preferably 80 mass% or more. The upper limit of the above content is not particularly limited, and may also be 100 mass%. When the specific resin is polyimide, the total content of the repeating unit represented by formula (1-1) and the repeating unit represented by formula (4) relative to the total mass of the specific resin is preferably 50 mass% or more, more preferably 70 mass% or more, further preferably 80 mass% or more, and particularly preferably 90 mass% or more. The upper limit of the above content is not particularly limited, and may also be 100 mass%. Furthermore, when the specific resin contains a repeating unit represented by formula (1-1), it may contain two or more repeating units represented by formula (1-1) having different structures. In this case, the total amount is preferably within the above range. When the specific resin contains a repeating unit represented by formula (4), it may contain two or more repeating units represented by formula (4) having different structures. In this case, the total amount is preferably within the above range.

[Dissolution rate] The resin composition of the present invention preferably contains a resin having a dissolution rate of 0.01 to 0.2 μm/sec in cyclopentanone for a resin film having a film thickness of 10 μm as a specific resin. The lower limit of the above dissolution rate is preferably 0.02 μm/sec or more, and more preferably 0.05 μm/sec or more. The upper limit of the above dissolution rate is preferably 0.2 μm/sec or less, and more preferably 0.15 μm/sec or less.

The above-mentioned film for measuring the dissolution rate of a specific resin can be obtained, for example, by preparing a solution in which a specific resin is dissolved in a solvent, applying the solution to a substrate such as a silicon wafer, and drying as needed. When drying is performed, the film thickness after drying becomes 10 μm.

As a solvent for dissolving the specific resin used to prepare the above solution, γ-butyrolactone can be used. If it is difficult to implement that the specific resin is not dissolved in γ-butyrolactone, the solvent can be appropriately changed to a solvent that dissolves the specific resin, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide, etc. The content of the specific resin in the above solution can be set to 30% by mass relative to the total mass of the solvent. However, if it is difficult to form a 10μm film with the above content, or the solubility of the specific resin is small and cannot be prepared, the above content can also be appropriately set to, for example, between 10 and 60% by mass. Furthermore, if a 10μm film cannot be obtained, the value can be obtained by measuring the film thickness that can be formed and converting it to a film thickness of 10μm.

As a substrate, a silicon wafer can be used. If it is difficult to form a film with a thickness of 10 μm on a silicon wafer, other substrates with different properties such as surface wettability can be used.

There is no particular limitation on the method of applying the resin composition to the substrate, as long as the film thickness is 10 μm, and a spin coating method can be used. When it is difficult to form a film with a thickness of 10 μm by spin coating, a 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.

It is preferred that the drying be performed until the amount of solvent in the film becomes 0.1 mass % or less. There are no particular restrictions on drying conditions, and drying can be performed by heating. Moreover, when sufficient drying is difficult to perform only by heating, decompression can be further performed. Drying can be performed in the atmosphere. However, when the resin composition contains components that are easily modified by oxygen, it can also be performed under conditions such as nitrogen replacement and vacuum. There are no particular restrictions on drying methods, but examples include a heating plate. However, when the above-mentioned decompression, inert gas replacement, etc. are required, an oven with a decompression function, an oven with a gas replacement function, etc. can also be used. When drying by heating is performed, drying can be performed at a heating temperature of, for example, 110°C. However, when drying at 110°C is difficult, the drying temperature can 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 is performed, the drying time (time exposed to the above-mentioned heating temperature) can be, for example, 5 minutes. However, when drying within 5 minutes is difficult, the drying time can 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 is performed by heating, the heating rate is not particularly limited, and can be set to 5°C/minute, for example. When drying is difficult at the above heating rate, the heating rate can be appropriately changed between 1-12°C/minute or 2-10°C/minute depending on the type of solvent contained in the resin composition.

The dissolution rate of the film in cyclopentanone can be determined by immersing the silicon wafer with the film formed in cyclopentanone for 15 seconds and measuring the film thickness before and after immersion using an elliptical polarimeter. The film is immersed in cyclopentanone without heating other than the above drying. It is preferred that the amount of cyclopentanone used for immersion is 30 times the volume of the film. The temperature of cyclopentanone, film, and silicon wafer during immersion is set to 23°C. If the film is completely dissolved or the film thickness does not change at all, the dissolution rate can be calculated by appropriately changing the immersion time.

[Transmittance] When the resin composition of the present invention is used to form a cured product with a film thickness of 10 μm, the transmittance of the cured product at a wavelength of 365 nm is preferably 15% or more, more preferably 20% or more, and even more preferably 25% or more. The upper limit of the transmittance is not particularly limited and can be 100%. The cured product can be obtained, for example, by the following method: after applying the resin composition of the present invention on a substrate such as a silicon wafer, drying it, and exposing the entire surface with i-rays at an exposure energy of 500 mJ/ ^cm2 , the temperature is increased at a heating rate of 10°C/min in a nitrogen environment, and heated at 230°C for 180 minutes. The transmittance can be measured using a spectrophotometer. In addition, the above-mentioned substrate, the method of applying the composition to the substrate, the drying method, etc. can also be carried out by the same method as the above-mentioned dissolution rate measurement, and the preferred embodiment is also the same. As the heating method when heating at 230°C for 180 minutes, the same method as the drying method in the above-mentioned dissolution rate measurement can be used.

The weight average molecular weight (Mw) of the specific resin is preferably 3,000 to 100,000. The lower limit of the Mw is preferably 5,000 or more, more preferably 8,000 or more, and even more preferably 10,000 or more. The upper limit of the Mw is preferably 50,000 or less, more preferably 40,000 or less, and even more preferably 25,000 or less. By setting the weight average molecular weight to 3,000 or more, the folding resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties (e.g., elongation at break), the weight average molecular weight is particularly preferably 5,000 or more. The number average molecular weight (Mn) of the specific resin is preferably 1,000 to 40,000, more preferably 2,000 to 30,000, and further preferably 5,000 to 20,000. The molecular weight dispersion of the specific resin is preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.0 or more. The upper limit of the molecular weight dispersion of the polyimide is not particularly limited, for example, preferably 7.0 or less, more preferably 6.5 or less, further preferably 6.0 or less, further preferably 4.5 or less, and particularly preferably 3.0 or less. In this specification, the molecular weight dispersion is a value calculated by weight average molecular weight/number average molecular weight. When the resin composition contains multiple resins as specific resins, it is preferred that the weight average molecular weight, number average molecular weight and dispersion of at least one resin are within the above ranges. It is also preferred that the weight average molecular weight, number average molecular weight and dispersion calculated by treating the multiple resins as one resin are within the above ranges.

[Method for producing specific resin] The specific resin can be obtained by, for example, the following methods: a method of reacting tetracarboxylic dianhydride with diamine at low temperature, a method of reacting tetracarboxylic dianhydride with diamine at low temperature to obtain polyamide and esterifying with a condensation agent or an alkylating agent, a method of obtaining a diester from tetracarboxylic dianhydride and alcohol and then reacting the diester in the presence of diamine and a condensation agent, a method of obtaining a diester from tetracarboxylic dianhydride and alcohol and then halogenating the remaining dicarboxylic acid with a halogenating agent and then reacting the diester with diamine, etc. Among the above-mentioned production methods, the method of obtaining a diester from tetracarboxylic dianhydride and alcohol and then halogenating the remaining dicarboxylic acid with a halogenating agent and then reacting the diester with diamine is more preferred. Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, trifluoroacetic anhydride, and the like. Examples of the alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, triethyl orthoformate, and the like. Examples of the halogenating agent include sulfinyl chloride, oxalyl chloride, phosphinoyl chloride, and the like. Furthermore, when polyimide is to be obtained as a specific resin, the following method can be used for synthesis: a method of completely imidizing the resin obtained by the above method using a known imidization reaction method; or a method of stopping the imidization reaction midway and introducing a part of the imide structure; and further a method of introducing a part of the imide structure by mixing the completely imidized polymer with the polyimide precursor. In addition, other known methods for synthesizing polyimide can also be applied. In the method for producing a specific resin, it is preferred to use an organic solvent when performing the reaction. The organic solvent may be one or more. As an organic solvent, it can be appropriately determined according to the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (DME), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc. In the method for producing a specific resin, it is preferred to add an alkaline compound during the reaction. The alkaline compound may be one or more. The alkaline compound can be appropriately determined according to the raw material, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-aminopyridine, etc.

-Capping agent- In the method for producing a specific resin, in order to further improve the storage stability, it is preferred to cap the carboxylic anhydride, anhydride derivative or amine group remaining at the resin end of the specific resin. When capping the carboxylic anhydride and anhydride derivative remaining at the resin end, monoalcohols, phenols, thiols, thiophenols, monoamines, etc. can be listed as the capping agent. In terms of reactivity and film stability, monoalcohols, phenols, and monoamines are more preferred. Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol, secondary alcohols such as isopropanol, 2-butanol, cyclohexanol, cyclopentanol, and 1-methoxy-2-propanol, and tertiary alcohols such as tertiary butanol and adamantanol. Preferred phenol compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene. Moreover, as preferred monoamine compounds, there can be mentioned aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy -7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these can be used, and multiple different terminal groups can be introduced by reacting multiple end-capping agents. In addition, when the amine group at the end of the resin is capped, it can be capped with a compound having a functional group that can react with the amine group. Preferable end-capping agents for amino groups are carboxylic anhydride, carboxylic acid chloride, carboxylic acid bromide, sulfonic acid chloride, sulfonic acid anhydride, sulfonic acid carboxylic anhydride, etc., and carboxylic acid anhydride and carboxylic acid chloride are more preferred. Preferable compounds of carboxylic anhydride include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, etc. Preferable compounds of carboxylic acid chloride include acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, neopentanoyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyl chloride, stearyl chloride, benzoyl chloride, etc. In addition, the end of the resin can be reacted with an amino acid in a compound having an amino group and a hydroxyl group, such as p-aminophenol, and then the hydroxyl group can be reacted with a compound that reacts with a hydroxyl group, such as 6-butenediimidehexyl chloride. By such a reaction, a cis-butenediimide group can be introduced into the end of a specific resin. In addition, by using a diamine having a polymerizable group such as a cis-butenediimide group as a raw material, i.e., a diamine, when polymerizing a specific resin, a polymerizable group can be introduced into the specific resin.

Furthermore, by reacting a compound represented by the following formula (T-1) with a resin having a carboxylic acid (or carboxylic anhydride) at the end, the structure represented by the above formula (TA-1) or formula (TA-3) can be introduced into the resin. [Chemical formula 32] In formula (T-1), when a31 is 1, L ³¹ represents a single bond or an a31+1 valent linking group, when a31 is 2 or more, L ³¹ represents an a31+1 valent linking group, Z ³¹ represents a single bond, -O- or -NR ^N -, ^RN represents a hydrogen atom or a monovalent organic group, A ¹ represents a group having at least one group selected from the group consisting of a linear or branched monovalent aliphatic hydrocarbon group having 6 or more carbon atoms, and a cyclic aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted by a linear aliphatic hydrocarbon group having 4 or more carbon atoms, and a31 represents an integer of 1 or more. In the formula (T-1), preferred embodiments of L ³¹ , Z ³¹ , A ¹ and a31 are the same as preferred embodiments of L ³¹ , Z ³¹ , A ¹ and a31 in the formula (R-31).

Furthermore, by reacting a compound represented by the following formula (T-2) with a resin having an amine group at the end, the structure represented by the above formula (TA-2) can be introduced into the resin. [Chemical formula 33] In formula (T-2), ^RT represents a hydrogen atom or a halogen atom, ^RN represents a hydrogen atom or a monovalent organic group, when a32 is 1, ^L32 represents a single bond or an a32+1 valent linking group, when a32 is 2 or more, ^L32 represents an a32+1 valent linking group, ^Z32 represents a single bond, -O- or ^-NRN- , ^RN represents a hydrogen atom or a monovalent organic group, ^A1 represents a group having at least one group selected from the group consisting of a linear or branched monovalent aliphatic hydrocarbon group having 6 or more carbon atoms and a cyclic aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted by a linear aliphatic hydrocarbon group having 4 or more carbon atoms, and a32 represents an integer of 1 or more.

In formula (T-2), ^RT is preferably a hydrogen atom or a chlorine atom. In formula (T-2), preferred embodiments of L ³² , Z ³² , A ¹ and a32 are the same as preferred embodiments of L ³² , Z ³² , A ¹ and a32 in formula (R-32).

Furthermore, by reacting a compound represented by the following formula (T-3) with a resin having a carboxylic acid (or carboxylic anhydride) at the end, the structure represented by the above formula (TA-3) can be introduced into the resin. [Chemical formula 34] In formula (T-3), when a31 is 1, L ³¹ represents a single bond or an a31+1 valent linking group, when a31 is 2 or more, L ³¹ represents an a31+1 valent linking group, Z ³¹ represents a single bond, -O- or -NR ^N -, ^RN represents a hydrogen atom or a monovalent organic group, A ¹ represents a group having at least one group selected from the group consisting of a linear or branched monovalent aliphatic hydrocarbon group having 6 or more carbon atoms, and a cyclic aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted by a linear aliphatic hydrocarbon group having 4 or more carbon atoms, and a31 represents an integer of 1 or more. In the formula (T-3), preferred embodiments of L ³¹ , Z ³¹ , A ¹ and a31 are the same as preferred embodiments of L ³¹ , Z ³¹ , A ¹ and a31 in the formula (R-31).

-Solid precipitation- The method for producing a specific resin may include a step of solid precipitation. Specifically, after filtering the water absorption byproduct of the dehydration condensation agent coexisting in the reaction solution as needed, the obtained polymer component is added to a poor solvent such as water, aliphatic lower alcohol or a mixture thereof to precipitate the polymer component, thereby precipitating it as a solid and drying it to obtain the specific resin. In order to increase the degree of purification, the specific resin may be repeatedly subjected to operations such as redissolution, reprecipitation, and drying. It may also further include a step of removing ionic impurities using an ion exchange resin.

[Specific example] As specific examples of the specific resin, polyimide SP-1 to SP-23 in the embodiments described below can be cited, but the present invention is not limited thereto.

[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, more preferably 40% by mass or more, more preferably 50% by mass or more, and most preferably 60% by mass or more relative to 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, more preferably 98% by mass or less, more preferably 97% by mass or less, and even more preferably 95% by mass or less relative to the total solid content of the resin composition. The resin composition of the present invention may contain only one specific resin, or may contain two or more specific resins. When containing two or more types, the total amount is preferably within the above range.

The resin composition of the present invention preferably contains at least two resins. Specifically, the resin composition of the present invention may contain two or more specific resins and other resins described below in total, or may contain two or more specific resins, but it is preferred to contain two or more specific resins.

<Resin A2> The first resin composition preferably further contains a resin A2 which is a polyimide precursor. Resin A2 preferably contains a repeating unit represented by the following formula (3-1). [Chemical Formula 35] In formula (3-1), X ³ represents an organic group having 4 or more carbon atoms, Y ³ represents an organic group having 4 or more carbon atoms, A ³ and A ⁴ each independently represent an oxygen atom or -NR ^N -, RN ^each independently represents a hydrogen atom or a monovalent organic group, R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent organic group, R ² each independently represents a group represented by the following formula (R-2), and n represents an integer greater than 0. [Chemical Formula 36] In formula (R-2), ^L2 represents a b2+1 valent linking group, ^Z2 represents a b1+1 valent organic group, ^A2 represents a methacryloyloxy group, an acryloxy group, a methacrylamide group, an acrylamide group, a vinyl group, a styryl group, an allyl group or a vinyl ether group, b1 represents an integer greater than 1 and less than the maximum number of substituents of ^Z2 , b2 represents an integer greater than 1, and * represents a bonding site with ^Y2 in formula (2-1) or ^Y3 in formula (3-1).

In formula (3-1), preferred embodiments of ^X3 and ^Y3 are the same as preferred embodiments of ^X1 and ^Y1 in formula (1-1).

In formula (3-1), ^A3 and ^A4 are preferably both oxygen atoms. Preferred embodiments of ^RN are as described above.

In formula (3-1), ^R3 and ^R4 each independently represent a hydrogen atom or a monovalent organic group. As the monovalent organic group, a linear or branched alkyl group, a cyclic alkyl group, an aromatic group or a polyalkylene group is preferred. Furthermore, at least one of ^R3 and ^R4 preferably contains a polymerizable group, and it is more preferred that both contain a polymerizable group. It is also preferred that at least one of ^R3 and ^R4 contains two or more polymerizable groups. As the polymerizable group, a group capable of undergoing a crosslinking reaction by the action of heat, free radicals, etc. is preferred, and a free radical polymerizable group is preferred. Specific examples of polymerizable groups include groups having ethylenic unsaturated bonds, alkoxymethyl groups, hydroxymethyl groups, acyloxymethyl groups, epoxy groups, cyclohexyl groups, benzoxazolyl groups, blocked isocyanate groups, and amino groups. As free radical polymerizable groups possessed by the polyimide precursor, groups having ethylenic unsaturated bonds are preferred. As groups having ethylenic unsaturated bonds, vinyl groups, allyl groups, isoallyl groups, 2-methylallyl groups, groups having aromatic rings directly bonded to vinyl groups (e.g., vinylphenyl groups), (meth)acrylamide groups, (meth)acryloyloxy groups, groups represented by the following formula (III), and the like are preferred. Groups represented by the following formula (III) are preferred.

[Chemical formula 37]

In formula (III), R ²⁰⁰ represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, preferably a hydrogen atom or a methyl group. In formula (III), * represents a bonding site with other structures. 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 polyalkylene group. Preferred examples of R ²⁰¹ include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, dodecamethylene, 1,2-butanediyl, 1,3-butanediyl, -CH ₂ CH (OH) CH ₂ -, polyalkyleneoxy groups, more preferred alkylene groups such as ethylene and propylene, -CH ₂ CH (OH) CH ₂ -, cyclohexyl, polyalkyleneoxy groups, and even more preferred alkylene groups such as ethylene and propylene or polyalkyleneoxy groups. In the present invention, polyalkyleneoxy groups refer to groups formed by direct bonding of two or more alkyleneoxy groups. The alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different. When the polyalkoxyl group includes a plurality of alkoxyl groups with different alkylene groups, the arrangement of the alkoxyl groups in the polyalkoxyl group may be a random arrangement, a block arrangement, or an alternating arrangement. The carbon number of the alkylene group (including the carbon number of the substituent when the alkylene group has a substituent) is preferably 2 or more, 2 to 10 is more preferred, 2 to 6 is more preferred, 2 to 5 is further preferred, 2 to 4 is further preferred, 2 or 3 is particularly preferred, and 2 is the most preferred. In addition, the alkylene group may have a substituent. As preferred substituents, alkyl groups, aryl groups, halogen atoms, etc. can be listed. In addition, the number of alkoxyl groups contained in the polyalkoxyl group (the number of repetitions of the polyalkoxyl group) is preferably 2 to 20, 2 to 10 is more preferred, and 2 to 6 is further preferred. As the polyalkyleneoxy group, polyethyleneoxy, polypropyleneoxy, polytrimethyleneoxy, polytetramethyleneoxy or a group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded are preferred in terms of solvent solubility and solvent resistance, polyethyleneoxy or polypropyleneoxy is more preferred, and polyethyleneoxy is further preferred. In the group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, may be arranged in blocks, may be arranged in alternating patterns, etc. The preferred aspect of the number of repetitions of the ethyleneoxy group and the like in these groups is as described above.

