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

Abstract

The present invention addresses the problem of providing a resin composition capable of forming a cured product having excellent flatness and excellent adhesion and mechanical strength even after being exposed to a high-temperature and high-humidity environment, a transfer film, a cured product, a laminate, a method for producing a cured product, a method for producing a laminate, a method for producing a semiconductor device, and a semiconductor device. A resin composition according to the present invention contains a polyimide resin, a compound having a radically polymerizable group, and a halogen element. The halogen element content is 0.001-300 ppm relative to the total mass of the total solid content of the resin composition.

Description

Resin composition, transfer film, cured product, laminate, method for manufacturing a cured product, method for manufacturing a laminate, method for manufacturing a semiconductor device, and semiconductor device

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

[0002] In modern times, resin materials manufactured from resin compositions containing resins are utilized in various fields. Polyimide, in particular, is used in a wide range of applications due to its excellent heat resistance and insulating properties. For example, in semiconductor devices for packaging, it is used as an insulating film, encapsulant, and protective film. Furthermore, polyimide is known to be used in the form of resin compositions containing polyimide or polyimide precursors in the aforementioned applications.

[0003] For example, Patent Document 1 describes a negative-type photosensitive resin composition comprising (A) a polyimide precursor, (B) a photopolymerization initiator, and (C) a compound containing a group that can be polymerized by the action of an acid, base, or radical ([Claim 1]). Patent Document 2 also describes a photosensitive resin composition comprising a polyimide precursor, a thermobase generator, and a radical polymerizable compound ([Claim 1][Claim 4]).

[0004] Japanese Patent Publication No. 2019-066754, International Publication No. 2019 / 189110

[0005] The present inventors investigated curable resin compositions described in Patent Documents 1 and 2, etc., and found that the flatness of the resulting cured product may be poor, and that the adhesion and mechanical strength of the cured product may decrease after exposure to a high-temperature, high-humidity environment.

[0006] Therefore, the object of the present invention is to provide a resin composition, a transfer film, a cured product, a laminate, a method for manufacturing a cured product, a method for manufacturing a laminate, a method for manufacturing a semiconductor device, and a semiconductor device, which can form a cured product that has excellent flatness and excellent adhesion and mechanical strength even after exposure to a high temperature and high humidity environment.

[0007] As a result of diligent research into the above-mentioned problems, the present inventors have discovered that in a resin composition containing a polyimide resin, a compound having a radical polymerizable group, and a halogen element, if the halogen element content is set to 0.001 to 300 ppm relative to the total mass of the total solids in the resin composition, a cured product with excellent flatness, adhesion, and mechanical strength can be formed even after exposure to high temperature and high humidity environments, thus completing the present invention. In other words, the present inventors have found that the above-mentioned problems can be solved by the following configuration.

[0008] [1] A resin composition comprising a polyimide resin, a compound having a radical polymerizable group, and a halogen element, wherein the content of the halogen element is 0.001 to 300 ppm relative to the total mass of the total solids of the resin composition. [2] The resin composition according to [1], wherein the content of the halogen element is 0.001 to 500 ppm relative to the mass of the polyimide resin. [3] The resin composition according to [1] or [2], wherein the polyimide resin is a polyimide resin having a radical polymerizable group. [4] The resin composition according to any one of [1] to [3], wherein the polyimide resin has repeating units represented by formula (1) described later. [5] The resin composition according to [4], wherein R in formula (1) described later is an organic group having an aromatic group. [6] The resin composition according to any one of [1] to [5], wherein the halogen element is at least one element selected from the group consisting of fluorine, chlorine, bromine, and iodine. [7] The resin composition according to any one of [1] to [6], further comprising at least one of a photopolymerization initiator and a thermal polymerization initiator. [8] The resin composition according to any one of [1] to [7], further comprising a migration inhibitor. [9] The resin composition according to any one of [1] to [8], further comprising an organometallic complex.

[10] The resin composition according to any one of [1] to [9], used for forming an interlayer insulating film for a redistribution layer.