In formula (3-1), when R ³ is a hydrogen atom or R ⁴ is a hydrogen atom, the polyimide precursor can form a conjugate 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.

In formula (3-1), ^R3 and ^R4 are groups having ethylenically unsaturated bonds and ^X3 preferably has a structure formed by removing two or more hydrogen atoms from a structure represented by any one of formulas (V-1) to (V-4). Preferred embodiments of the structure formed by removing two or more hydrogen atoms from a structure represented by any one of formulas (V-1) to (V-4) are as described above.

In formula (R-2), ^L2 is preferably a group represented by the following formula (L-2). [Chemical Formula 38] In formula (L-2), ^Lx2 represents a b2+1 valent linking group, b2 represents an integer greater than 1, * represents a bonding site with ^Y1 in formula (1-1), and # represents a bonding site with ^Z2 in formula (R-2). ^Lx2 is preferably an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, further preferably an alkylene group having 1 to 4 carbon atoms, and particularly preferably a methylene group. Preferred aspects of b2 in formula (L-2) are the same as preferred aspects of b2 in formula (R-2).

^Z2 in the formula (R-2) represents a b1+1 valent organic group, preferably an aromatic group or an aliphatic hydrocarbon ring group, and more preferably an aromatic group. The aromatic group may be any of an aromatic hydrocarbon group and a heteroaromatic ring group, but an aromatic hydrocarbon ring group or a heteroaromatic ring group containing a nitrogen atom as a ring member is preferred. As the aromatic hydrocarbon ring in the aromatic hydrocarbon ring group, an aromatic hydrocarbon ring having 6 to 20 carbon atoms is preferred, an aromatic hydrocarbon ring having 6 to 10 carbon atoms is more preferred, and a benzene ring is further preferred. Examples of the heteroaromatic ring in the heteroaromatic ring group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, an imidazole ring, a triazole ring, a tetrazole ring, an oxadiazole ring, a pyridine ring, a pyridine ring, a pyridine ring, a triazole ring, an indole ring, an indazole ring, a benzimidazole ring, and a purine ring. Examples of the aliphatic ring in the cyclic aliphatic group include an aliphatic hydrocarbon ring having 5 to 20 carbon atoms, a pyrrolidine ring, a pyrroline ring, a pyrazolidine ring, an imidazolidinyl ring, a tetrahydrofuran ring, a tetrahydrothiophene ring, a piperidine ring, a piperidine ring, a tetrahydropyran ring, a dioxane ring, and an oxoquinoline ring. Among these, Z ² is preferably a benzene ring, a cyclohexane ring, or an adamantane ring, and more preferably a benzene ring.

^A2 in the formula (R-2) is preferably a methacryloyloxy group, an acryloxy group, a vinyl group or a vinyl ether group, more preferably a vinyl group or a vinyl ether group, and even more preferably a vinyl group.

In formula (R-2), b1 is preferably an integer of 1 to 4, and an integer of 1 to 2 is more preferably. In addition, the embodiment in which b1 is 1 is also one of the preferred embodiments of the present invention. In formula (R-2), b2 represents an integer greater than 1, and 1 or 2 is preferably, and 1 is further preferably.

Furthermore, the number of ester bonds contained in formula (R-2) is preferably 1 or 0.

In formula (3-1), n is preferably an integer from 0 to 4, and more preferably an integer from 0 to 2.

Resin A2 may contain one or more types of repeating units represented by formula (3-1). It may also contain structural isomers of the repeating units represented by formula (3-1). Of course, resin A2 may contain other types of repeating units in addition to the repeating units of formula (3-1).

As an embodiment of the resin A2 of the present invention, the content of the repeating unit represented by the formula (3-1) is 50 mol% or more of all the repeating units. The above content is more preferably 70 mol% or more, more preferably 90 mol% or more, and even more preferably more than 90 mol%. The upper limit of the above content is not particularly limited, and all the repeating units in the resin A2 except the terminal can be the repeating units represented by the formula (3-1).

The weight average molecular weight (Mw) of resin A2 is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and further preferably 15,000 to 40,000. Moreover, the number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and further preferably 4,000 to 20,000. The molecular weight dispersion of resin A2 is preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.0 or more. The upper limit of the molecular weight dispersion of resin A2 is not particularly limited, but, for example, 7.0 or less is preferably, 6.5 or less is more preferably, and 6.0 or less is further preferably. Furthermore, when the resin composition contains multiple resins A2, it is preferred that the weight average molecular weight, number average molecular weight and dispersion of at least one resin A2 are within the above ranges. Furthermore, it is also preferred that the weight average molecular weight, number average molecular weight and dispersion calculated by treating the multiple resins A2 as one resin are within the above ranges.

[Content] The content of resin A2 in the first resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more relative to the total solid content of the resin composition. Moreover, the above content is preferably 70% by mass or less, and even more preferably 60% by mass or less. The content of resin A in the first resin composition relative to the total content of resin A and resin A2 is preferably 5 to 70% by mass, and even more preferably 20 to 60% by mass.

<Resin A3> The first resin composition may further contain a polyimide resin A3 which does not correspond to the above-mentioned resin A. Preferably, the resin A3 contains a repeating unit represented by the following formula (2-1). [Chemical Formula 39] In formula (2-1), ^X2 represents an organic group having 4 or more carbon atoms, ^Y2 represents an organic group having 4 or more carbon atoms, ^R2 each independently represents a group represented by the following formula (R-2), and n represents an integer greater than 1. [Chemical formula 40] In formula (R-2), ^L2 represents a b2+1 valent linking group, ^Z2 represents a b1+1 valent organic group, ^A2 represents a methacryloyloxy group, an acryloxy group, a methacrylamide group, an acrylamide group, a vinyl group, a styryl group, an allyl group or a vinyl ether group, b1 represents an integer greater than 1 and less than the maximum number of substituents of ^Z2 , b2 represents an integer greater than 1, and * represents a bonding site with ^Y2 in formula (2-1) or ^Y3 in formula (3-1).

In formula (2-1), preferred embodiments of ^X2 and ^Y2 are the same as preferred embodiments of ^X1 and ^Y1 in formula (1-1).

In the formula (2-1), the preferred embodiment of the formula (R-2) in R ² is the same as the preferred embodiment of the formula (R-2) in the above formula (3-1).

In formula (2-1), n is preferably an integer of 1 to 4, and more preferably 1 or 2.

Resin A3 may contain one or more repeating units represented by formula (2-1). It may also contain structural isomers of the repeating units represented by formula (2-1). Of course, resin A3 may contain other types of repeating units in addition to the repeating units of formula (2-1).

As an embodiment of the resin A3 of the present invention, the content of the repeating unit represented by the formula (2-1) is 30 mol% or more of all the repeating units. More preferably, the content is 50 mol% or more. The upper limit of the content is not particularly limited, and all the repeating units in the resin A3 except the terminal can be the repeating units represented by the formula (2-1).

Resin A3 may have the above-mentioned specific substituent. The preferred embodiment of the specific substituent is the same as the preferred embodiment of the specific substituent in Resin A. Resin A3 also preferably has a structure represented by any one of the above-mentioned formulas (TA-1) to (TA-3). The preferred embodiment of the structure represented by the formula is as described above.

The weight average molecular weight (Mw) of resin A3 is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and further preferably 15,000 to 40,000. Moreover, the number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and further preferably 4,000 to 20,000. The molecular weight dispersion of resin A3 is preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.0 or more. The upper limit of the molecular weight dispersion of the polyimide precursor is not particularly specified, but for example, 7.0 or less is preferably, 6.5 or less is more preferably, and 6.0 or less is further preferably. In this specification, the molecular weight dispersion is a value calculated by weight average molecular weight/number average molecular weight. In addition, when the resin composition contains a plurality of resins A3 as specific resins, it is preferred that the weight average molecular weight, number average molecular weight and dispersion of at least one resin A3 are within the above ranges. In addition, it is also preferred that the weight average molecular weight, number average molecular weight and dispersion calculated by treating the plurality of resins A3 as one resin are within the above ranges.

[Content] The content of resin A3 in the first resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more relative to the total solid content of the resin composition. Furthermore, the above content is preferably 70% by mass or less, and even more preferably 60% by mass or less. The content of resin A in the first resin composition relative to the total content of resin A and resin A3 is preferably 20 to 80% by mass, and even more preferably 30 to 70% by mass.

<Resin C> The second resin composition contains resin C, which contains at least one of the repeating units represented by formula (2-1) and formula (3-1). Resin C is a resin that does not correspond to resin B. The preferred embodiments of formula (2-1) and formula (3-1) in resin C are as described above. When resin C is a polyimide containing a repeating unit represented by formula (2-1), the preferred embodiment of resin C is the same as the preferred embodiment of resin A3 described above. When resin C is a polyimide precursor containing a repeating unit represented by formula (3-1), the preferred embodiment of resin C is the same as the preferred embodiment of resin A2 described above.

As an embodiment when the resin C is a polyimide precursor, the content of the repeating unit represented by the formula (3-1) is 50 mol% or more of all the repeating units. The total content is more preferably 70 mol% or more, more preferably 90 mol% or more, and even more preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all the repeating units in the resin C except the terminal can be the repeating units represented by the formula (3-1).

The weight average molecular weight (Mw) of resin C is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and further preferably 15,000 to 40,000. Moreover, the number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and further preferably 4,000 to 20,000. The molecular weight dispersion of resin C is preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.0 or more. The upper limit of the molecular weight dispersion of the polyimide precursor is not particularly specified, but for example, 7.0 or less is preferred, 6.5 or less is more preferred, and 6.0 or less is further preferred. Furthermore, when the resin composition contains multiple resins C, it is preferred that the weight average molecular weight, number average molecular weight and dispersion of at least one resin C are within the above ranges. Furthermore, it is also preferred that the weight average molecular weight, number average molecular weight and dispersion calculated by treating the multiple resins C as one resin are within the above ranges.

The content of resin C in the second resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more relative to the total solid content of the resin composition. In addition, the above content is preferably 70% by mass or less, and even more preferably 60% by mass or less. The content of resin B in the second resin composition relative to the total content of resin B and resin C is preferably 20-80% by mass, and even more preferably 30-70% by mass.

<Other resins> The resin composition of the present invention may contain other resins different from the above-mentioned specific resin, resin A2, resin A3 and resin C (hereinafter also referred to as "other resins"). As other resins, there can be listed resins that are different from the specific resin, resin A2, resin A3, and resin C and correspond to polyimide precursors, polyimide, polybenzoxazole precursors, polybenzoxazole, polyamide imide precursors, polyamide imide, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth) acrylic resins, (meth) acrylamide resins, amine resins, butyral resins, styrene resins, polyether resins, polyester resins, and the like. As other polyimide precursors, other polyimides, polybenzoxazole precursors, polybenzoxazoles, polyamide imide precursors, and polyamide imide, the compounds described in paragraphs 0017 to 0138 of International Publication No. 2022/145355 can be cited. The above descriptions are incorporated into this specification.

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, more preferably 1% by mass or more, more preferably 2% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more relative to the total solid content of the resin composition. Relative to the total solid content of the resin composition, the content of the other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, more preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less. As a preferred embodiment of the resin composition of the present invention, it can also be set to an embodiment in which the content of other resins is low. In the above embodiment, relative to the total solid content of the resin composition, the content of other resins is preferably 20% by mass or less, 15% by mass or less is more preferred, 10% by mass or less is further preferred, 5% by mass or less is further preferred, and 1% by mass or less is further preferred. The lower limit of the above content is not particularly limited, and 0% by mass or more is sufficient. Furthermore, when the resin composition of the present invention contains other resins, the content of the specific resin relative to the total content of the specific resin and other resins is preferably 10 to 90 mass %, more preferably 10 to 60 mass %, and even more preferably 20 to 50 mass %. The resin composition of the present invention may contain only one other resin or may contain two or more other resins. When containing two or more, the total amount is preferably within the above range.

<Polymerizable compound> The resin composition of the present invention contains a polymerizable compound.

The melting point of the polymerizable compound is preferably below 25°C. By setting the melting point below 25°C, the coating film can flow easily during drying and heating, thereby improving the flatness of the cured product.

In particular, from the perspective of reducing the dielectric constant of the cured product, it is preferred that the polymerizable compound contain a compound having a ClogP value of 3.0 or more, and it is more preferred that the compound contain a compound having a ClogP value of 3.0 or more and having an aromatic ring structure or an aliphatic ring structure having 6 or more carbon atoms.

In this specification, the ClogP value of a compound is defined as follows. The determination of the octanol-water partition coefficient (logP value) can usually be carried out by the flask immersion method described in JIS Japanese Industrial Standard Z7260-107 (2000). In addition, the octanol-water partition coefficient (logP value) can also be estimated by a computational chemical method or an empirical method instead of actual measurement. As calculation methods, Crippen’s fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)), Viswanadhan’s fragmentation method (J. Chem. Inf. Comput. Sci., 29, 163 (1989)), Broto’s fragmentation method (Eur. J. Med. Chem.-Chim. Theor., 19, 71 (1984)), etc. are known. In the present invention, Crippen’s fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)) is used. The ClogP value refers to a value obtained by calculating the common logarithm logP of the partition coefficient P between 1-octanol and water. Regarding the method or software used in the calculation of the ClogP value, publicly known ones can be used. Unless otherwise specified, the ClogP program embedded in the system PCModels of Daylight Chemical Information Systems is used in the present invention.

The ClogP value is preferably 4.0 or more, and more preferably 6.0 or more. In addition, the upper limit of the ClogP value is not particularly limited, and is preferably 15.0 or less.

The aromatic ring structure may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, but an aromatic hydrocarbon ring is preferred, and a benzene ring is more preferred. In terms of lowering the dielectric constant of the cured product, a condensed ring such as a fluorene ring is preferred. As an aliphatic ring structure having 6 or more carbon atoms, an aliphatic ring structure having 6 to 30 carbon atoms is preferred, and an aliphatic ring structure having 6 to 20 carbon atoms is more preferred. As an aliphatic ring structure having 6 or more carbon atoms, monocyclic rings such as a cyclohexane ring, dicyclopentane ring, and polycyclic rings such as a tricyclic [5.2.1.0 ^2,6 ] decane ring can be cited, and polycyclic rings are preferred.

The polymerizable compound having a ClogP value of 3.0 or more (especially, a compound having a ClogP value of 3.0 or more and having an aromatic ring structure or an aliphatic ring structure having 6 or more carbon atoms) is preferably a compound containing a group having an ethylenic unsaturated bond, and a compound containing two or more groups having an ethylenic unsaturated bond is more preferably. Moreover, a compound containing two groups having an ethylenic unsaturated bond is also preferably. Moreover, the polymerizable compound having a ClogP value of 3.0 or more (especially, a compound having a ClogP value of 3.0 or more and having an aromatic ring structure or an aliphatic ring structure having 6 or more carbon atoms) is preferably a compound corresponding to the free radical crosslinking agent described later.

Specific examples of polymerizable compounds having a ClogP value of 3.0 or more include the following compounds, but are not limited thereto. [Chemical Formula 41]

As the polymerizable compound, there can be mentioned free radical crosslinking agents or other crosslinking agents.

[Free radical crosslinking agent] The resin composition of the present invention preferably contains a free radical crosslinking agent. The free radical crosslinking agent is a compound having a free radical polymerizable group. As the free radical polymerizable group, a group containing an ethylenic unsaturated bond is preferred. As the above-mentioned group containing an ethylenic unsaturated bond, there can be listed vinyl, allyl, vinylphenyl, (meth)acryl, butylene diimide, (meth)acrylamide, etc. Among them, (meth)acryl, (meth)acrylamide, and vinylphenyl are preferred, and in terms of reactivity, (meth)acryl is more preferred.

The free radical crosslinking agent is preferably a compound having one or more ethylenic unsaturated bonds, but a compound having two or more ethylenic unsaturated bonds is more preferred. The free radical crosslinking agent may have three or more ethylenic unsaturated bonds. As the compound having two or more ethylenic unsaturated bonds, a compound having 2 to 15 ethylenic unsaturated bonds is preferred, a compound having 2 to 10 ethylenic unsaturated bonds is more preferred, and a compound having 2 to 6 ethylenic unsaturated bonds is further preferred. In terms of the film strength of the obtained pattern (cured product), the resin composition of the present invention also preferably contains a compound having two ethylenic unsaturated bonds and a compound having three or more ethylenic unsaturated bonds.

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.

Specific examples of free radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides, preferably esters of unsaturated carboxylic acids and polyol compounds and amides of unsaturated carboxylic acids and polyvalent amine compounds. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, thiohydrides, etc., and monofunctional or polyfunctional isocyanates or epoxides, and dehydration condensation reaction products of monofunctional or polyfunctional carboxylic acids, etc. can also be preferably used. Moreover, the addition reaction products of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols, and the substitution reaction products of unsaturated carboxylic acid esters or amides with removable substituents such as halogen groups or tosyloxy groups and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. Moreover, as another example, the above-mentioned unsaturated carboxylic acids can also be replaced by unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, and the like. As a specific example, the description of paragraphs 0113 to 0122 of Japanese Patent Publication No. 2016-027357 can be referred to, and the contents are incorporated into this specification.

The radical crosslinking agent is preferably a compound having a boiling point of 100° C. or higher at normal pressure. Examples of the compound having a boiling point of 100° C. or higher at normal pressure include the compounds described in paragraph 0203 of International Publication No. 2021/112189. The contents are incorporated into this specification.

Preferred radical crosslinking agents other than those mentioned above include radical polymerizable compounds described in paragraphs 0204 to 0208 of International Publication No. 2021/112189, and the contents are incorporated into this specification.

As the radical crosslinking agent, dipentatriol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentatriol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.), A-TMMT (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.)), dipentatriol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentatriol hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), A-DPH (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.) and the structure in which the (meth)acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues is preferred. These oligomer types can also be used.

As commercially available free radical crosslinking agents, for example, there can be mentioned tetrafunctional acrylate SR-494 having four vinyloxy chains, bifunctional methacrylate SR-209, 231, 239 having four vinyloxy chains (all manufactured by Sartomer Company, Inc.), hexafunctional acrylate DPCA-60 having six pentyloxy chains, trifunctional acrylate TPA-330 having three isobutyloxy chains (all manufactured by Nippon Kayaku Co., Ltd.), urethane oligomers UAS-10 and UAB-140 (all manufactured by NIPPON PAPER INDUSTRIES CO., LTD.), NK ESTER M-40G, NK ESTER 4G, NK ESTER M-9300, NK ESTER A-9300, UA-7200 (all 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, AI-600 (all manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION.), etc.

As free radical crosslinking agents, urethane acrylates described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765, and urethane compounds having an ethylene oxide skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also preferred. As the radical crosslinking agent, compounds having an amino structure or a sulfide structure in the molecule described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-Open No. 01-105238 can also be used.

The free radical crosslinking agent can be a free radical crosslinking agent having an acid group such as a carboxyl group or a phosphoric acid group. The free radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a free radical crosslinking agent having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound is more preferably. The following compound is particularly preferred: in the free radical crosslinking agent having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound, the aliphatic polyhydroxy compound is neopentyl triol or dipentyl triol. As commercially available products, for example, polyacid-modified acrylic oligomers M-510 and M-520 manufactured by TOAGOSEI CO., LTD. can be cited.

The acid value of the free radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH/g, and more preferably 1 to 100 mgKOH/g. As long as the acid value of the free radical crosslinking agent is within the above range, the operability in production is excellent and the developing property is excellent. In addition, the polymerizability is good. The above acid value is measured according to the description of JIS K 0070:1992.

In terms of pattern resolution and film stretchability, it is preferable to use a bifunctional methacrylate or acrylate as the resin composition. As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-Hexanediol dimethacrylate, dihydroxymethyl-tricyclodecane diacrylate, dihydroxymethyl-tricyclodecane dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO (propylene oxide) adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, EO-modified isocyanuric acid diacrylate, EO-modified isocyanuric acid dimethacrylate, other bifunctional acrylates with urethane bonds, bifunctional methacrylates with urethane bonds. Two or more of these may be used in combination as needed. Furthermore, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate having a polyethylene glycol chain weight of about 200. In terms of suppressing the warping of the pattern (cured product), the resin composition of the present invention can preferably use a monofunctional free radical crosslinking agent as a free radical crosslinking agent. As monofunctional free radical crosslinking agents, it is preferred to use 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-hydroxymethyl (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate and other (meth)acrylic acid derivatives, N-vinylpyrrolidone, N-vinylcaprolactam and other N-vinyl compounds, allyl glycidyl ether and the like. As monofunctional free radical crosslinking agents, compounds having a boiling point of 100°C or above at normal pressure are also preferred in order to suppress volatility before exposure. In addition, as free radical crosslinking agents with two or more functional groups, allyl compounds such as diallyl phthalate and triallyl trimellitate can be cited.

When a free radical crosslinking agent is contained, the content of the free radical crosslinking agent is preferably more than 0 mass % and less than 60 mass % relative to the total solid content of the resin composition. The lower limit is more preferably 5 mass % or more. The upper limit is more preferably 50 mass % or less, and even more preferably 30 mass % or less.

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

[Other crosslinking agents] The resin composition of the present invention preferably contains other crosslinking agents different from the above-mentioned free radical crosslinking agents. Other crosslinking agents refer to crosslinking agents other than the above-mentioned free radical crosslinking agents. It is preferred that the compound has multiple groups in the molecule that promote the reaction of forming covalent bonds with other compounds in the composition or their reaction products by the photosensitization of the above-mentioned photoacid generator or photoalkali generator, and it is more preferred that the compound has multiple groups in the molecule that promote the reaction of forming covalent bonds with other compounds in the composition or their reaction products by the action of acid or base. It is preferred that the above-mentioned acid or base is an acid or base generated from the photoacid generator or photoalkali generator in the exposure step. As other crosslinking agents, the compounds described in paragraphs 0179 to 0207 of International Publication No. 2022/145355 can be cited. The above description is incorporated into this specification.

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

The photo-radical polymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 L·mol ^-1 ·cm ^-1 in the wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of the compound can be measured by a known method. For example, it is preferably measured by an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.

As the photoradical polymerization initiator, any known compound can be used. For example, alkyl halides derivatives (e.g., compounds having a trioxane skeleton, compounds having a diazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, hexaarylbiimidazoles, oxime compounds such as oxime derivatives, organic peroxides, sulfur 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, iron aromatic complexes, etc. can be listed. For details of the above, please refer to paragraphs 0165 to 0182 of Japanese Patent Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219, which are incorporated into this specification. In addition, the compounds described in paragraphs 0065 to 0111 of Japanese Patent Publication No. 2014-130173 and Japanese Patent No. 6301489, MATERIAL STAGE 37～60p, vol.19, No.3, 2019, the photopolymerization initiator described in International Publication No. 2018/221177, the photopolymerization initiator described in International Publication No. 2018/110179, the photopolymerization initiator described in Japanese Patent Publication No. 2019-043864, the photopolymerization initiator described in Japanese Patent Publication No. 2019-044030, and the peroxide-based initiator described in Japanese Patent Publication No. 2019-167313, the contents of which are incorporated into this specification.

Examples of the ketone compound include compounds described in paragraph 0087 of Japanese Patent Application Laid-Open No. 2015-087611, the contents of which are incorporated herein. Among commercially available products, KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds and acylphosphine compounds can be preferably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators described in Japanese Patent Publication No. 10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, and the contents are incorporated into this specification.

As the α-hydroxyketone-based initiator, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127 (all manufactured by BASF) can be used.

As the α-aminoketone-based initiator, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.

As the aminoacetophenone-based initiator, the acylphosphine oxide-based initiator, and the metallocene compound, for example, the compounds described in paragraphs 0161 to 0163 of International Publication No. 2021/112189 can also be preferably used. The contents are incorporated into this specification.

As the photo-radical polymerization initiator, oxime compounds can be preferably cited. By using oxime compounds, the exposure tolerance can be more effectively improved. Oxime compounds have a wider exposure tolerance (exposure margin) and also function as a photohardening accelerator, so they are particularly preferred.

Specific examples of oxime compounds include compounds described in Japanese Patent Application Publication No. 2001-233842, compounds described in Japanese Patent Application Publication No. 2000-080068, compounds described in Japanese Patent Application Publication No. 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), and compounds described in Journal of Photopolymer Science and Technology. The compounds described in Japanese Unexamined Patent Application (1995, pp. 202-232), the compounds described in Japanese Unexamined Patent Application No. 2000-066385, the compounds described in Japanese Unexamined Patent Application No. 2004-534797, the compounds described in Japanese Unexamined Patent Application No. 2017-019766, the compounds described in Japanese Patent No. 6065596, the compounds described in International Publication No. 20 The compounds described in 15/152153, the compounds described in International Publication No. 2017/051680, the compounds described in Japanese Patent Publication No. 2017-198865, the compounds described in paragraphs 0025 to 0038 of International Publication No. 2017/164127, the compounds described in International Publication No. 2013/167515, etc., the contents of which are incorporated into this specification.

Preferred oxime compounds include, for example, compounds having the following structures: 3-(benzoyloxy(imino))butan-2-one, 3-(acetyloxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetyloxy(imino))pentan-3-one, 2-(acetyloxy(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 preferred to use the oxime compound as a photoradical polymerization initiator. The oxime compound used as a photoradical polymerization initiator has a linking group >C=N-O-C(=O)- in the molecule.

[Chemical formula 42]

Commercially available products of oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, photoradical polymerization initiator 2 described in JP-A-2012-014052), TR-PBG-304 and TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION), DFI-091 (manufactured by Daito Chemix Corporation), and SpeedCure PDO (manufactured by SARTOMER ARKEMA). In addition, an oxime compound having the following structure can also be used. [Chemical Formula 43]

As a photoradical polymerization initiator, for example, an oxime compound having a fluorene ring described in paragraphs 0169 to 0171 of International Publication No. 2021/112189, an oxime compound having a carbazole ring and at least one benzene ring being a naphthalene ring, and an oxime compound having a fluorine atom can also be used. In addition, an oxime compound having a nitro group described in paragraphs 0208 to 0210 of International Publication No. 2021/020359, an oxime compound having a benzofuran skeleton, and an oxime compound having a hydroxyl substituent bonded to the carbazole skeleton can also be used. These contents are incorporated into this specification.

In addition, as the photopolymerization initiator, the compounds described in paragraphs 0113 to 0117 of Japanese Patent Application Laid-Open No. 2023-058585 can also be used. This description is incorporated into the present application specification.

When the resin composition contains a photopolymerization initiator, the content thereof is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, more preferably 0.5 to 15 mass %, and even more preferably 1.0 to 10 mass % relative to the total solid content of the resin composition. The photopolymerization initiator may contain only one type or two or more types. When two or more photopolymerization initiators are contained, the total amount is preferably within the above range. Furthermore, since the photopolymerization initiator sometimes also acts as a thermal polymerization initiator, the crosslinking using the photopolymerization initiator is sometimes further promoted by heating with an oven, a heating plate, etc.

[Sensitizer] The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The electronically excited sensitizer comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, etc., and produces electron transfer, energy transfer, heat, etc. As a result, the thermal radical polymerization initiator and the photoradical polymerization initiator cause chemical changes and decompose, and generate free radicals, acids or bases. As the sensitizers that can be used, compounds such as benzophenone series, michler's ketone series, coumarin series, pyrazole azo series, anilino azo series, triphenylmethane series, anthraquinone series, anthracene series, anthrapyridone series, benzylidene series, oxycyanine series, pyrazolotriazole azo series, pyridone azo series, cyanine series, phenathiophene series, pyrrolopyrazole azo methine series, phthalocyanine series, benzopyran series, indigo series, etc. can be used. As the sensitizer, for example, michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminophenylallylidenedihydroindanone, p- Dimethylaminobenzylene dihydroindanone, 2-(p-dimethylaminophenylbiphenyl)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthylthiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3- Ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-toluenediethanolamine, N-phenylethanolamine, 4-phenoxybenzophenone, isoamyl dimethylaminobenzoate , isoamyl diethylaminobenzoate, 2-benzimidazole, 1-phenyl-5-benzyltetrazolyl, 2-benzthiazole, 2-(p-dimethylaminostyrene)benzoxazole, 2-(p-dimethylaminostyrene)benzothiazole, 2-(p-dimethylaminostyrene)naphthalene (1,2-d)thiazole, 2-(p-dimethylaminobenzyl)styrene, diphenylacetylamide, benzanilide, N-methylacetylanilide, 3',4'-dimethylacetylanilide, etc. Other sensitizing dyes can be used. For details of sensitizing dyes, please refer to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which is incorporated into this specification.

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 even more preferably 0.5 to 10 mass % relative to the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more.

[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, Japan, 2005), pages 683-684. As chain transfer agents, for example, a group of compounds having -SS-, -SO ₂ -S-, -NO-, SH, PH, SiH and GeH in the molecule, dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds having a thiocarbonylthio group used for RAFT (Reversible Addition Fragmentation chain Transfer) polymerization, etc. can be used. These can generate free radicals by donating hydrogen to low-activity free radicals, or can generate free radicals by deprotonating after oxidation. In particular, a thiol compound can be preferably used.

In addition, the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219 can also be used as chain transfer agents, and the contents are incorporated into this specification.

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. The chain transfer agent may be only one or two or more. When there are two or more chain transfer agents, the total amount thereof is preferably within the above range.

In addition, the polymerization initiator is preferably a photoacid generator. As the photoacid generator, a photoacid generator that generates free radicals is preferred. Specifically, a compound that absorbs light and decomposes to generate free radicals and extracts hydrogen from a solvent or the acid generator itself to generate an acid is preferred.

As the photoacid generator, for example, quinone diazide compounds, oxime sulfonate compounds, organic halogenated compounds, organic borate compounds, disulfonium compounds, onium salts, etc. can be listed, and onium salts are preferred. As the onium salt, diazonium salts, phosphonium salts, selenium salts, iodonium salts, etc. can be listed.

Furthermore, the onium salt is a salt of a cation and anion having an onium structure, and the cation and anion may be bonded by covalent bonding or not. That is, the onium salt may be an intramolecular salt having a cation part and anion part in the same molecular structure, or an intermolecular salt formed by ionic bonding between cation molecules and anion molecules of different molecules, but intermolecular salts are preferred. Furthermore, in the composition of the present invention, the cation part or cation molecule and the anion part or anion molecule may be bonded by ionic bonding or may be dissociated.

[Sirconium salt] In the present invention, the term "sirconium salt" refers to a salt of a cation and an anion of zinc.

- Copper cation - As the copper cation, a tertiary copper cation is preferred, and a triaryl copper cation is more preferred. In addition, as the copper cation, a cation represented by the following formula (103) is preferred. [Chemical formula 44]

In formula (103), R ⁸ to R ¹⁰ each independently represent a alkyl group. R ⁸ to R ¹⁰ each independently represent an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group. R ⁸ to R ¹⁰ may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyloxy group. Among these, as a substituent, an alkyl group or an alkoxy group is preferred, a branched alkyl group or an alkoxy group is more preferred, and a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms is further preferred. R ⁸ to R ¹⁰ may be the same group or different groups, but the same group is preferred in terms of synthetic suitability.

-Anions- There are no particular limitations on the anions and they may be selected in consideration of the acid to be generated. Examples of the anions include boron anions such as B(C ₆ F ₅ ) ₄ ^- , BF ₄ ^- , phosphorus anions such as (Rf) _n PF _6-n ^- , PF ₃ (C ₂ F ₅ ) ₃ ^- , PF ₆ ^- , antimony anions such as SbF ₆ ^- , other carboxylic acid anions, sulfonic acid anions, and the like.

[Iodine salt] In the present invention, an iodine salt refers to a salt of an iodine cation and an anion. Examples of the anion include the same anions as those in the above-mentioned zirconia salt, and the preferred embodiment is also the same.

-Ion cation- As the iodine cation, a diaryl iodine cation is preferred. Also, as the iodine cation, a cation represented by the following formula (104) is preferred. [Chemical Formula 45]

In formula (104), R ¹¹ and R ¹² each independently represent a alkyl group. R ¹¹ and R ¹² each independently represent an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group. R ¹¹ and R ¹² may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyloxy group. Among these, as a substituent, an alkyl group or an alkoxy group is preferred, a branched alkyl group or an alkoxy group is more preferred, and a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms is further preferred. R ¹¹ and R ¹² may be the same group or different groups, but the same group is preferred in terms of synthetic suitability.

[Phosphonium salt] In the present invention, phosphonium salt means a salt of a phosphonium cation and an anion. Examples of the anion include the same anions as those in the above-mentioned zirconia salt, and the preferred embodiments are also the same.

-Phosphonium cation- As the phosphonium cation, a quaternary phosphonium cation is preferred, and examples thereof include tetraalkylphosphonium cations and triarylmonoalkylphosphonium cations. Furthermore, as the phosphonium cation, a cation represented by the following formula (105) is preferred. [Chemical Formula 46]

In formula (105), R ¹³ to R ¹⁶ each independently represent a hydrogen atom or a alkyl group. R ¹³ to R ¹⁶ each independently represent an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group. R ¹³ to R ¹⁶ may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyloxy group. Among these, as a substituent, an alkyl group or an alkoxy group is preferred, a branched alkyl group or an alkoxy group is more preferred, and a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms is further preferred. R ¹³ to R ¹⁶ may be the same group or different groups, but the same group is preferred in terms of synthetic suitability.

The content of the photoacid generator relative to the total solid content of the resin composition is preferably 0.1 to 20 mass %, more preferably 0.5 to 18 mass %, further preferably 0.5 to 10 mass %, further preferably 0.5 to 3 mass %, and further preferably 0.5 to 1.2 mass %. The photoacid generator can be used alone or in combination. When multiple types are used in combination, the total amount thereof is preferably within the above range. In addition, in order to impart photosensitivity to the desired light source, it is also preferred to use it in combination with a sensitizer.

In addition, the resin composition of the present invention contains two or more polymerization initiators as polymerization initiators, which is also one of the preferred embodiments of the present invention. Specifically, the resin composition of the present invention preferably contains a photopolymerization initiator and the thermal polymerization initiator described below, or contains the above-mentioned photoradical polymerization initiator and the above-mentioned photoacid generator.

By containing a photopolymerization initiator and a thermal polymerization initiator described later, it is sometimes possible to form a pattern by exposure and to easily perform free radical polymerization during curing by the heating step described later, thereby improving performance such as chemical resistance. As the content ratio when containing a photopolymerization initiator and a thermal polymerization initiator described later, the content of the thermal polymerization initiator is preferably 20 to 70 mass % relative to the total content of the photopolymerization initiator and the thermal polymerization initiator, and more preferably 30 to 60 mass %.

By containing a photo-radical polymerization initiator and a photo-acid generator, performance such as resolution may be improved. As for the content ratio when a photo-polymerization initiator and a photo-acid generator are contained, the content of the photo-acid generator is preferably 20 to 70 mass %, and more preferably 30 to 60 mass %, relative to the total content of the photo-polymerization initiator and the photo-acid generator.

[Thermal polymerization initiator] As a thermal polymerization initiator, for example, a thermal free radical polymerization initiator can be cited. A thermal free radical polymerization initiator is a compound that generates free radicals by heat energy and initiates or promotes the polymerization reaction of a polymerizable compound. By adding a thermal free radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can also be carried out, thereby further improving the solvent resistance.

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 into the present specification.

When the resin composition contains a thermal polymerization initiator, the content thereof is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, and even more preferably 0.5 to 15 mass % relative to the total solid content of the resin composition. The thermal polymerization initiator may contain only one kind or two or more kinds. When two or more kinds of thermal polymerization initiators are contained, the total amount is preferably within the above range.

<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 organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfones, amides, ureas, and alcohols.

Examples of the 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 alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.) ethyl 2-methoxypropionate, etc.)), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc. are preferred.

As the ethers, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl thiourea acetate, ethyl thiourea 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, dipropylene glycol dimethyl ether and the like can be listed as preferred ones.

As the ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone and the like are preferably mentioned.

Preferred examples of the cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

As the sulfoxides, for example, dimethyl sulfoxide can be cited as a preferred one.

As the amides, 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-formylthiophene, N-acetylthiophene and the like are preferably mentioned.

As the urea, N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone and the like are preferred.

As alcohols, there may be mentioned 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, methylbenzyl alcohol, n-pentanol, methylpentanol and diacetone alcohol.

In terms of improving the properties of the coated surface, it is also preferred that the solvent be in the form of a mixture of two or more solvents.

In the present invention, one solvent selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl celulose 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, levulose ketone and dihydrolevulose ketone, or a mixed solvent consisting of two or more of the above is preferred. It is particularly preferred to use dimethyl sulfoxide and γ-butyrolactone, dimethyl sulfoxide and γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide and γ-butyrolactone, 3-methoxy-N,N-dimethylpropionamide, γ-butyrolactone and dimethyl sulfoxide together, or N-methyl-2-pyrrolidone and ethyl lactate together. It is also one of the better aspects of the present invention to further add about 1 to 10% by mass of toluene relative to the total mass of the solvent to the solvent used in combination. In particular, in terms of the storage stability of the resin composition, the aspect containing γ-valerolactone as a solvent is also one of the better aspects of the present invention. In this embodiment, the content of γ-valerolactone relative to the total mass of the solvent is preferably 50 mass% or more, more preferably 60 mass% or more, and even more preferably 70 mass% or more. In addition, the upper limit of the above content is not particularly limited and can be 100 mass%. The above content can be determined by considering the solubility of the specific resin and other components contained in the resin composition. Furthermore, when dimethyl sulfoxide and γ-valerolactone are used together, relative to the total mass of the solvent, it is preferred that the solvent contains 60-90 mass% of γ-valerolactone and 10-40 mass% of dimethyl sulfoxide, more preferably 70-90 mass% of γ-valerolactone and 10-30 mass% of dimethyl sulfoxide, and even more preferably 75-85 mass% of γ-valerolactone and 15-25 mass% of dimethyl sulfoxide.