[11] A transfer film having a temporary support and a composition layer containing the resin composition according to any one of [1] to

[10] .

[12] A cured product obtained by curing the resin composition according to any one of [1] to

[10] .

[13] A cured product obtained by curing a resin composition containing a polyimide resin, a compound having a radical polymerizable group, and a halogen element, wherein the content of the halogen element is 0.001 to 300 ppm with respect to the mass of the cured product.

[14] A laminate comprising two or more layers made of the cured product described in

[12] or

[13] , wherein a metal layer is included between any of the layers made of the cured product.

[15] A method for producing a cured product, comprising a film-forming step of applying the resin composition described in any of [1] to

[10] onto a substrate to form a film.

[16] A method for producing a cured product according to

[15] , comprising an exposure step of selectively exposing the above film and a developing step of developing the above film using a developer to form a pattern.

[17] A method for producing a cured product according to

[15] or

[16] , comprising a heating step of heating the above film at 50 to 450°C.

[18] A method for producing a laminate, comprising a method for producing a cured product according to any one of

[15] to

[17] .

[19] A method for producing a semiconductor device, comprising a method for producing a cured product according to any one of

[15] to

[17] .

[20] A semiconductor device, comprising a cured product according to

[12] or

[13] .

[0009] As shown below, the present invention provides a resin composition, transfer film, cured product, laminate, method for manufacturing a cured product, method for manufacturing a laminate, method for manufacturing a semiconductor device, and semiconductor device, which can form a cured product with excellent flatness and excellent adhesion and mechanical strength even after exposure to high temperature and high humidity environments.

[0010] Figure 1 is a schematic diagram showing a cross-section of a test vehicle used for copper adhesion testing after high-temperature and high-humidity testing.

[0011] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments explicitly stated. In this specification, numerical ranges represented by the symbol "~" mean a range that includes the numerical values ​​before and after "~" as the lower and upper limits, respectively. In this specification, the term "process" includes not only independent processes but also processes that are indistinguishable from other processes as long as the intended effect of the process is achieved. In the notation of groups (atomic groups) in this specification, notations that do not specify substituted or unsubstituted include both groups (atomic groups) with substituents and groups (atomic groups) without substituents. For example, "alkyl group" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of light used for exposure include the emission line spectrum of mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet (EUV) light, X-rays, electron beams, and other active light or radiation. In this specification, "(meth)acrylate" means both or either "acrylate" and "methacrylate," "(meth)acrylic" means both or either "acrylic" and "methacrylic," and "(meth)acryloyl" means both or either "acryloyl" and "methacryloyl." In this specification, Me in structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, total solids means the total mass of all components of the composition excluding the solvent. In this specification, solids concentration is the mass percentage of the components other than the solvent relative to the total mass of the composition. In this specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​measured using gel permeation chromatography (GPC) and are defined as polystyrene equivalent values ​​unless otherwise specified.In this specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, by using an HLC-8220GPC (manufactured by Tosoh Corporation) and connecting Guard Column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) in series as columns. Unless otherwise specified, these molecular weights shall be measured using NMP (N-methyl-2-pyrrolidone) as the eluent. However, if NMP is unsuitable as an eluent, such as in cases of low solubility, THF (tetrahydrofuran) may be used. Unless otherwise specified, detection in GPC measurements shall be performed using a UV (ultraviolet) wavelength 254 nm detector. In this specification, when the positional relationship of each layer constituting a laminate is described as "up" or "down," it is sufficient that there are other layers above or below the reference layer among the multiple layers of interest. That is, a third layer or element may be interposed between the reference layer and the other layers, and the reference layer and the other layers do not need to be in contact. Unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "up," or, if there is a resin composition layer, the direction from the substrate to the resin composition layer is referred to as "up," and the opposite direction is referred to as "down." Note that this setting of up and down directions is for convenience in this specification, and in actual embodiments, the "up" direction in this specification may differ from vertically upward. In this specification, unless otherwise specified, a composition may contain two or more compounds corresponding to each component contained in the composition. Also, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component. In this specification, unless otherwise specified, the temperature is 23°C, the atmospheric pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, ppm means parts per million. In this specification, preferred embodiment combination is more preferred embodiment.