In terms of coating properties, the content of the solvent is preferably set to an amount where the total solid content concentration of the resin composition of the present invention reaches 5 to 80 mass %, more preferably 5 to 75 mass %, more preferably 10 to 70 mass %, and even more preferably 20 to 70 mass %. The solvent content can be adjusted according to the desired thickness of the coating and the coating method. When two or more solvents are contained, it is preferably that the total is within the above range.

<Metal Adhesion Improver> In terms of improving adhesion to metal materials used in electrodes or wiring, the resin composition of the present invention preferably contains a metal adhesion improver. Examples of metal adhesion improvers include silane coupling agents having alkoxysilyl groups, aluminum-based adhesion promoters, titanium-based adhesion promoters, compounds having sulfonamide structures and compounds having thiourea structures, phosphoric acid derivative compounds, β-ketoester compounds, and amino compounds.

[Silane coupling agent] As a silane coupling agent, for example, the compound described in paragraph 0316 of International Publication No. 2021/112189 and the compound described in paragraphs 0067 to 0078 of Japanese Patent Publication No. 2018-173573 can be listed, and these contents are incorporated into this specification. In addition, as described in paragraphs 0050 to 0058 of Japanese Patent Publication No. 2011-128358, it is also preferred to use two or more different silane coupling agents. It is also preferred to use the following compounds as silane coupling agents. In the following formula, Me represents a methyl group and Et represents an ethyl group. In addition, the following R can list the structure of the end-capping agent derived from the blocked isocyanate group. As the end-capping agent, it can be selected according to the stripping temperature, and alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, active methylene compounds, etc. can be listed. For example, in terms of setting the stripping temperature to 160 to 180°C, caprolactam is preferred. As a commercial product of such a compound, X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be listed.

[Chemical formula 47] [Chemical formula 48]

As other silane coupling agents, for example, vinyl trimethoxysilane, vinyl triethoxysilane, 2-(3,4-epoxyhexyl)ethyl trimethoxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyl diethoxysilane, 3-glycidoxypropyl triethoxysilane, p-phenylene trimethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryloxypropyl Oxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-butylenepropylmethyldimethoxysilane, 3-butylenepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more. In addition, as a silane coupling agent, an oligomer-type compound having a plurality of alkoxysilyl groups can also be used. As such an oligomer-type compound, there can be listed compounds containing a repeating unit represented by the following formula (S-1). [Chemical Formula 49] In formula (S-1), ^RS1 represents a monovalent organic group, ^RS2 represents a hydrogen atom, a hydroxyl group or an alkoxy group, and n represents an integer of 0 to 2. ^RS1 preferably has a structure containing a polymerizable group. Examples of the polymerizable group include a group having an ethylenically unsaturated bond, an epoxide group, an oxacyclobutane group, a benzoxazolyl group, a blocked isocyanate group, an amine group, and the like. As the group having an ethylenic unsaturated bond, there can be mentioned 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., vinylphenyl, etc.), a (meth)acrylamide group, a (meth)acryloxy group, etc., preferably a vinylphenyl group, a (meth)acrylamide group or a (meth)acryloxy group, more preferably a vinylphenyl group or a (meth)acryloxy group, and further preferably a (meth)acryloxy group. ^RS2 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 the formula (S-1) contained in the oligomer type compound may be the same. Here, in the oligomer type compound, it is preferred that n is 1 or 2 in at least one of the multiple repeating units represented by the formula (S-1), more preferably 1 or 2 in at least two of them, and even more preferably 1 in at least two of them. As such an oligomer type compound, a commercially available product can be used, and as a commercially available product, for example, KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be cited.

[Aluminum-based bonding aid] Examples of aluminum-based bonding aids include tri(ethyl acetylacetate)aluminum, tri(acetylacetone)aluminum, and diisopropyl ethyl acetylacetate aluminum.

As other metal adhesion improvers, compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Laid-Open No. 2014-186186 and sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Application Laid-Open No. 2013-072935 can also be used, and these contents are incorporated into this specification.

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 setting it to above the lower limit, the adhesion between the pattern and the metal layer becomes good, and by setting it to below the upper limit, the heat resistance and mechanical properties of the pattern become good. The metal adhesion improver can be only one kind or two or more kinds. When two or more kinds are used, it is preferably that the total is within the above range.

<Migration inhibitor> The resin composition of the present invention preferably further contains a migration inhibitor. By containing a migration inhibitor, for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, it is possible to effectively inhibit metal ions originating from the metal layer (or metal wiring) from migrating into the film.

Migration inhibitors are not particularly limited, and examples thereof include compounds having a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxadiazole ring, thiazole ring, pyrazole ring, isoxadiazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, oxadiazole ring, 2H-pyranyl ring, 6H-pyranyl ring, trioxadiazole ring), compounds having thiourea and thiohydrin, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

Among them, the resin composition of the present invention preferably contains an azole compound. An azole compound is a compound containing an azole structure, and an azole structure refers to a five-membered ring structure containing a nitrogen atom as a ring member, and a five-membered ring structure containing two or more nitrogen atoms as ring members is preferred. Specifically, the azole structure can be exemplified by an imidazole structure, a triazole structure, a tetrazole structure, etc. Such as benzimidazole, benzotriazole, etc., these structures can form polycyclic rings with other ring structures by condensation, etc. In addition, as a compound having an azole structure, a compound in which a group represented by the following formula (R-1) or the following formula (R-2) is directly bonded to the azole structure is also preferred. [Chemical Formula 50] In formula (R-1), R ¹ represents a monovalent organic group, and * represents a bonding site with the azole structure. In formula (R-2), R ² represents a hydrogen atom or a monovalent organic group, R ³ represents a monovalent organic group, and * represents a bonding site with the azole structure. In formula (R-1), R ¹ is preferably a alkyl group or a group represented by a bond between a alkyl group and at least one group selected from the group consisting of -O-, -C(=O)-, -S-, -S(=O) ₂ -, and -NR ^N -. ^RN is as described above. As the above-mentioned alkyl group, an aliphatic alkyl group, an aromatic alkyl group, or a group represented by a combination thereof is preferred. Moreover, the total carbon number of R ¹ is preferably 1 to 30, preferably 2 to 25, and more preferably 3 to 20. The bonding site of R ¹ to the carbonyl group in formula (R-1) is preferably a alkyl group or -NR ^N -. In formula (R-1), * represents the bonding site to the azole structure, and the bonding site to the carbon atom which is a ring member of the azole structure is preferred. In formula (R-2), R ² is preferably a hydrogen atom. When R ² is a monovalent organic group, R ² is preferably a alkyl group or a group represented by a bond between a alkyl group and at least one group selected from the group consisting of -O-, -C(=O)-, -S-, -S(=O) ₂ - and -NR ^N -. ^RN is as described above. As the above-mentioned alkyl group, an aliphatic alkyl group, an aromatic alkyl group or a group represented by a combination thereof is preferred. When R ² is a monovalent organic group, the total carbon number is preferably 1 to 30, preferably 2 to 25, and more preferably 3 to 20. When R ² is a monovalent organic group, the bonding site of R ² to the nitrogen atom in formula (R-2) is preferably a alkyl group or -C(=O)-. In formula (R-2), R ³ is preferably a alkyl group or a group represented by a bond between a alkyl group and at least one group selected from the group consisting of -O-, -C(=O)-, -S-, -S(=O) ₂ -, and -NR ^N -. ^RN represents a hydrogen atom or a alkyl group, preferably a hydrogen atom. As the above-mentioned alkyl group, an aliphatic alkyl group, an aromatic alkyl group, or a group represented by a combination thereof is preferred. When R ³ is a monovalent organic group, the total carbon number is preferably 1 to 30, preferably 2 to 25, and more preferably 3 to 20. The bonding site of R ³ to the nitrogen atom in formula (R-2) is preferably a alkyl group or -C(=O)-. In formula (R-2), * represents the bonding site to the azole structure, and the bonding site to the carbon atom that is a ring member of the azole structure is preferably.

As a migration inhibitor, an ion capture agent that captures anions such as halogen ions can also be used.

As other migration inhibitors, the rust inhibitor described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, the compound described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, the compound described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, the compound described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, the compound described in paragraph 0166 of International Publication No. 2015/199219, etc. can be used, and the contents are incorporated into this specification.

As specific examples of migration inhibitors, the following compounds can be cited.

[Chemical formula 51]

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 %, relative to the total solid content of the resin composition.

The number of migration inhibitors may be one or more. When there are two or more migration inhibitors, the total amount thereof is preferably within the above range.

<Light absorber> The resin composition of the present invention preferably contains a compound (light absorber) whose absorbance at the exposure wavelength decreases due to exposure. As light absorbers, compounds described in paragraphs 0159 to 0183 of International Publication No. 2022/202647 and compounds described in paragraphs 0088 to 0108 of Japanese Patent Publication No. 2019-206689 can be cited. These contents are incorporated into this specification.

In particular, in terms of improving the adhesion to the substrate, the resin composition of the present invention preferably further contains the above-mentioned azole compound and the above-mentioned silane coupling agent. By containing these compounds, it is easy to maintain the adhesion to the substrate even after the cured product is exposed to high temperature and high humidity conditions.

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

Specific examples of the polymerization inhibitor include compounds described in paragraph 0310 of International Publication No. 2021/112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1-oxyl radical, phenanthroline, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N-dioxide, etc. The contents are incorporated into this specification.

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

The polymerization inhibitor may be one or more. When the polymerization inhibitor is two or more, the total amount thereof is preferably within the above range.

<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, alkali generators, anti-agglomeration agents, phenolic compounds, other polymer compounds, plasticizers and other additives (e.g., defoamers, flame retardants, etc.). By appropriately containing these ingredients, the properties of the film such as physical properties can be adjusted. For these components, for example, reference can be made to paragraphs 0183 and later of Japanese Patent Publication No. 2012-003225 (paragraph 0237 of the corresponding U.S. Patent Application Publication No. 2013/0034812), paragraphs 0101 to 0104, 0107 to 0109 of Japanese Patent Publication No. 2008-250074, etc., and these contents are incorporated into this specification. When these additives are blended, it is preferred that their total content be set to 3% by mass or less of the solid content of the resin composition of the present invention.

[Inorganic particles] Specific examples of inorganic particles include calcium carbonate, calcium phosphate, silicon dioxide, kaolin, talc, titanium dioxide, aluminum oxide, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.

The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further 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 a primary particle size and a volume average particle size. The volume average particle size can be measured, for example, by a dynamic light scattering method based on Nanotrac WAVE II EX-150 (manufactured by NIKKISO CO., LTD.). When the above measurement is difficult to perform, it can also be measured by a centrifugal sedimentation light transmission method, an X-ray transmission method, or a laser diffraction/scattering method.

[Organic titanium compound] By including an organic titanium compound in the resin composition, a resin layer with excellent chemical resistance can be formed even when hardening at low temperatures.

As the organic titanium compounds that can be used, organic groups bonded to titanium atoms via covalent bonds or ionic bonds can be listed. Specific examples of organic titanium compounds are shown in the following I) to VII): I) Titanium chelate compounds: In terms of good storage stability of the resin composition and the ability to obtain a good curing pattern, titanium chelate compounds having two or more alkoxy groups are more preferred. Specific examples are bis(triethanolamine)diisopropoxytitanium, di(n-butoxy)bis(2,4-pentanedioate)titanium, diisopropoxybis(2,4-pentanedioate)titanium, diisopropoxybis(tetramethylpimelate)titanium, diisopropoxybis(ethyl acetylacetate)titanium, etc. II) Tetraalkoxy titanium compounds: for example, tetra(n-butoxy)titanium, tetraethoxytitanium, tetra(2-ethylhexyloxy)titanium, tetraisobutoxytitanium, tetraisopropoxytitanium, tetramethoxytitanium, tetramethoxypropoxytitanium, tetramethylphenoxytitanium, tetra(n-nonyloxy)titanium, tetra(n-propoxy)titanium, tetrastearyloxytitanium, tetra[bis{2,2-(allyloxymethyl)propoxy}]titanium, etc. III) Titanium cyclopentadiene compounds: for example, pentamethylcyclopentadiene trimethoxytitanium, bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc. IV) Monoalkoxy titanium compounds: for example, tris(dioctyl phosphate)isopropoxytitanium, tris(dodecyl benzenesulfonate)isopropoxytitanium, etc. V) Titanium oxide compounds: for example, bis(glutaric acid ester) titanium oxide, bis(tetramethyl pimelate) titanium oxide, phthalocyanine titanium oxide, etc. VI) Titanium tetraacetylacetonate compounds: for example, titanium tetraacetylacetonate, etc. VII) Titanium ester coupling agent: for example, isopropyl tridodecylbenzenesulfonyl titanium ester, etc.

Among them, as an organic titanium compound, in terms of better chemical resistance, at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxy titanium compounds and III) titanocene compounds is preferred. In particular, diisopropoxybis(ethyl acetylacetate)titanium, tetra(n-butoxy)titanium and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

Furthermore, as an organic titanium compound or in place of the organic titanium compound, a compound represented by the following formula (T-1) is also preferably contained. [Chemical Formula 52] In formula (T-1), M is titanium, zirconium or eurium, l1 is an integer from 0 to 2, l2 is 0 or 1, l1+l2×2 is an integer from 0 to 2, m is an integer from 0 to 4, n is an integer from 0 to 2, l1+l2+m+n×2=4, ^R11 is each independently a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted alkoxy group or a substituted or unsubstituted phenoxy group, ^R12 is a substituted or unsubstituted alkyl group, ^R2 is each independently a group having a structure represented by the following formula (T-2), ^R3 is each independently a group having a structure represented by the following formula (T-2), and ^XA is each independently an oxygen atom or a sulfur atom. [Chemical Formula 53] In formula (T-2), X ¹ to X ³ each independently represent -C(-*)= or -N=, * represents a bonding site with other structures, and # represents a bonding site with a metal atom.

In formula (T-1), M is preferably titanium in terms of storage stability of the composition. In formula (T-1), the state in which l1 and l2 are 0 is also one of the preferred states of the present invention. In formula (T-1), m is preferably 2 or 4, and 2 is more preferred. In formula (T-1), n is preferably 1 or 2, and 1 is more preferred. Here, in formula (T-1), l1 and l2 are 0 and m is also preferably 0, 2 or 4.

In formula (T-1), R ¹¹ is preferably a substituted or unsubstituted cyclopentadienyl ligand from the perspective of the stability of the specific metal complex. The cyclopentadienyl, alkoxy and phenoxy groups in R ¹¹ may be substituted, but the unsubstituted aspect is also one of the preferred aspects of the present invention.

In formula (T-1), R ¹² is preferably a alkyl group having 1 to 20 carbon atoms, and more preferably a alkyl group having 2 to 10 carbon atoms. The alkyl group in R ¹² may be any of an aliphatic alkyl group and an aromatic alkyl group, and an aromatic alkyl group is preferred. The aliphatic alkyl group may be a saturated aliphatic alkyl group or an unsaturated aliphatic alkyl group, but a saturated aliphatic alkyl group is preferred. The aromatic alkyl group is preferably an aromatic alkyl group having 6 to 20 carbon atoms, and more preferably an aromatic alkyl group having 6 to 10 carbon atoms, and even more preferably a phenylene group. As a substituent in R ¹² , a monovalent substituent is preferred, and a halogen atom or the like can be mentioned. When R ¹² is an aromatic alkyl group, it may have an alkyl group as a substituent. In the formula (T-1), R ¹² is preferably an unsubstituted phenylene group. In the formula (T-1), the phenylene group in R ¹² is preferably a 1,2-phenylene group.

In formula (T-1), m is 2 or more, and when there are 2 or more R ² , the structures of the 2 or more R ² may be the same or different. In formula (T-1), n is 2 or more, and when there are 2 or more R ³ , the structures of the 2 or more R ³ may be the same or different.

In formula (T-2), X ¹ to X ³ each independently represent -C(-*)= or -N=, preferably at least one represents -C(-*)=, and more preferably at least two represent -C(-*)=.

Specific examples of the compound represented by formula (T-1) include compounds corresponding to I-5 to I-8 in Examples, but are not limited thereto.

When the resin composition contains an organic titanium compound, the content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the specific resin. When the content is 0.05 parts by mass or more, the heat resistance and chemical resistance of the obtained hardened pattern become better, and when it is 10 parts by mass or less, the storage stability of the composition is better.

When an organic titanium compound is contained, the 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 parts by mass or more, the heat resistance and chemical resistance of the obtained hardened pattern become better, and when it is 10 parts by mass or less, the storage stability of the composition is better. As other additives, the compounds described in paragraphs 0249 to 0282 and paragraphs 0316 to 0358 of International Publication No. 2022/145355 can be listed. The above description is incorporated into this specification.

<Characteristics of the resin composition> The viscosity of the resin composition of the present invention can be adjusted by adjusting the solid content concentration of the resin composition. In terms of the coating film thickness, 1,000 mm ² /s to 12,000 ^{mm 2} /s is preferred, 2,000 mm ² /s to 10,000 ^{mm 2} /s is more preferred, and 2,500 mm ² /s to 8,000 mm ² /s is further preferred. Within the above range, a highly uniform coating film can be easily obtained. If it is 1,000 mm ² /s or more, it is easy to apply the film with the required film thickness as an insulating film for redistribution wiring, for example, and if it is 12,000 mm ² /s or less, a coating film with excellent coating surface appearance can be obtained.

<Restrictions on the substances contained in the resin composition> The water content of the resin composition of the present invention is preferably less than 2.0 mass %, more preferably less than 1.5 mass %, and even more preferably less than 1.0 mass %. If it is less than 2.0%, the storage stability of the resin composition is improved. As a method for maintaining the water content, it can be listed that the humidity under the storage conditions is adjusted, the porosity of the storage container during storage is reduced, etc.

In terms of insulation, 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, nickel, etc., but exclude metals contained as complexes of organic compounds and metals. When multiple metals are contained, the total of the metals is preferably within the above range.

Furthermore, as a method for reducing the metal impurities accidentally contained in the resin composition of the present invention, the following methods can be cited: selecting a raw material with a low metal content as a raw material constituting the resin composition of the present invention, filtering the raw material constituting the resin composition of the present invention through a filter, lining the inside of the device with polytetrafluoroethylene or the like and performing distillation under conditions that suppress contamination as much as possible, etc.

Regarding the resin composition of the present invention, if the use as a semiconductor material is considered, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and more preferably less than 200 mass ppm in terms of wiring corrosion. Among them, the content of halogen ions is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and more preferably less than 0.5 mass ppm. As halogen atoms, chlorine atoms and bromine atoms can be listed. It is preferred that the total of chlorine atoms and bromine atoms or chlorine ions and bromine ions are respectively within the above range. As a method for adjusting the content of halogen atoms, ion exchange treatment, etc. can be preferably listed.

As a container for the resin composition of the present invention, a conventionally known container can be used. As a container, in order to suppress the mixing of impurities into the raw materials or the resin composition of the present invention, it is also preferable to use a multi-layer bottle having an inner wall of the container composed of six types of six layers of resins or a bottle having a seven-layer structure formed of six types of resins. As such a container, for example, the container described in Japanese Patent Publication No. 2015-123351 can be cited.

<Cured resin composition> By curing the resin composition of the present invention, a cured resin composition can be obtained. The cured resin composition of the present invention is a cured resin composition. The curing of the resin composition is preferably performed by heating, and the heating temperature is preferably 120°C to 400°C, more preferably 140°C to 380°C, and particularly preferably 170°C to 350°C. The shape of the cured resin composition is not particularly limited, and can be selected from a film, rod, spherical, granular, etc. according to the application. In the present invention, the cured product is preferably a film. By patterning the resin composition, the shape of the cured product can be selected according to the purpose of forming a protective film on the wall, forming a conductive through hole, adjusting impedance, electrostatic capacitance or internal stress, and providing a heat dissipation function. The film thickness of the cured product (film composed of the cured product) is preferably 0.5μm or more and 150μm or less. The shrinkage rate when curing the resin composition of the present invention is preferably 50% or less, 45% or less is more preferably, and 40% or less is further preferably. Here, the shrinkage rate refers to the percentage of the volume change of the resin composition before and after curing, which can be calculated according to the following formula. Shrinkage rate [%] = 100-(volume after curing ÷ volume before curing) × 100

<Characteristics of the cured product of the 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, it may become a cured product with 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.

The transmittance of the cured product at a wavelength of 365 nm is preferably 15% or more, more preferably 20% or more, and more preferably 25% or more. The upper limit of the above transmittance is not particularly limited and can be 100%. The above transmittance is measured using a known spectrophotometer.

<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 performed by a conventionally known method. As the mixing method, mixing using a stirring blade, mixing using a ball mill, mixing by rotating a tank, etc. can be listed. The temperature during mixing is preferably 10 to 30°C, and more preferably 15 to 25°C.

For the purpose of removing foreign matter such as dust or particles in the resin composition of the present invention, it is preferred to perform filtering using a filter. Regarding the pore size of the filter, for example, 5 μm or less is preferred, 1 μm or less is more preferred, 0.5 μm or less is further preferred, and 0.1 μm or less is further preferred. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. When the material of the filter is polyethylene, HDPE (high-density polyethylene) is more preferred. The filter can be pre-cleaned with an organic solvent. In the filtering step of the filter, multiple filters can be connected in series or in parallel for use. When using multiple filters, filters with different pore sizes or materials can be used in combination. As a connection example, for example, the following example can be listed: a HDPE filter with a pore size of 1 μm is used as the first stage, and a HDPE filter with a pore size of 0.2 μm is used as the second stage, and the two are connected in series. In addition, various materials can be filtered multiple times. When filtering is repeated multiple times, it can be cycle filtering. In addition, pressure filtering can be performed. When performing pressurized filtration, the applied pressure is preferably, for example, 0.01 MPa or more and 1.0 MPa or less, 0.03 MPa or more and 0.9 MPa or less, 0.05 MPa or more and 0.7 MPa or less, and 0.05 MPa or more and 0.5 MPa or less. In addition to filtering using a filter, impurity removal using an adsorbent can also be performed. Filtering and impurity removal using an adsorbent can also be combined. As an adsorbent, a known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be listed. After filtering with a filter, a step of placing the resin composition filled in the bottle under reduced pressure for degassing may be performed.

(Method for producing a cured product) The method for producing a cured product of the present invention preferably includes a film forming step of applying a resin composition to a substrate to form a film. The method for producing a cured product preferably includes the film forming step, an exposure step of selectively exposing the film formed by the film forming step, and a developing step of developing the film exposed by the exposure step with a developer to form a pattern. The method for producing a cured product preferably includes at least one of the film forming step, the exposure step, the developing step, a heating step of heating the pattern obtained by the developing step, and a post-development exposure step of exposing the pattern obtained by the developing step. Furthermore, it is also preferred that the method for producing a cured product includes the above-mentioned film forming step and the step of heating the above-mentioned film. The details of each step are described below.

<Film-forming step> The resin composition of the present invention can be used in a film-forming step of applying it 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.

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

When a resin composition is applied to the surface of a resin layer (eg, a layer composed of a hardened material) or the surface of a metal layer to form a film, the resin layer or the metal layer becomes a base.

As a method of applying the resin composition to the substrate, coating is preferred. As the method to be applied, specifically, dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating and inkjet coating can be listed. In terms of uniformity of film thickness, spin coating, slit coating, spray coating or inkjet coating is preferred, and in terms 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 or the coating conditions according to the method used, a film of the desired thickness can be obtained. In addition, the coating method can be appropriately selected according to the shape of the substrate. If it is a circular substrate such as a wafer, spin coating, spray coating, inkjet method, etc. are preferred. If it is a rectangular substrate, slit coating, spray coating, inkjet method, 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. In addition, a method of transferring the coating film previously applied by the above-mentioned applying method and formed on the pseudo support to the substrate can also be applied. Regarding the transfer method, the production method described in paragraphs 0023, 0036 to 0051 of Japanese Patent Publication No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Publication No. 2006-047592 can also be preferably used. In addition, a step of removing excess film at the end of the substrate can also be performed. Examples of such a step include edge bead rinse (EBR) and back rinse. The following pre-wetting step can also be adopted: before applying the resin composition to the substrate, various solvents are applied to the substrate to improve the wettability of the substrate and then the resin composition is applied.

<Drying step> After the film forming step (layer forming step), the film may be subjected to a step of drying the formed film (layer) in order to remove the solvent (drying step). That is, the method for producing a hardened product of the present invention may include a drying step of drying the film formed by the film forming step. The drying step is preferably performed 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. In addition, drying may be performed by reducing the pressure. The drying time may be 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

<Exposure step> The above-mentioned film can be provided for an exposure step of selectively exposing the film. The method for manufacturing a cured product may include an exposure step of selectively exposing the film formed by the film forming step. Selective exposure refers to exposing a portion of the film. In addition, by selective exposure, an exposed area (exposed portion) and an unexposed area (non-exposed portion) are formed on the film. The exposure amount is not particularly limited as long as it can cure the resin composition of the present invention. For example, when converted to exposure energy at a wavelength of 365nm, 50 to 10,000mJ/ ^cm2 is preferred, and 200 to 8,000mJ/ ^cm2 is more preferred.

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

Regarding exposure wavelength, in terms of its relationship with the light source, we can cite (1) semiconductor lasers (wavelengths of 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelength 436nm), h-rays (wavelength 405nm), i-rays (wavelength 365nm), wide wavelengths (3 wavelengths of g, h, and i-rays), (4) excimer lasers, KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), F ₂ Excimer laser (wavelength 157nm), (5) extreme ultraviolet light; EUV (wavelength 13.6nm), (6) electron beam, (7) secondary harmonic 532nm, third harmonic 355nm of YAG laser, etc. With regard to the resin composition of the present invention, exposure using a high-pressure mercury lamp is particularly preferred, and exposure using i-rays is more preferred in terms of exposure sensitivity. The exposure method is not particularly limited as long as it is a method of exposing at least a portion of the film composed of the resin composition of the present invention, but examples thereof include exposure using a mask, exposure using a laser direct imaging method, etc.

<Post-exposure heating step> The above-mentioned film can be provided for a step of heating after exposure (post-exposure heating step). That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the film exposed by the exposure step. The post-exposure heating step can be performed after the exposure step and before the development step. The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, and more preferably 60°C to 120°C. The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, and more preferably 1 minute to 10 minutes. The heating rate in the post-exposure heating step is preferably 1 to 12°C/minute from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10°C/minute, and even more preferably 3 to 10°C/minute. In addition, the heating rate can be appropriately changed during the heating process. There is no particular limitation on the heating method in the post-exposure heating step, and a known heating plate, oven, infrared heater, etc. can be used. In addition, when heating, it is also preferable to circulate an inert gas such as nitrogen, helium, and argon in an environment with a low oxygen concentration.

<Developing step> The film after exposure can be subjected to a developing step of forming a pattern by developing with a developer. That is, the method for producing a hardened product of the present invention may include a developing step of forming a pattern by developing the film exposed by the exposure step with a developer. The pattern is formed by removing one of the exposed portion and the non-exposed portion of the film by developing. Here, the development of removing the non-exposed portion of the film by the developing step is referred to as negative development, and the development of removing the exposed portion of the film by the developing step is referred to as positive development.

[Developer] As the developer used in the developing step, there can be exemplified an alkaline aqueous solution or a developer containing an organic solvent.

When the developer is an alkaline aqueous solution, examples of alkaline compounds that can be contained in the alkaline aqueous solution include inorganic bases, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts, preferably 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, , tetrapropylamine hydroxide, tetrabutylamine hydroxide, tetrapentylamine hydroxide, tetrahexylamine hydroxide, tetraoctylamine hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, piperidine, and more preferably TMAH. The content of the alkaline compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass, based on the total mass of the developer.

When the developer contains an organic solvent, the compounds described in paragraph 0387 of International Publication No. 2021/112189 can be used as the organic solvent. The contents are incorporated into this specification. In addition, as alcohols, preferably methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, triethylene glycol, etc. can also be listed, and as amides, preferably N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. can also be listed.

When the developer contains an organic solvent, the organic solvent can be used alone or in combination of two or more. 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 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.

When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50 mass % or more, more preferably 70 mass % or more, further preferably 80 mass % or more, and particularly preferably 90 mass % or more. Furthermore, the above content may also be 100 mass %.

The developer may further contain other components. As other components, for example, a known surfactant or a known defoaming agent can be listed.

[Developer supply method] As long as the desired pattern can be formed, there is no particular limitation on the developer supply method, and there are the following methods: a method of immersing a substrate formed with a film in the developer, a method of supplying the developer to the film formed on the substrate using a nozzle for immersion development, or a method of continuously supplying the developer. There is no particular limitation on the type of nozzle, and examples include a straight nozzle, a shower nozzle, and a mist nozzle. In terms of the permeability of the developer, the removability of the non-image area, and the efficiency in manufacturing, the method of supplying the developer with a straight nozzle or the method of continuously supplying the developer with a mist nozzle is preferred, and in terms of the permeability of the developer to the image area, the method of supplying the developer with a mist nozzle is more preferred. In addition, the following steps may be adopted: after continuously supplying the developer with a direct nozzle, the substrate is rotated to remove the developer from the substrate, and after rotating and drying, the developer is continuously supplied with a direct nozzle again, and the substrate is rotated to remove the developer from the substrate. This step may also be repeated several times. As a method for supplying the developer in the developing step, there can be listed: a step of continuously supplying the developer to the substrate, a step of keeping the developer on the substrate in a substantially static state, a step of vibrating the developer on the substrate using ultrasound or the like, and a step of combining these steps, etc.

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

In the developing step, the pattern may be cleaned (rinsed) with a rinse solution after being treated with a developer. Alternatively, a rinse solution may be supplied before the developer in contact with the pattern is completely dried.

[Rinsing liquid] When the developer is an alkaline aqueous solution, water, for example, can be used as the rinse liquid. When the developer is a developer containing an organic solvent, 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.

As the organic solvent when the rinse liquid contains an organic solvent, the same organic solvent as the organic solvent exemplified when the developer contains an organic solvent can be listed. It is preferable that the organic solvent contained in the rinse liquid is different from the organic solvent contained in the developer, and it is more preferable that the organic solvent has a lower solubility in the pattern than the organic solvent contained in the developer.

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

When the rinse liquid contains an organic solvent, the organic solvent is preferably 50 mass % or more, more preferably 70 mass % or more, and even more preferably 90 mass % or more relative to the total mass of the rinse liquid. Alternatively, the organic solvent may be 100 mass % relative to the total mass of the rinse liquid.

The rinse solution may further contain other components. As other components, for example, a known surfactant or a known defoaming agent can be listed.

[Method for supplying the rinse liquid] As long as the desired pattern can be formed, there is no particular limitation on the method for supplying the rinse liquid. The following methods are available: a method of immersing the substrate in the rinse liquid, a method of supplying the rinse liquid to the substrate by a liquid pile, a method of supplying the rinse liquid to the substrate by spraying, a method of continuously supplying the rinse liquid to the substrate by a straight nozzle, etc. In terms of the permeability of the rinse liquid, the removal of the non-image area, and the efficiency in manufacturing, there are methods of supplying the rinse liquid using a shower nozzle, a straight nozzle, a spray nozzle, etc. The method of continuous supply using a spray nozzle is preferred. In terms of the permeability of the rinse liquid to the image area, the method of supplying using a spray nozzle is more preferred. There is no particular limitation on the type of nozzle, and straight nozzles, shower nozzles, spray nozzles, etc. can be listed. That is, the rinsing step is preferably a step of supplying or continuously supplying the rinsing liquid to the film after exposure using a direct nozzle, and more preferably a step of supplying the rinsing liquid using a spray nozzle. As a method of supplying the rinsing liquid in the rinsing step, there can be adopted a step of continuously supplying the rinsing liquid to the substrate, a step of keeping the rinsing liquid in a substantially static state on the substrate, a step of vibrating the rinsing liquid on the substrate using ultrasound or the like, and a step of combining these.

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.

<Heating step> The pattern obtained by the developing step (the pattern after washing when the washing step is performed) can be subjected to a heating step of heating the pattern obtained by the above-mentioned development. That is, the method for producing a hardened product of the present invention may include a heating step of heating the pattern obtained by the developing step. Furthermore, the method for producing a hardened product of the present invention may also include a heating step of heating a pattern obtained by other methods without the developing step or a film obtained by the film forming step. In the heating step, a resin such as a polyimide precursor is cyclized to become a resin such as a polyimide. In addition, crosslinking of unreacted crosslinking groups in the specific resin or the crosslinking agent other than the specific resin is also performed. As the heating temperature (maximum heating temperature) in the heating step, 50 to 450°C is preferred, 150 to 350°C is more preferred, 150 to 250°C is further preferred, 160 to 250°C is further preferred, and 160 to 230°C is particularly preferred.

The heating step is preferably a step of promoting the cyclization reaction of the polyimide precursor in the pattern by heating and utilizing the action of the alkali generated by the alkali generator.

The heating in the heating step is preferably performed at a heating rate of 1 to 12°C/min from the temperature at the start of heating to the maximum heating temperature. The above heating rate is preferably 2 to 10°C/min, and 3 to 10°C/min is further preferred. By setting the heating rate to 1°C/min or more, productivity can be ensured and excessive volatilization of acid or solvent can be prevented. By setting the heating rate to 12°C/min or less, the residual stress of the hardened material can be alleviated. In addition, in the case of an oven capable of rapid heating, it is preferably performed at a heating rate of 1 to 8°C/sec from the temperature at the start of heating to the maximum heating temperature, 2 to 7°C/sec is further preferred, and 3 to 6°C/sec is further preferred.

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

The heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and further preferably 15 to 240 minutes.

In particular, when forming a multi-layer laminate, in terms of inter-layer adhesion, the heating temperature is preferably 30°C or higher, 80°C or higher, 100°C or higher, and 120°C or higher. The upper limit of the above heating temperature is preferably 350°C or lower, 250°C or lower, and 240°C or lower.

Heating can be performed in stages. For example, the following steps can be performed: heating from 25°C to 120°C at 3°C/min and maintaining at 120°C for 60 minutes, heating from 120°C to 180°C at 2°C/min and maintaining at 180°C for 120 minutes. In addition, as described in the specification of U.S. Patent No. 9159547, it is also preferred to perform the treatment while irradiating with ultraviolet rays. This pretreatment step can improve the properties of the membrane. The pretreatment step can be performed in a short time of about 10 seconds to 2 hours, and 15 seconds to 30 minutes is more preferred. The pretreatment step can be set as a step of more than two stages. For example, the first stage pretreatment step can be carried out in the range of 100 to 150°C, and then the second stage pretreatment step can be carried out in the range of 150 to 200°C. Furthermore, cooling can be carried out after heating, and the cooling speed at this time is preferably 1 to 5°C/minute.

Regarding the heating step, in order to prevent the decomposition of the specific resin, it is preferable to conduct the heating step in a low oxygen concentration environment by circulating an inert gas such as nitrogen, helium, or argon and conducting the heating step under reduced pressure. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less. The heating method in the heating step is not particularly limited, and examples thereof include a heating plate, an infrared furnace, an electric oven, a hot air oven, an infrared oven, and the like.

<Post-development exposure step> The pattern obtained by the development step (the pattern after washing when the washing step is performed) may be subjected to a post-development exposure step for exposing the pattern after the development step, instead of or in addition to the heating step. That is, the method for producing a hardened product of the present invention may include a post-development exposure step for exposing the pattern obtained by the development step. The method for producing a hardened 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. In the post-development exposure step, for example, the cyclization reaction of the polyimide precursor by the photosensitization of the photobase generator, the removal reaction of the acid-decomposable group by the photosensitization of the photoacid generator, etc. can be promoted. In the post-development exposure step, at least a part of the pattern obtained in the development step is sufficient to be exposed, but it is preferred that the entire pattern is exposed. The exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ/ ^cm2 , and more preferably 100 to 15,000 mJ/ ^cm2 , calculated as the exposure energy at the wavelength where the photosensitive compound has sensitivity. Regarding the post-development exposure step, for example, it can be performed using the light source in the above-mentioned exposure step, preferably using broadband light.

<Metal layer forming step> The pattern obtained by the developing step (preferably the pattern provided for at least one of the heating step and the post-development exposure step) can also be provided for the metal layer forming step of forming a metal layer on the pattern. That is, the method for producing a hardened 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 the pattern provided for at least one of the heating step and the post-development exposure step).

The metal layer is not particularly limited, and existing metals can be used. Examples thereof 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 further preferred.

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

The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm, based on the thickest portion.

<Application> As the manufacturing method of the cured product of the present invention or the field of the cured product, insulating films for electronic components, interlayer insulating films for redistribution layers, stress buffer films, etc. can be listed. In addition, sealing films, substrate materials (base films or cover films of flexible printed circuit boards, interlayer insulating films) or the formation of patterns by etching on insulating films for mounting purposes such as the above can be listed. For such uses, for example, you can refer to Science & Technology Co., Ltd. "High-functionalization and application technology of polyimide" April 2008, Kakimoto Masaaki/supervised, CMC Technical Library "Basics and development of polyimide materials" November 2011, Japan Polyimide and Aromatic Polymer Research Association/ed. "Latest Polyimide Fundamentals and Applications" NTS, August 2010, etc.

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 offset printing plates or screen plates, etching of formed parts, and producing protective varnishes and dielectric layers in electronics, especially microelectronics.