[0012] [Resin Composition] The resin composition of the present invention is a resin composition containing a polyimide resin, a compound having a radically polymerizable group, and a halogen element. The content of the halogen element contained in the resin composition of the present invention is 0.001 to 300 ppm based on the total mass of the total solid content of the resin composition.

[0013] As described above, in the resin composition of the present invention, the content of the halogen element contained in the resin composition is 0.001 to 300 ppm based on the total mass of the total solid content of the resin composition. Therefore, the resin composition is excellent in flatness, and can form a cured product excellent in adhesiveness and mechanical strength even after being exposed to a high-temperature and high-humidity environment. The reason why this effect is exhibited is not clear in detail, but the present inventors speculate as follows. First, since the resin contained in the resin composition of the present invention is a polyimide resin, unlike a polyimide precursor, thermal shrinkage due to imidization does not occur during heating, so it is presumed that the flatness of the cured product is improved. Further, since the content of the halogen element is 0.001 to 300 ppm, the surface of an adjacent layer (e.g., a metal conductive part, etc.) of the cured product is activated by an oxidation reaction or the like, it is presumed that the adhesiveness and mechanical strength are improved even after exposure to a high-temperature and high-humidity environment. From the results of comparative examples described later, when the content of the halogen element exceeds 300 ppm, the adhesiveness and mechanical strength decrease, so it is presumed that migration of the halogen element occurs at the interface with the adjacent layer.

[0014] Hereinafter, the polyimide resin, the compound having a radically polymerizable group, the halogen element, and optional components contained in the resin composition of the present invention will be described in detail, and the halogen element, which is one of the characteristic components, will be described in detail first.

[0015] [Halogen Element] As described above, the resin composition of the present invention contains a halogen element in an amount of 0.001 to 300 ppm based on the total mass of the total solid content of the resin composition. Here, the halogen element refers to an element belonging to Group 17 of the periodic table. In the present invention, the content of a halogen element refers to a value measured by the following procedure, and when a plurality of halogen elements are contained, it refers to the total value of the measured contents of each halogen element. First, after preparing or obtaining the resin composition, it is allowed to stand still for 3 days at room temperature (23.0°C ± 0.5°C, relative humidity 50% ± 10%). Thereafter, the total amount of halogen elements (the total amount of free halogen elements and covalently bonded halogen elements) in the resin composition is measured. Specifically, the resin composition is combusted and decomposed at 800°C, the decomposed gas is absorbed into ultrapure water, and the total amount of halogen elements in the resin composition is determined by ion chromatography. The ion chromatography system consists of IC-1000 manufactured by Dionex and an IonPac AS12A (4 mm) column, with an eluent of 0.3 mM NaHCO ３ / 2.7 mM Na ２ CO ３ as the aqueous solution, the measurement is performed at a flow rate of 1.5 mL / min.

[0016] The halogen element contained in the resin composition of the present invention may be a halogen element derived from raw materials used in the synthesis of other components (for example, polyimide resins, compounds having radical polymerizable groups, etc.), that is, a halogen element as a trace component that may be contained in other components. Therefore, in the present invention, examples of methods for increasing the content of a halogen element include a method of using a raw material containing a large amount of a halogen element as a raw material for components such as a polyimide resin, a method of adding a halogen component (for example, NaCl, organic halogen, etc.), and a method of using an additive containing halogen as a trace component. Examples of methods for reducing the content of a halogen element include a method of using a raw material with a low content of a halogen element as a raw material for components such as a polyimide resin, and a method of purifying components such as a polyimide resin (for example, reprecipitation, ion exchange, etc.).

[0017] As described above, the halogen element content in the resin composition is 0.001 to 300 ppm relative to the total mass of the total solids in the resin composition, but is preferably 0.005 to 100 ppm, more preferably 0.01 to 50 ppm, even more preferably 0.05 to 10 ppm, and particularly preferably 0.1 to 5.0 ppm.