(Laminar body and method for manufacturing the laminated body) The laminated body of the present invention refers to a structure having a plurality of layers composed of the hardened material of the present invention. The laminated body is a laminated body including two or more layers composed of hardened materials, and may also be a laminated body including three or more layers. Among the two or more layers composed of the hardened materials contained in the laminated body, at least one layer is a layer composed of the hardened material of the present invention. In terms of suppressing the shrinkage of the hardened material or deformation of the hardened material accompanying the shrinkage, it is also preferred that all the layers composed of hardened materials contained in the laminated body are layers composed of the hardened material of the present invention.

That is, the method for manufacturing the laminate of the present invention preferably includes the method for manufacturing the hardened product of the present invention, and more preferably includes repeating the method for manufacturing the hardened product of the present invention several times.

The laminate of the present invention preferably includes two or more layers consisting of a hardened material, and preferably includes a metal layer between any of the layers consisting of the hardened material. The metal layer is preferably formed by the metal layer forming step. That is, the method for manufacturing the laminate of the present invention preferably further includes a metal layer forming step of forming a metal layer on the layer consisting of a hardened material between multiple hardened material manufacturing methods. The preferred embodiment of the metal layer forming step is as described above. As the above-mentioned laminate, for example, a laminate having a layer structure including at least three layers, namely, a layer composed of a first hardened material, a metal layer, and a layer composed of a second hardened material, can be cited as a preferred one. It is preferred that both the layer composed of the first hardened material and the layer composed of the second hardened material are layers composed of the hardened material of the present invention. The resin composition of the present invention used to form the layer composed of the first hardened material and the resin composition of the present invention used to form the layer composed of the second hardened material may be compositions of the same composition or compositions of different compositions. The metal layer in the laminate of the present invention can be preferably used as metal wiring such as a redistribution layer.

<Lamination step> The method for manufacturing a laminated body of the present invention preferably includes a lamination step. The lamination step is a series of steps including performing (a) a film forming step (layer forming step), (b) an exposure step, (c) a developing step, (d) a heating step, and at least one of a post-development exposure step on the surface of a pattern (resin layer) or a metal layer in sequence again. However, it is possible to repeat at least one of (a) a film forming step, (d) a heating step, and a post-development exposure step. Furthermore, it is possible to include (e) a metal layer forming step after at least one of (d) a heating step and a post-development exposure step. The layering step may of course further include the above-mentioned drying step, etc. as appropriate.

When a further layering step is performed after the layering step, a surface activation treatment step may be further performed after the exposure step, after the heating step, or after the metal layer forming step. Plasma treatment is exemplified as the surface activation treatment. Details of the surface activation treatment will be described later.

The above-mentioned lamination step is preferably performed 2 to 20 times, and more preferably 2 to 9 times. For example, in the case of resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, it is preferred that the resin layer has a structure of more than 2 layers and less than 20 layers, and it is further preferred that the resin layer has a structure of more than 2 layers and less than 9 layers. The composition, shape, film thickness, etc. of the above-mentioned layers may be the same or different.

In the present invention, after the metal layer is provided, it is preferred that a cured product (resin layer) of the resin composition of the present invention is further formed to cover the metal layer. Specifically, there can be cited an embodiment in which the following sequence of (a) film forming step, (b) exposure step, (c) development step, (d) heating step and at least one of the post-development exposure step, and (e) metal layer forming step is repeated, or an embodiment in which the following sequence of (a) film forming step, (d) heating step and at least one of the post-development exposure step, and (e) metal layer forming step is repeated. By alternately performing the step of laminating the resin composition layer (resin layer) of the present invention and the step of forming the metal layer, the resin composition layer (resin layer) of the present invention and the metal layer can be alternately laminated.

(Surface activation treatment step) The method for manufacturing a laminate of the present invention preferably includes a surface activation treatment step of performing surface activation treatment on at least a portion of the above-mentioned metal layer and the resin composition layer. The surface activation treatment step is usually performed after the metal layer forming step, but the metal layer forming step can also be performed after the above-mentioned development step (preferably after at least one of the heating step and the post-development exposure step) and after performing the surface activation treatment step on the resin composition layer. The surface activation treatment can be performed only on at least a portion of the metal layer, or only on at least a portion of the resin composition layer after exposure, or on at least a portion of each of the metal layer and the resin composition layer after exposure. It is preferred to perform the surface activation treatment on at least a portion of the metal layer, and it is preferred to perform the surface activation treatment on a portion or all of the area of the metal layer where the resin composition layer is formed on the surface. In this way, by performing the surface activation treatment on the surface of the metal layer, the adhesion with the resin composition layer (film) disposed on the surface can be improved. It is also preferred to perform the surface activation treatment on a portion or all of the resin composition layer (resin layer) after exposure. In this way, by performing a surface activation treatment on the surface of the resin composition layer, the adhesion with the metal layer or resin layer provided on the surface after the surface activation treatment can be improved. In particular, when the resin composition layer is hardened, such as when negative development is performed, it is not easy to be damaged by the surface treatment, so that the adhesion is easily improved. The surface activation treatment can be implemented, for example, by the method described in paragraph 0415 of International Publication No. 2021/112189. This content is incorporated into this specification.

(Semiconductor device and method for manufacturing the same) The present invention also discloses a semiconductor device including the cured product or laminate of the present invention. Furthermore, the present invention also discloses a method for manufacturing a semiconductor device including a method for manufacturing the cured product or laminate of the present invention. As a specific example of a semiconductor device in which the resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer, reference can be made to paragraphs 0213 to 0218 and FIG. 1 of Japanese Patent Publication No. 2016-027357, which are incorporated into this specification. [Example]

The present invention is further specifically described below by way of examples. The materials, usage amounts, ratios, processing contents, processing sequences, etc. shown in the following examples can be appropriately changed without departing from the main purpose 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 mass standards.

<Resin Synthesis> [Synthesis of 6-cis-butenediimidohexanoyl chloride (M-1)] In an eggplant-shaped flask equipped with a thermometer and a calcium chloride tube, 7.92 g (37.5 mmol) of 6-cis-butenediimidohexanoic acid was dissolved in 30 g of tetrahydrofuran, and 0.1 g of N,N'-dimethylformamide was added. The mixture was cooled to 0°C while being stirred with a magnetic stirrer. Then, 4.85 g (38.25 mmol) of oxalyl chloride was added dropwise, and the mixture was stirred at 0°C to 10°C for 1 hour. Then, the temperature was raised to 25°C and stirred for 2 hours to synthesize 6-cis-butenediimidohexanoyl chloride (M-1). [Chemical formula 54]

[Synthesis of M-2 to M-4] The compounds represented by the following formulae (M-2), (M-3) and (M-4) were synthesized in the same manner as the above-mentioned 6-butene diimidoyl chloride (M-1). [Chemical Formula 55]

[Synthesis Example SP-1: Synthesis of Polyimide (SP-1)] 30.0 g (57.64 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride was dissolved in 130 g of N-methylpyrrolidone (NMP). Next, 3.20 g (12.39 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane, 7.89 g (37.18 mmol) of m-tolidine, and 2.78 g (11.53 mmol) of hexadecylamine were added while washing with 50 g of NMP, and the mixture was stirred at 20° C. to 50° C. for 30 minutes. Then, 10 g of toluene was added, and the mixture was reacted at 200° C. for 4 hours while nitrogen was flowing, and then cooled to 25° C. Then, a THF solution of 6-cis-butenediimidoyl chloride (M-1) synthesized in the above (content of M-1: 37.5 mmol), 6.13 g (77.5 mmol) of pyridine, and 0.10 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl free radical were added, and the mixture was reacted at 25°C for 2 hours, then heated to 45°C and stirred for 10 hours. Then, the reaction solution was cooled to 25°C, diluted with 200 g of tetrahydrofuran, and the reaction solution was added dropwise to a mixed solution of 2.0 L of methanol and 0.5 L of water, and the mixture was stirred for 15 minutes, and then the polyimide resin was filtered. Next, the resin was re-pulped with 1 L of water and filtered, and then re-pulped with 1 L of methanol and filtered, and dried at 40° C. under reduced pressure for 10 hours. Next, the dried resin was dissolved in 300 g of tetrahydrofuran, and 40 g of ion exchange resin (MB-1: manufactured by ORGANO CORPORATION) was added, stirred for 4 hours, and after filtering to remove the ion exchange resin, the polyimide resin was precipitated in 2 L of methanol and stirred for 15 minutes. The polyimide resin was filtered and dried at 45°C for 1 day under reduced pressure to obtain polyimide (SP-1). The weight average molecular weight of the obtained polyimide (SP-1) was 23,700 and the number average molecular weight was 8,900. Polyimide (SP-1) is a resin having a repeating unit represented by the following formula SP-1. The structure of the repeating unit was determined by ¹ H-NMR spectrum. In the following structure, the subscript in parentheses represents the molar ratio of each structure. [Chemical Formula 56]

[Synthesis Examples SP-2 to SP-6: Synthesis of Polyimides (SP-2 to SP-6)] SP-2 to SP-6 were synthesized by the same method as SP-1 except that 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride, 2,2-bis(3-amino-4-hydroxyphenyl) propane and hexadecylamine were appropriately changed to have the following structures. Polyimides (SP-2) to (SP-6) are resins having repeating units represented by the following formulas SP-2 to SP-6, respectively. The structure of each repeating unit was determined by ¹ H-NMR spectrum. In the following structures, the subscripts in parentheses represent the molar ratio of each structure. The weight average molecular weight and number average molecular weight of these resins are shown in the table below. [Chemical formula 57] [Chemical formula 58] [Chemical formula 59] [Chemical formula 60] [Chemical formula 61]

[Synthesis Examples SP-7 to SP-23: Synthesis of Polyimides (SP-7 to SP-23)] SP-7 to SP-23 were synthesized by the same method as SP-1 except that 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride, 2,2-bis(3-amino-4-hydroxyphenyl) propane and hexadecylamine were appropriately changed to obtain resins of the following structures. Polyimides (SP-7) to (SP-23) are resins having repeating units represented by the following formulas SP-7 to SP-23, respectively. The structure of each repeating unit was determined by ¹ H-NMR spectroscopy. In the following structures, the subscripts in parentheses represent the molar ratio of each structure. The weight average molecular weight and number average molecular weight of these resins are shown in the table below. [Chemical Formula 62] [Chemical formula 63] [Chemical formula 64] [Chemical formula 65] [Chemical formula 66] [Chemical formula 67] [Chemical formula 68] [Chemical formula 69] [Chemical formula 70] [Chemical formula 71] [Chemical formula 72] [Chemical formula 73] [Chemical formula 74] [Table 1] Resin Weight average molecular weight Number average molecular weight Cis-butylene diimide value (mmol/g) Imidization rate (%) SP-1 23,700 8,900 0.62 More than 99% SP-2 12,500 5,300 0.46 More than 99% SP-3 25,200 10,200 0.73 More than 99% SP-4 18,700 7,500 0.87 More than 99% SP-5 20,000 8,200 0.93 More than 99% SP-6 13,300 5,600 0.59 More than 99% SP-7 21,200 8,300 0.63 More than 99% SP-8 16,900 6,500 0.63 More than 99% SP-9 24,000 9,800 0.79 More than 99% SP-10 19,800 8,000 1.04 More than 99% SP-11 30,600 12,000 1.21 More than 99% SP-12 9,500 4,100 1.56 More than 99% SP-13 18,600 7,300 0.60 More than 99% SP-14 20,100 7,900 0.73 More than 99% SP-15 40,600 15,000 0.65 More than 99% SP-16 16,700 7,100 1.25 More than 99% SP-17 15,500 6,700 0.84 More than 99% [Table 2] Weight average molecular weight Number average molecular weight Cis-butylene diimide value (mmol/g) Imidization rate (%) SP-18 38,100 15,100 0.85 More than 99% SP-19 27,500 10,600 1.25 More than 99% SP-20 22,300 9,200 0.84 More than 99% SP-21 44,500 17,100 1.42 More than 99% SP-22 33,500 13,000 1.05 More than 99% SP-23 18,800 7,900 1.15 More than 99%

[Synthesis Example ST-1: Synthesis of polyimide (ST-1)] 30.00 g (57.64 mmol) of 4,4'-(4,4'-isopropylidene diphenyloxy) diphthalic anhydride was dissolved in 150 g of N-methylpyrrolidone (NMP). Then, 5.36 g (24.79 mmol) of HAB (manufactured by Wakayama Energy Chemical Industry Trade Corporation), 9.13 g (24.79 mmol) of 4,4'-bis(3-aminophenoxy)biphenyl, 2.51 g (10.38 mmol) of hexadecylamine and 10 g of toluene were added while washing with 30 g of NMP, and after stirring for 15 minutes, the mixture was reacted at 200°C for 4 hours while nitrogen was flowing, and then cooled to 25°C. Next, 15.3 g (100 mmol) of 4-(chloromethyl)styrene, 16.6 g (120 mmol) of potassium carbonate, 1.66 g (12 mmol) of potassium iodide, and 0.1 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical were added, and the mixture was reacted at 95°C for 15 hours, then cooled to 25°C, diluted with 150 g of tetrahydrofuran, and the salt in the reaction solution was filtered with filter paper. Next, the reaction solution was added dropwise to a mixture of 1.8 L of methanol and 0.6 L of water, and the mixture was stirred for 15 minutes, and then the polyimide resin was filtered. Next, the resin was re-pulped with 1 L of water and filtered, and then re-pulped with 1 L of methanol and filtered, and dried at 40° C. under reduced pressure for 8 hours. Next, the dried resin was dissolved in 300 g of tetrahydrofuran, and 40 g of ion exchange resin (MB-1: manufactured by ORGANO CORPORATION) was added, stirred for 4 hours, and after filtering to remove the ion exchange resin, the polyimide resin was precipitated in 2 L of methanol and stirred for 15 minutes. The polyimide resin was filtered and dried at 45°C for 1 day under reduced pressure to obtain a polyimide resin (ST-1). The weight average molecular weight of the obtained polyimide resin ST-1 was 19,700 and the number average molecular weight was 8,000. Polyimide (ST-1) is a resin having a repeating unit represented by the following formula ST-1. The structure of the repeating unit was determined by ¹ H-NMR spectrum. In the following structure, the subscript in parentheses represents the molar ratio of each structure. [Chemical Formula 75]

[Synthesis Examples ST-2 to ST-5: Synthesis of Polyimide (ST-2) to (ST-5)] ST-2 to ST-5 were synthesized by the same method as ST-1, except that the diamine raw material was appropriately changed according to the following structure and 4-(chloromethyl)styrene was changed to 1-chlorododecane or 3-chloropropyl methacrylate. Polyimide (ST-2) to (ST-5) are resins having repeating units represented by the following formulas ST-2 to ST-5, respectively. The structure of each repeating unit was determined by ¹ H-NMR spectrum. In the following structure, the subscript in parentheses represents the molar ratio of each structure. In addition, the weight average molecular weight and number average molecular weight of these resins are recorded in the table below. [Chemical Formula 76] [Chemical formula 77]

[Table 3] Weight average molecular weight Number average molecular weight Imidization rate (%) ST-1 19,700 8,000 More than 99% ST-2 10,100 4,700 More than 99% ST-3 33,500 12,900 More than 99% ST-4 15,500 6,700 More than 99% ST-5 20,100 8,100 More than 99%

<Synthesis of polyimide precursor> [Synthesis Example SA-1: Synthesis of polyimide precursor (SA-1)] 19.83 g (38.1 mmol) of 4,4'-(4,4'-isopropylenediphenoxy)diphthalic anhydride, 10.12 g (77.8 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 13.40 g (169 mmol) of pyridine, and 70 g of diethylene glycol monomethyl ether were mixed and stirred at 60°C for 5 hours to produce a diester of 4,4'-(4,4'-isopropylenediphenoxy)bis(phthalic anhydride) and glycerol dimethacrylate. Next, after the mixture was cooled to -10°C, 9.53 g (79.2 mmol) of thionyl chloride was added dropwise over 90 minutes, and the mixture was stirred for 2 hours to obtain a white precipitate of pyridinium hydrochloride. Next, a solution obtained by dissolving 7.12 g (33.5 mmol) of m-tolidine in 100 mL of NMP (N-methyl-2-pyrrolidone) was added dropwise over 2 hours. Next, 10.0 g (217 mmol) of ethanol was added, and the mixture was stirred for 2 hours. Next, the polyimide protopolymer resin was precipitated in 4 L of water, and the water-polyimide protopolymer resin mixture was stirred at 500 rpm for 15 minutes. The polyimide proto-resin was filtered, stirred again in 4 L of water for 30 minutes, filtered again, and dried at 40°C for 2 days. Next, the dried resin was dissolved in 200 g of tetrahydrofuran, 50 g of ion exchange resin (MB-1: manufactured by ORGANO CORPORATION) was added, and stirred for 6 hours. Next, the polyimide proto-resin was precipitated in 4 L of water, and the water-polyimide proto-resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was filtered and dried at 45°C for two days under reduced pressure to obtain a polyimide precursor (SA-1). The weight average molecular weight of the obtained polyimide precursor (SA-1) was 24,600 and the number average molecular weight was 9,400. The imidization rate of the polyimide precursor (SA-1) was less than 3%. [Chemical Formula 78]

<Synthesis of diamine> [Synthesis of dinitro compound (A-1)] In a flask equipped with a condenser and a stirrer, 26.0 g (0.2 mol) of 2-hydroxyethyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation) and 17.4 g (0.22 mol) of dehydrated pyridine (manufactured by FUJIFILM Wako Pure Chemical Corporation) were dissolved in 78 g of ethyl acetate, and the mixture was cooled to 5° C. or below. Next, 48.4 g (0.21 mol) of 3,5-dinitrobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 145 g of ethyl acetate, and the solution was added dropwise to the flask over 1 hour using a dropping funnel. After the addition was completed, the mixture was stirred at a temperature below 10°C for 30 minutes, and then the temperature was raised to 25°C and stirred for 3 hours. The reaction solution was then diluted with 600 mL of ethyl acetate (CH ₃ COOEt), transferred to a separatory funnel, and washed with 300 mL of water, 300 mL of saturated sodium bicarbonate, 300 mL of dilute hydrochloric acid, and saturated saline, in that order. After separation and washing, the mixture was dried with 30 g of magnesium sulfate, concentrated and vacuum dried using an evaporator to obtain 61.0 g of a dinitro compound (A-1). The NMR spectrum confirmed that the compound was a dinitro compound (A-1). The dinitro compound (A-1) was analyzed by ¹ H-NMR. The results are shown below. ¹ H-NMR data (deuterated chloroform, 400 MHz, internal standard: tetramethylsilane) δ (ppm) = 1.97 (s, 3H), 4.55-4.57 (m, 2H), 4.70-4.73 (m, 2H), 5.63 (s, 1H), 6.16 (s, 1H), 9.16-9.17 (d, 2H), 9.24-9.25 (d, 1H)

<Synthesis of diamine (AA-1)> In a flask equipped with a condenser and a stirrer, 27.9 g (500 mmol) of reduced iron (manufactured by FUJIFILM Wako Pure Chemical Corporation), 5.9 g (110 mmol) of ammonium chloride (manufactured by FUJIFILM Wako Pure Chemical Corporation), 3.0 g (50 mmol) of acetic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation), and 0.03 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were weighed, and 200 mL of isopropyl alcohol (IPA) and 30 mL of pure water were added and stirred. Then, 16.2 g of the dinitro compound (A-1) was added little by little over 1 hour, and stirred for 30 minutes. Next, the external temperature was raised to 85°C and stirred for 2 hours. After cooling to below 25°C, the mixture was filtered using CELITE (registered trademark). The filtrate was concentrated using a rotary evaporator and dissolved in 800 mL of ethyl acetate. The mixture was transferred to a separatory funnel and washed twice with 300 mL of saturated sodium bicarbonate, and then washed with 300 mL of water and 300 mL of saturated saline. After separation and washing, the mixture was dried with 30 g of magnesium sulfate, concentrated using an evaporator, and vacuum dried to obtain 11.0 g of diamine (AA-1). The NMR spectrum confirmed that the mixture was diamine (AA-1). ¹ H-NMR data (deuterated chloroform, 400 MHz, internal standard: tetramethylsilane) δ (ppm) = 1.95 (s, 3H), 3.68 (s, 4H), 4.45-4.47 (m, 2H), 4.50-4.53 (m, 2H), 5.58 (s, 1H), 6.14 (s, 1H), 6.19-6.20 (t, 1H), 6.77-6.78 (d, 2H) [Chemical formula 79]

<Synthesis of polyimide precursor resin (SA-2)> In a flask equipped with a condenser and a stirrer, 14.1 g (47.8 mmol) of oxydiphthalic dianhydride was suspended in 100 g of diethylene glycol dimethyl ether while removing water. Then, 13.4 g (100 mmol) of diethylene glycol monoethyl ether and 16.8 g (132 mmol) of pyridine were added and stirred at 80°C for 5 hours. Then, after the mixture was cooled to -20°C, 11.9 g (100 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridine hydrochloride was obtained. Next, the mixture was heated to room temperature and stirred for 2 hours, then 30 mL of N-methylpyrrolidone (NMP) was added, and a solution obtained by dissolving 10.3 g (39 mmol) of diamine (AA-1) in 50 mL of NMP was added dropwise over 1 hour. During the addition of the diamine, the viscosity increased. Next, 6.0 g (188 mmol) of methanol and 0.05 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours. Next, the polyimide proto-driver resin was precipitated in 3 liters of water, and the water-polyimide proto-driver resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 3 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried at 45°C for 1 day under reduced pressure. The molecular weight of the polyimide precursor (SA-2) was Mw=14,300 and Mn=6,500. The structure of the polyimide precursor (SA-2) was a structure represented by the following formula (SA-2). In addition, the imidization rate of the polyimide precursor (SA-2) was less than 3%. [Chemical formula 80]

[Synthesis of polyimide precursor (SA-3)] Polyimide precursor (SA-3) was synthesized by the same method as the synthesis of polyimide precursor (SA-2). The molecular weight of polyimide precursor (SA-3) was Mw = 12,500, Mn = 5,600. In addition, the imidization rate of polyimide precursor (SA-3) was less than 3%. [Chemical formula 81]

<Synthesis of comparative compound A-1> 25.6 g (57.64 mmol) of 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride was dissolved in 100 g of N-methylpyrrolidone (NMP). Then, 21.3 g (51.88 mmol) of 4,4'-isopropylidenebis[(4-aminophenoxy)benzene] and 0.76 g (6.92 mmol) of p-aminophenol were added while rinsing with 60 g of NMP, and the mixture was stirred at 20°C to 50°C for 30 minutes. Then, 10 g of toluene was added, and the mixture was reacted at 200°C for 4 hours while nitrogen was flowing, and then cooled to 25°C. Then, the THF solution (10.5 mmol) of 6-butene diimide hexanoyl chloride synthesized in the above, 1.19 g (15 mmol) of pyridine, and 0.10 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl free radical were added, and the mixture was reacted at 25°C for 2 hours, then heated to 45°C and stirred for 10 hours. Then, the reaction solution was cooled to 25°C, diluted with 200 g of tetrahydrofuran, and the reaction solution was added dropwise to a mixture of 2.0 L of methanol and 0.5 L of water, and the mixture was stirred for 15 minutes, and then the polyimide resin was filtered. Next, the resin was re-pulped with 1 L of water and filtered, and then re-pulped with 1 L of methanol and filtered, and dried at 40° C. under reduced pressure for 10 hours. Next, the dried resin was dissolved in 300 g of tetrahydrofuran, and 40 g of ion exchange resin (MB-1: manufactured by ORGANO CORPORATION) was added, stirred for 4 hours, and after filtering to remove the ion exchange resin, the polyimide resin was precipitated in 2 L of methanol and stirred for 15 minutes. The polyimide resin was filtered and dried at 45°C for 1 day under reduced pressure to obtain a polyimide resin (A-1). The weight average molecular weight of the obtained polyimide resin A-1 was 28,800 and the number average molecular weight was 10,900. [Chemical Formula 82]

<Synthesis of comparative compound A-2> In a dry reactor equipped with a flat-bottom joint (equipped with a stirrer, a condenser and an internal thermometer), 44.43 g (121.3 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 57.29 g (125.0 mmol) of 1,4-Phenylene Bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylate) were added while removing water, and 492.43 g of γ-butyrolactone was added, and the mixture was stirred at 60°C for 1.5 hours. Next, after adding 50 mL of toluene, nitrogen was flowed at a flow rate of 200 mL/min, while the temperature was raised to 180°C, stirred for 3 hours, and then cooled to room temperature. The obtained polymerization solution was diluted with acetone to prepare a dilution solution, and then the dilution solution was added dropwise to a mixed solution of water/methanol = 3/1, thereby precipitating a white solid. The obtained white solid was recovered and vacuum dried at a temperature of 120°C, thereby obtaining 90 g of a polymer. Next, 73.86 g (150.0 mmol in terms of hydroxyl group) of the polymer obtained above, 21.17 g (150.0 mmol) of 2-isocyanatoethyl acrylate (also referred to as AOI, manufactured by Showa Denko KK) and 828.26 g of γ-butyrolactone (GBL) were added to a reaction vessel equipped with a stirrer and a cooling tube. Thereafter, the temperature was raised to 120°C while stirring, and the mixture was reacted for 6 hours. Next, the obtained reaction solution was diluted with acetone to prepare a dilution, and the dilution was then added dropwise to a mixed solution of water/methanol = 2/1, thereby precipitating a white solid. The obtained white solid was recovered and vacuum dried at 40°C to obtain 71.8 g of A-2. The weight average molecular weight (Mw) of A-2 was 78,500, and the number average molecular weight (Mn) was 30,200. The structure of A-2 was confirmed by ¹ H-NMR spectroscopy to be the main component of the structure represented by the following formula (A-2). The measurement results of ¹ H-NMR showed that the introduction rate of the crosslinking group was 55%. [Chemical formula 83]

<Examples and Comparative Examples> In each example, the components listed in the following table were mixed to obtain each resin composition. In addition, in each comparative example, the components listed in the following table were mixed to obtain each comparative composition. Specifically, the content of each component listed in the table was set to the amount (mass parts) listed in the "addition amount" column of each column of the table. The obtained resin composition and comparative composition were pressure filtered using a polytetrafluoroethylene filter with a pore width of 0.5μm. In addition, in the table, the record of "-" indicates that the composition does not contain the corresponding component.

[Table 4] Resin Polymeric compounds Solvent Polymerization initiator Migration inhibitors Metal Adhesion Improver Polymerization inhibitor Metal Complex Hardening conditions Development method (developer) Resolution Flatness Insulation reliability Relative dielectric constant (Dk) Dielectric loss tangent (Df) Type Addition amount Type Addition amount Type Addition amount Type Addition amount Type Addition amount Type Addition amount Type Addition amount Type Addition amount temperature Hardening time Embodiment 1 SP-1 30.8 B-1 5.5 GBL 61 OXE-02 1.65 E-1 0.1 F-4 0.7 G-1 0.04 I-3 0.2 230℃ 3 hours Cyclopentanone A A B A A Embodiment 2 SP-2 30.5 B-1 6.0 GBL 61 OXE-02 1.7 E-2 0.1 F-5 0.7 G-2 0.04 - - 200℃ 3 hours Cyclopentanone A A B B B Embodiment 3 SP-3 30 B-1/ B-4 4.0/ 1.5 DMSO/γ-V 61.5 OXE-01/ CPI-310B 1.0 /0.7 E-3 0.1 F-6 0.7 G-2 0.04 - - 230℃ 5 hours Cyclopentanone B B B A A Embodiment 4 SP-4 30 B-3 5.5 DMSO/GBL 62 OXE-02 1.65 E-4 0.1 F-1 0.7 G-2 0.04 - - 230℃ 3 hours Cyclopentanone A A B A A Embodiment 5 SP-5 30 B-1 6.5 DMSO/GBL 61 OXE-01 1.65 E-5 0.1 F-1 0.7 G-2 0.04 - - 200℃ 2 hours Cyclopentanone A B B B B Embodiment 6 SP-6 30.8 B-1 5.5 GBL 61 OXE-02 1.65 E-6 0.1 F-1 0.7 G-2 0.05 I-3 0.2 170℃ 3 hours Cyclopentanone B B B B B Embodiment 7 SP-7 30.2 B-1 6.3 GBL 61 OXE-02 1.65 E-7 0.1 F-1 0.7 G-2 0.04 - - 230℃ 3 hours Cyclopentanone B A B A A Embodiment 8 SP-8 29.9 B-2 6.6 GBL 61 OXE-02 1.65 E-2 0.1 F-2 0.7 G-2 0.04 - - 230℃ 3 hours Cyclopentanone A B B B B Embodiment 9 SP-9 30.7 B-5 6.8 γ-V 60 OXE-01 1.65 E-2 0.1 F-3 0.7 G-2 0.04 - - 230℃ 1 hour Cyclopentanone A A B A A Embodiment 10 SP-10 30.5 B-3 /B-5 3 /3.5 NMP 60 OXE-01 /D-1 1.5 /0.5 E-2 0.1 F-4 0.7 G-3 0.04 I-1 0.2 230℃ 2 hours Cyclopentanone B A B B B Embodiment 11 SP-12 30.8 B-1 5.5 GBL 61 OXE-02 1.65 E-1 0.1 F-4 0.7 G-1 0.04 I-3 0.2 230℃ 3 hours Cyclopentanone A A B B B Embodiment 12 SP-13 30.5 B-1 6.0 GBL 61 OXE-02 1.7 E-2 0.1 F-5 0.7 G-2 0.04 - - 200℃ 3 hours Cyclopentanone B A B B B Embodiment 13 SP-14 30.8 B-1 5.5 GBL 61 OXE-02 1.65 E-1 0.1 F-4 0.7 G-1 0.04 I-3 0.2 230℃ 3 hours Cyclopentanone B A B A B Embodiment 14 SP-15 30.8 B-1 5.5 GBL 61 OXE-02 1.65 E-6 0.1 F-1 0.7 G-2 0.05 I-3 0.2 230℃ 3 hours Cyclopentanone B B B A A Embodiment 15 SP-1 /ST-1 16.3 /16.3 B-1 5.0 GBL 60 OXE-01 1.27 E-7 0.15 F-6 0.7 G-4 0.08 I-2 0.2 230℃ 3 hours Cyclopentanone A A A A A Embodiment 16 SP-1 /ST-2 16.3 /16.3 B-1 5.2 GBL 60 OXE-01 1.27 E-7 0.15 F-6 0.7 G-4 0.08 - - 230℃ 3 hours Cyclopentanone A A A A A

[Table 5] Resin Polymeric compounds Solvent Polymerization initiator Migration inhibitors Metal Adhesion Improver Polymerization inhibitor Metal Complex Hardening conditions Development method (developer) Resolution Flatness Insulation reliability Relative dielectric constant (Dk) Dielectric loss tangent (Df) Type Addition amount Type Addition amount Type Addition amount Type Addition amount Type Addition amount Type Addition amount Type Addition amount Type Addition amount temperature Hardening time Embodiment 17 SP-3 /ST-4 26.1 /6.5 B-1 5.3 NMP 60 OXE-02 1.2 E-2 0.12 F-1 0.7 G-4 0.08 - - 230℃ 3 hours Cyclopentanone B B A B B Embodiment 18 SP-9 /ST-5 26.1 /6.5 B-1 5.3 DMSO/GBL 60 OXE-02 1.2 E-2 0.12 F-6 0.7 G-5 0.08 - - 230℃ 3 hours Cyclopentanone A A B B B Embodiment 19 SP-1 /ST-3 26.1 /6.5 B-1 5.3 DMSO/GBL 60 OXE-02 1.2 E-2 0.12 F-6 0.7 G-5 0.08 - - 230℃ 3 hours Cyclopentanone A B A B A Embodiment 20 SP-1 /SP-10 26.1 /6.5 B-1 5.3 DMSO/GBL 60 OXE-02 1.2 E-2 0.12 F-6 0.7 G-5 0.08 - - 230℃ 3 hours Cyclopentanone B A B B A Embodiment 21 SP-1 /SP-13 16.2 /16.2 B-1 5.0 GBL 60 OXE-01 /Irgacure784 1.17 /0.5 E-7 0.15 F-6 0.7 G-4 0.08 - - 230℃ 1 hour Cyclopentanone A A B A B Embodiment 22 SP-3 /ST-3 16.3 /16.3 B-1 5.2 GBL 60 OXE-01 1.27 E-7 0.15 F-6 0.7 G-4 0.08 - - 230℃ 3 hours Cyclopentanone B B A B B Embodiment 23 SP-1 /SA-1 26.1 /6.5 B-1 5.3 NMP 60 OXE-02 1.2 E-2 0.12 F-1 0.7 G-4 0.08 - - 230℃ 3 hours Cyclopentanone A B B B B Embodiment 24 SP-1 /SP-11 16.3 /15.3 B-1 6.0 GBL 60 OXE-01 1.27 E-7 0.15 F-6 0.7 G-4 0.08 I-2 0.2 230℃ 3 hours Cyclopentanone A B B A A Embodiment 25 SP-1 31.3 B-1 6.0 DMSO/GBL 61 OXE-02 1.65 - - - - G-2 0.05 - - 230℃ 3 hours Cyclopentanone A A B A A Embodiment 26 SP-16 30.8 B-1 5.5 GBL 61 OXE-02 1.65 E-6 0.1 F-1 0.7 G-2 0.05 I-3 0.2 170℃ 3 hours Cyclopentanone B A A B B Embodiment 27 SP-17 30.2 B-1 6.3 GBL 61 OXE-02 1.65 E-7 0.1 F-1 0.7 G-2 0.04 - - 230℃ 3 hours Cyclopentanone B B B B B Embodiment 28 SP-4 /SA-2 22.6 /10.0 B-1 5.3 NMP 60 OXE-02 1.2 E-2 0.12 F-1 0.7 G-4 0.08 - - 230℃ 3 hours Cyclopentanone A A A B B Embodiment 29 SP-9 /SA-3 20 /12.6 B-1 5.3 GBL 60 OXE-02 1.2 E-2 0.12 F-1 0.7 G-4 0.08 - - 230℃ 3 hours Cyclopentanone A A B A A Embodiment 30 SP-18 31.5 B-1 6.0 GBL 60 OXE-02 1.65 E-7 0.1 F-5 0.7 G-2 0.05 - - 230℃ 3 hours Cyclopentanone A B A A A Embodiment 31 SP-19 31.5 B-1 6.0 GBL 60 OXE-02 1.65 E-7 0.1 F-5 0.7 G-2 0.05 - - 230℃ 3 hours Cyclopentanone A A A B A Embodiment 32 SP-20 31.5 B-1 5.8 GBL 60 OXE-02 1.65 E-7 0.1 F-1 0.7 G-2 0.05 I-3 0.2 230℃ 3 hours Cyclopentanone B B B B B

[Table 6] Resin Polymeric compounds Solvent Polymerization initiator Migration inhibitors Metal Adhesion Improver Polymerization inhibitor Metal Complex Hardening conditions Development method (developer) Resolution Flatness Insulation reliability Relative dielectric constant (Dk) Dielectric loss tangent (Df) Type Addition amount Type Addition amount Type Addition amount Type Addition amount Type Addition amount Type Addition amount Type Addition amount Type Addition amount temperature Hardening time Embodiment 33 SP-21 31.5 B-1 6.0 GBL 60 OXE-02 1.65 E-7 0.1 F-5 0.7 G-2 0.05 - - 170℃ 3 hours Cyclopentanone B B B B A Embodiment 34 SP-22 31.5 B-1 6.0 GBL 60 OXE-02 1.65 E-7 0.1 F-5 0.7 G-2 0.05 - - 200℃ 3 hours Cyclopentanone A B A B A Embodiment 35 SP-23 31.5 B-1 6.0 GBL 60 OXE-02 1.65 E-7 0.1 F-5 0.7 G-2 0.05 - - 230℃ 3 hours Cyclopentanone A A A A A Comparison Example 1 A-1 30 B-1 7.5 NMP 60 OXE-02 1.3 E-2 0.2 F-1 0.7 G-2 0.1 I-1 0.2 230℃ 3 hours Cyclopentanone E C D C C Comparison Example 2 A-2 30 B-1 7.5 NMP 60 OXE-01 1.3 E-2 0.2 F-3 0.7 G-2 0.1 I-2 0.2 230℃ 3 hours Cyclopentanone C D C D D

[Resin (cyclized resin or its precursor)] ・SP-1 to SP-23: SP-1 to SP-23 synthesized in the above, SP-1 to SP-23 correspond to the above resin A and resin B. ・ST-1 to ST-5: ST-1 to ST-5 synthesized in the above, ST-1 to ST-15 correspond to the above resin A3 and resin C. ・SA-1 to SA-3: SA-1 to SA-3 synthesized in the above, SA-1 to SA-3 correspond to the above resin A2 and resin C. ・A-1 to A-2: Synthetic product of the above (comparative example)

[Polymerizable compounds] ・B-1: 1,12-dodecanediol dimethacrylate (melting point: 25°C or less) ・B-2: 1,9-nonanediol dimethacrylate (melting point: 25°C or less) ・B-3: 1,10-decanediol dimethacrylate (melting point: 25°C or less) ・B-4: SR-209 (manufactured by Sartomer Company, Inc., melting point: 25°C or less) ・B-5: ADPH: dipentaethrol hexaacrylate (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd., melting point: 25°C or less)

[Solvent] ・DMSO: dimethyl sulfoxide ・GBL: γ-butyrolactone ・NMP: N-methylpyrrolidone ・γ-V: γ-valerolactone In the table, "DMSO/GBL" means that DMSO and GBL were mixed at a mixing ratio (mass ratio) of DMSO:GBL = 20:80, and "DMSO/γ-V" means that DMSO and γ-V were mixed at a mixing ratio (mass ratio) of DMSO:γ-V = 20:80.