[0018] In the present invention, for the reason that adhesion and mechanical strength are better even after exposure to a high temperature and high humidity environment, the halogen element content in the resin composition is preferably 0.001 to 500 ppm, more preferably 0.01 to 100 ppm, and even more preferably 0.1 to 7.0 ppm relative to the mass of the polyimide resin described later.

[0019] Furthermore, in the present invention, the amount of free halogen elements contained in the resin composition is preferably 0.0001 to 100 ppm, more preferably 0.001 to 10 ppm, and even more preferably 0.01 to 1 ppm, relative to the total mass of the total solids of the resin composition. Here, the amount of free halogen elements refers to the value measured by the following procedure, and if multiple halogen elements are contained, it refers to the sum of the measured values ​​of the content of each halogen element. First, after preparing or obtaining the resin composition, it is left to stand at room temperature (23.0°C ± 0.5°C, relative humidity 50% ± 10%) for 3 days. After that, the total amount of free halogen elements in the resin composition is measured. Specifically, the ion concentration measurement is performed at 23.0°C using a ThermoFicher ICS-3000. Based on the measurement results, the content of halogen element ions in the resin composition was determined under the following measurement conditions. <Measurement conditions> 2 g of the resin composition was weighed and added to 4 mL of NMP, and stirred in a shaker for 10 minutes to dissolve. Further, 30 mL of deionized water is added and the mixture is stirred for 10 minutes using a shaker. Insoluble components are removed using a centrifuge (himac CF15RN), and the mixture is filtered through a disc filter (DISMIC JP050AN) before use. 1 mL of the processed sample solution is automatically inserted into the column by an autosampler. • Guard column for anion analysis: IonPac AS4A-SC (4 mm x 250 mm) • Guard column pump flow rate: 0.500 mL / min • Separation column for anion analysis: IonPac AS4A-SZ (4 mm x 50 mm) • Sample introduction line pump flow rate: 0.500 mL / min • Anion chemical suppressor: ACRS-500 (for 4 mm)

[0020] In the present invention, for the reason that adhesion is better even after exposure to a high temperature and high humidity environment, it is preferable that the halogen element contained in the resin composition is at least one element selected from the group consisting of fluorine, chlorine, bromine, and iodine, and more preferably at least one element selected from the group consisting of chlorine, bromine, and iodine.

[0021] [Polyimide Resin] The resin composition of the present invention contains a polyimide resin. Here, polyimide resin refers to a resin having repeating units containing imide groups in its molecular chain, and preferably a resin having repeating units containing imide ring structures in its molecular chain. Furthermore, if the polyimide resin is a linear resin, it is preferable that the polyimide resin is a resin having repeating units containing imide groups in its main chain, and more preferably a resin having repeating units containing imide ring structures in its main chain. In this specification, "main chain" refers to the relatively longest bonding chain in the resin molecule, and "side chain" refers to the other bonding chains. In this specification, imide group refers to a structure represented by *-C(=O)N(-*)C(=O)-*, where * represents a bonding site with another structure, preferably a bonding site with a carbon atom, and more preferably a bonding site with a quaternary carbon atom. In this specification, imide ring structure refers to a ring structure that includes all of the two carbon atoms and nitrogen atoms in the above imide as ring members. The imide ring structure is preferably a five-membered ring. The polyimide resin may be a so-called polyamideimide, which has amide groups in its molecular chain in addition to imide groups. In this specification, an amide group refers to a structure represented by *-C(=O)N(-#)-*, where * represents a bonding site with another structure, preferably a bonding site with a carbon atom, and more preferably a bonding site with a quaternary carbon atom. Also, # represents a bonding site with another structure, preferably a bonding site with a hydrogen atom or a carbon atom, and more preferably a bonding site with a hydrogen atom.