[Polymerization initiator (all trade names)] ・OXE-01: IRGACURE OXE 01 (manufactured by BASF) ・OXE-02: IRGACURE OXE 02 (manufactured by BASF) ・OXE-03: IRGACURE OXE 03 (manufactured by BASF) ・Irgacure784: Irgacure784 (manufactured by BASF) ・CPI-310B (manufactured by San-Apro Ltd.) ・D-1: Benzoyl peroxide (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Migration inhibitor] ・E-1 to E-7: Compounds with the following structures [Chemical formula 84]

[Metal Adhesion Improver] ・F-1 to F-3: Compounds with the following structures [Chemical Formula 85]・F-4: X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.) ・F-5: KBM-51073 (manufactured by Shin-Etsu Chemical Co., Ltd.) ・F-6: X-12-1214A (manufactured by Shin-Etsu Chemical Co., Ltd.)

[Polymerization inhibitor] ・G-1: 1,4-benzoquinone ・G-2: 4-methoxyphenol ・G-3: 1,4-dihydroxybenzene ・G-4: Compound with the following structure [Chemical formula 86]・G-5: 2-Nitroso-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Metal complex] ・I-1: TC-750 (manufactured by Matsumoto Fine Chemical Co. Ltd.) ・I-2: TC-401 (manufactured by Matsumoto Fine Chemical Co. Ltd.) ・I-3: Compound having the following structure [Chemical formula 87]

<Evaluation> [Evaluation of transmittance] When the resin composition obtained in each embodiment is used to form a cured product with a film thickness of 10 μm, the transmittance of the cured product at a wavelength of 365 nm is 15% or more. The cured product is obtained, for example, by the following method: the resin composition of the present invention is applied to a substrate such as a silicon wafer, dried, and exposed to the entire surface with i-rays at an exposure energy of 500 mJ/ ^cm2 , and then heated at a heating rate of 10°C/min in a nitrogen environment and heated at 230°C for 180 minutes.

[Evaluation of resolution] The resin composition used in each of the examples and the comparative examples was applied in layers on the surface of the copper thin layer of the resin substrate on which the copper thin layer was formed by the spin coating method, and dried at 100°C for 5 minutes to form a resin composition layer with a film thickness of 5 μm. Then, exposure was performed using a stepper (FPA-3000 i5 (manufactured by Canon Inc.) at NA = 0.50 and 300 mJ/cm ^2. Exposure was performed at a wavelength of 365 nm through a hole pattern mask having a hole pattern with a diameter of 3 to 20 μm formed at a scale of 1 μm. Next, develop with the developer listed in the "Developing Method (Developer)" column of the table for 15 seconds, rinse with PGMEA for 30 seconds, and then heat at a rate of 10°C/min in a nitrogen environment, and heat at the temperature and curing time listed in the "Curing Conditions" column of the table to obtain a hole pattern with a diameter of 3 to 20μm. The formed hole pattern was evaluated using the following evaluation criteria. The evaluation results are recorded in the "Resolution" column of the table. Image analysis was performed using SEM (scanning electron microscope), and when the residual film rate at the bottom of the hole was less than 1%, it was judged to be resolvable. It can be said that the smaller the hole pattern can be formed, the better the resolution is, for example, A, B or C is better. In addition, for examples that were not evaluated, "-" is recorded in the "Resolution" column of the table. -Evaluation Criteria- A: Able to resolve hole patterns with diameters up to 3μm. B: Able to resolve hole patterns with a diameter of 5μm, but unable to resolve hole patterns with a diameter of 3μm. C: Able to resolve hole patterns with a diameter of 7μm, but unable to resolve hole patterns with a diameter of 5μm. D: Able to resolve hole patterns with a diameter of 10μm, but unable to resolve hole patterns with a diameter of 7μm. E: Unable to resolve hole patterns with a diameter of 10μm.

[Evaluation of Flatness] In each embodiment and each comparative example, a resin composition or a comparative composition was applied by spin coating on a silicon wafer having a 1:1 L/S (line width and spacing) pattern with a height of 15 μm and a width of 20 μm and a taper angle of 85 degrees to form a resin composition layer. The silicon wafer to which the obtained resin composition layer was applied was dried on a heating plate, thereby obtaining a resin composition layer with a uniform film thickness of about 20 μm in the space portion of the copper wiring on the silicon wafer. The resin composition layer was heated at a rate of 10°C/min in a nitrogen atmosphere, and heated at the temperature listed in the "Temperature" column of the "Curing Conditions" in the table for the time listed in the "Curing Time" column of the "Curing Conditions" in the table to obtain a hardened material. The hardened material obtained was measured for the indentation X (μm) of the hardened material in the space portion of the copper wiring using a scanning electron microscope (S-4800) (manufactured by Hitachi High-Technologies Corporation), and evaluated using the following criteria. The evaluation results are listed in the "Flatness" column of the table. FIG1 is a schematic cross-sectional view of a state where a hardened material is formed on a silicon wafer having copper wiring formed thereon. The silicon wafer 16 in FIG. 1 has a copper wiring 14, and a hardened material 12 is formed on the silicon wafer 16. Here, the hardened material 12 in the area on the silicon wafer 16 where the copper wiring 14 is not formed has a dent 18 of Xμm. The width W of the space portion of the copper wiring is 20μm, and the taper angle θ of the copper wiring is 85°. For example, it can be observed that the dent 18 is the difference between the total thickness h1 of the hardened material and the copper wiring at the center of the copper wiring and the thickness h2 of the hardened material at the center of the copper wiring space. The smaller the dent 18 (X), the better the flatness, and therefore, the better the evaluation, for example, A, B or C is better. -Evaluation criteria- A: X is 1μm or less. B: X exceeds 1μm and is 2μm or less. C: X exceeds 2μm and is less than 3μm. D: X exceeds 3μm.

[Evaluation of Dielectric Constant and Dielectric Loss Tangent] Each resin composition or comparative composition prepared in each embodiment and comparative example was applied to a 12-inch silicon wafer by spin coating, thereby forming a resin composition layer. The silicon wafer to which the obtained resin composition layer was applied was dried at 100°C for 5 minutes on a heating plate, thereby forming a resin composition layer with a uniform thickness of 15 μm on the silicon wafer. The resin composition layer on the silicon wafer was exposed to light with an exposure energy of 500 mJ/cm ² using a stepper (Nikon NSR 2005 i9C). The exposed resin composition layer (resin layer) was heated at a heating rate of 10°C/min in a nitrogen atmosphere. The resin composition layer (resin layer) was heated at the temperature listed in the "Temperature" column of the "Curing Conditions" in the table for the time listed in the "Curing Time" column of the "Curing Conditions" in the table to obtain a cured layer (resin layer) of the resin composition layer. The cured layer (resin film) was immersed in a 4.9 mass% hydrofluoric acid aqueous solution, and the cured film was peeled off from the silicon wafer. The relative dielectric constant (Dk) and dielectric loss tangent (Df) of the thin film samples at 28 GHz were measured by the resonator perturbation method. <Measurement method> Split cylinder resonator (CR-728) (Device structure) Network analyzer: N5230A (manufactured by KEYSIGHT) (Evaluation standard) Relative dielectric constant (Dk) A: The relative dielectric constant (Dk) of the film is less than 2.9. B: The relative dielectric constant (Dk) of the film is less than 2.9 to 3.0. C: The relative dielectric constant (Dk) of the film is less than 3.0 to 3.2. D: The relative dielectric constant (Dk) of the film is 3.2 or more.

Dielectric loss tangent (Df) A: Dielectric loss tangent (Df) is less than 0.06. B: Dielectric loss tangent (Df) is less than 0.06 to 0.08. C: Dielectric loss tangent (Df) is less than 0.08 to 0.010. D: Dielectric loss tangent (Df) is greater than 0.010.

[Evaluation of moisture resistance] The resin composition or comparative composition prepared in each embodiment and comparative example was applied in layers on a copper substrate by spin coating to form a resin composition layer or a comparative composition layer. The copper substrate on which the resin composition layer or the comparative composition layer was formed was dried on a heating plate at 100°C for 5 minutes, and a resin composition layer or a comparative composition layer having a thickness of 5 μm and a uniform thickness was formed on the copper substrate. The resin composition layer or the comparative composition layer on the copper substrate was exposed to i-rays at an exposure energy of 500 mJ/ ^cm2 using a mask having a square non-mask portion of 100 μm square, and then developed for 60 seconds using the developer listed in the "Developing method (Developer)" column of the table and rinsed with propylene glycol monomethyl ether acetate (PGMEA), thereby obtaining a square resin layer of 100 μm square. Furthermore, in a nitrogen environment, at the temperature listed in the "Temperature" column of the "Curing Conditions" in the table, and for the time listed in the "Curing Time" column of the "Curing Conditions" in the table, a resin layer (pattern) was formed by heating using a heating oven. The above-mentioned resin composition layer and the copper substrate were placed in a tank at a temperature of 100°C/humidity of 100%RH for 100 hours. A cross-sectional SEM (scanning microscope) measurement was performed, and the void area ratio between the copper substrate and the resin layer was evaluated. The void area ratio was calculated by the following formula. Void area ratio (%) = (area of voids observed by SEM measurement) / (total area of resin layer) × 100 Based on the obtained void area ratio value, the evaluation was performed according to the following evaluation criteria. It can be said that the smaller the void area ratio, the better the PCT (wet heat) resistance of the cured film, and it can be said that even after a long time, voids are unlikely to form between the metal layer and the cured product. A: The void area ratio is 0.2% or less. B: The void area ratio exceeds 0.2% and is 0.5% or less. C: The void area ratio exceeds 0.5% and is 1% or less. D: The void area ratio exceeds 1%.

From the above results, it can be seen that the cured product obtained by the resin composition of the present invention has a low dielectric loss tangent. It can be seen that the content of the structure represented by formula (A-1) relative to the mass of resin A is less than 0.2 mmol/g, and the cured products obtained by the compositions of Comparative Examples 1 and 2 that do not contain the repeating unit represented by formula (1-1) have a high dielectric loss tangent.

<Example 101> The resin composition used in Example 1 was applied in layers to the copper thin layer surface of the resin substrate having the copper thin layer formed on the surface by spin coating, and after drying at 100°C for 4 minutes to form a resin composition layer with a film thickness of 20 μm, it was exposed using a stepper (manufactured by Nikon Corporation, NSR1505 i6). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a pattern of 1:1 line width and spacing and a line width of 10 μm). After exposure, heating was performed at 100°C for 4 minutes. After the above heating, development was performed with cyclohexanone for 2 minutes, and rinsing was performed with PGMEA for 30 seconds to obtain a layer pattern. Then, in a nitrogen environment, the temperature was raised at a rate of 10°C/min to 230°C, and then maintained at 230°C for 3 hours to form an interlayer insulating film for the redistribution layer. The interlayer insulating film for the redistribution layer has excellent insulation properties. In addition, the results of using the interlayer insulating film for the redistribution layer to manufacture semiconductor devices confirmed that they worked normally.

12: Hardened material 14: Copper wiring 16: Silicon wafer 18: Dent H: Height of copper wiring h1: Total thickness of hardened material and copper wiring at the center of copper wiring h2: Thickness of hardened material at the center of the space of copper wiring W: Width of the space of copper wiring θ: Taper angle of copper wiring

FIG. 1 is a schematic cross-sectional view showing a state where a hardened material is formed on a silicon wafer having copper wiring formed thereon.

without.

Claims (25)

A resin composition comprising: a resin A which is a polyimide and contains a structure represented by the following formula (A-1) in an amount of 0.20 to 5 mmol/g relative to the mass of the resin A; a polymerization initiator; and a polymerizable compound, [Chemical Formula 1] In formula (A-1), L ^A1 represents a single bond or an m+1 valent linking group, R ^R1 each independently represents a hydrogen atom or an organic group, two R ^R1 may be linked, m represents an integer greater than 1, and * represents a bonding site with other atoms. A resin composition as described in claim 1, wherein the structure represented by the aforementioned formula (A-1) is contained in the side chain in resin A. The resin composition as described in claim 1 or claim 2, wherein the free radical polymerizable value of the resin A is 0.20 to 5 mmol/g. The resin composition as claimed in claim 1 or claim 2, wherein L ^A1 in the formula (A-1) contains an aromatic group or an aliphatic saturated hydrocarbon group having 4 or more carbon atoms. The resin composition as described in claim 1 or claim 2 further contains resin A2 as a polyimide precursor. The resin composition as claimed in claim 1 or claim 2, wherein the resin A contains a repeating unit represented by the following formula (1-1): [Chemical Formula 2] In formula (1-1), ^X1 represents an organic group having 4 or more carbon atoms, ^Y1 represents an organic group having 4 or more carbon atoms, ^R1 each independently represents a structure represented by the following formula (R-1), m represents an integer of 0 to 4, and n represents an integer of 1 or more. [Chemical formula 3] In the formula (R-1), ^L1 represents an a2+1 valent linking group, ^Z1 represents an aromatic group, a cyclic aliphatic group or a linear or branched aliphatic saturated hydrocarbon group, R ^R1 each independently represents a hydrogen atom or an organic group, two R ^R1s may be linked, a1 represents an integer greater than 1 and less than the maximum number of substituents of ^Z1 , a2 represents an integer greater than 1, and * represents a bonding site with ^X1 or ^Y1 in the formula (1-1). The resin composition as claimed in claim 6, wherein ^X1 and ^Y1 in formula (1-1) each contain a structure obtained by removing two or more hydrogen atoms from a structure represented by any one of the following formulas (V-1) to (V-4), [Chemical Formula 4] In formula (V-2), ^RX1 is independently a hydrogen atom, an alkyl group or a halogenated alkyl group. In formula (V-3), ^RX2 and ^RX3 are independently a hydrogen atom or a substituent. ^RX2 and ^RX3 may be bonded to form a ring structure. The resin composition as described in claim 6, which contains repeating units represented by formula (1-1) and has at least one group selected from the group consisting of a linear or branched monovalent aliphatic hydrocarbon group having 6 or more carbon atoms, and a cyclic aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted by a linear aliphatic hydrocarbon group having 4 or more carbon atoms. A resin composition comprising: a resin B comprising a repeating unit represented by the following formula (1-1); a resin C comprising at least one of the repeating units represented by the following formula (2-1) and the following formula (3-1); a polymerization initiator; and a polymerizable compound, [Chemical Formula 5] In formula (1-1), ^X1 represents an organic group having 4 or more carbon atoms, ^Y1 represents an organic group having 4 or more carbon atoms, ^Y1 is not bonded to the nitrogen atom via a linking group outside the repeating unit, ^R1 each independently represents a structure represented by the following formula (R-1), m represents an integer of 0 to 4, and n represents an integer of 1 or more, [Chemical Formula 6] In formula (R-1), ^L1 represents an a2+1 valent linking group, ^Z1 represents an aromatic group, a cyclic aliphatic group or a linear or branched aliphatic saturated hydrocarbon group, R ^R1 each independently represents a hydrogen atom or an organic group, two R ^R1s may be linked, a1 represents an integer greater than 1 and less than the maximum number of substituents of ^Z1 , a2 represents an integer greater than 1, and * represents a bonding site with ^X1 or ^Y1 in formula (1-1), [Chemical Formula 7] In formula (2-1), ^X2 represents an organic group having 4 or more carbon atoms, ^Y2 represents an organic group having 4 or more carbon atoms, ^R2 each independently represents a group represented by the following formula (R-2), and n represents an integer greater than 1. In formula (3-1), ^X3 represents an organic group having 4 or more carbon atoms, ^Y3 represents an organic group having 4 or more carbon atoms, ^A3 and ^A4 each independently represent an oxygen atom or -NR ^N -, ^RN represents a hydrogen atom or a monovalent organic group, ^R3 and ^R4 each independently represent a hydrogen atom or a monovalent organic group, ^R2 each independently represents a group represented by the following formula (R-2), and n represents an integer greater than 0. [Chemical Formula 8] In formula (R-2), ^L2 represents a b2+1 valent linking group, ^Z2 represents a b1+1 valent organic group, ^A2 represents a methacryloyloxy group, an acryloxy group, a methacrylamide group, an acrylamide group, a vinyl group, a styryl group, an allyl group or a vinyl ether group, b1 represents an integer greater than 1 and less than the maximum number of substituents of ^Z2 , b2 represents an integer greater than 1, and * represents a bonding site with ^Y2 in formula (2-1) or ^Y3 in formula (3-1). The resin composition as described in claim 9, wherein in formula (3-1), ^R3 and ^R4 are groups having ethylenically unsaturated bonds, and ^X3 has a structure obtained by removing two or more hydrogen atoms from a structure represented by any one of formulas (V-1) to (V-4). The resin composition as claimed in claim 9 or claim 10, wherein ^X1 and ^Y1 in formula (1-1) each contain a structure obtained by removing two or more hydrogen atoms from a structure represented by any one of the following formulas (V-1) to (V-4), [Chemical Formula 9] In formula (V-2), ^RX1 is independently a hydrogen atom, an alkyl group or a halogenated alkyl group. In formula (V-3), ^RX2 and ^RX3 are independently a hydrogen atom or a substituent. ^RX2 and ^RX3 may be bonded to form a ring structure. A resin composition as described in claim 9 or claim 10, wherein the resin B has at least one group selected from the group consisting of a linear or branched monovalent aliphatic hydrocarbon group having 6 or more carbon atoms, and a cyclic aliphatic hydrocarbon group in which one or more hydrogen atoms are replaced by a linear aliphatic hydrocarbon group having 4 or more carbon atoms. A resin composition as described in any one of claim 1, claim 2, claim 9 or claim 10, wherein when the resin composition is used to form a cured film having a film thickness of 10 μm, the transmittance of the cured film at a wavelength of 365 nm is 15% or more. A resin composition as described in any one of claim 1, claim 2, claim 9 or claim 10, wherein the melting point of the aforementioned polymerizable compound is below 25°C. A resin composition as described in any one of claim 1, claim 2, claim 9 or claim 10, wherein the ClogP of the aforementioned polymerizable compound is 3 or more. The resin composition as described in any one of claim 1, claim 2, claim 9 or claim 10 contains an azole compound and a silane coupling agent. The resin composition as described in any one of claim 1, claim 2, claim 9 or claim 10 is used to form an interlayer insulating film for a redistribution layer. A hardened material obtained by hardening the resin composition described in any one of claims 1 to 17. A laminate comprising two or more layers consisting of the hardened material as claimed in claim 18, and comprising a metal layer between any of the layers consisting of the hardened material. A method for producing a cured product, comprising a film forming step of applying the resin composition described in any one of claims 1 to 17 to a substrate to form a film. The method for manufacturing a hardened product as described in claim 20 comprises: an exposure step of selectively exposing the aforementioned film; and a development step of developing the aforementioned film using a developer to form a pattern. The method for manufacturing a cured product as described in claim 20 includes a heating step of heating the aforementioned film at 50 to 450°C. A method for manufacturing a laminate, comprising the method for manufacturing a hardened object as described in claim 20. A method for manufacturing a semiconductor device, comprising the method for manufacturing a hardened material as described in claim 20. A semiconductor device comprising the hardener described in claim 18.