[0022] The imidization rate of the polyimide is 60% or more, preferably 70% or more, more preferably 80% or more, even more preferably 90% or more, and particularly preferably 95% or more. The upper limit of the above imidization rate is not particularly limited and may be 100% or less. The above imidization rate is measured, for example, by the following method: the infrared absorption spectrum of the polyimide is measured, and the absorption peak originating from the imide structure, 1377 cm⁻¹, is identified. －１ The peak intensity P1 in the vicinity is determined. Next, the polyimide is heat-treated at 350°C for 1 hour, and then the infrared absorption spectrum is measured again, at 1377 cm⁻¹. －１Determine the nearby peak intensity P2. Using the obtained peak intensities P1 and P2, the imidization rate of the polyimide can be calculated based on the following formula: Imidization rate (%) = (Peak intensity P1 / Peak intensity P2) × 100

[0023] In the present invention, from the viewpoint of achieving both high resolution as a photosensitive composition and mechanical strength and chemical resistance after heat curing, it is preferable that the polyimide resin is a polyimide resin having radical polymerizable groups. Here, examples of radical polymerizable groups include groups containing ethylenically unsaturated bonds (hereinafter also abbreviated as "ethylenically unsaturated groups"), specifically vinyl groups, vinyl ether groups, allyl groups, isoallyl groups, 2-methylallyl groups, (meth)acrylamide groups, (meth)acryloyloxy groups, and styryl groups. Of these, (meth)acryloyloxy groups or styryl groups are preferred.

[0024] In the present invention, from the viewpoint of achieving both high resolution as a photosensitive composition and mechanical strength, chemical resistance, and flatness after heat curing, it is preferable that the polyimide resin has repeating units represented by the following formula (1).

[0025] In formula (1) above, R independently represents an organic group having a radical polymerizable group. n and m independently represent integers from 0 to 4, where n + m represents an integer of 1 or more. X represents an organic group having 4 or more carbon atoms. Y represents an organic group having 4 or more carbon atoms.

[0026] -R- In the above formula (1), R independently represents an organic group having a radical polymerizable group. As an organic group having a radical polymerizable group, an organic group having an aromatic group is preferred from the viewpoint of achieving both high resolution as a photosensitive composition and mechanical strength after heat curing, high glass transition temperature (Tg), chemical resistance, flatness, and elongation at break after exposure to a high temperature and high humidity environment. That is, an organic group having both an aromatic group and a radical polymerizable group is preferred. Here, an aromatic group refers to a group containing an aromatic ring, and examples include n-valent groups having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles. Examples of aromatic hydrocarbon rings include benzene rings, naphthalene rings, anthracene rings, and phenanthroline rings, and examples of aromatic heterocycles include furan rings, pyrrole rings, thiophene rings, pyridine rings, thiazole rings, and benzothiazole rings. Of these, benzene rings, thiazole rings, or benzothiazole rings are preferred.

[0027] As an organic group having an aromatic group, for example, the organic group represented by the following formula (R-1) is preferred. Formula (R-1) *-L-benzene ring-ethylenically unsaturated group In the above formula (R-1), * represents the bonding site with X or Y in the above formula (1). Also, L is a single bond, an alkylene group having 1 to 12 carbon atoms, or a -CH group having 1 to 12 carbon atoms. ２ The - represents a divalent linking group in which one or more -s are substituted with -O-, -S-, -NH-, -N(Q)-, or -CO-, where Q represents a monovalent organic group. Examples of ethylenically unsaturated groups are those exemplified above, and the preferred embodiments are similar.

[0028] -n and m- In formula (1) above, n and m each independently represent an integer of 0 or more. However, n + m represents an integer of 1 or more. n is preferably an integer between 0 and 4, more preferably an integer between 0 and 2, and even more preferably 0 or 1. The embodiment in which n is 0 is also one of the preferred embodiments of the present invention. m is preferably an integer of 1 or more, more preferably an integer between 1 and 4, and even more preferably 1 or 2.

[0029] -X- In the above formula (1), X represents an organic group having 4 or more carbon atoms. Here, the organic group having 4 or more carbon atoms preferably includes a structure obtained by removing 2 or more hydrogen atoms from a structure represented by any of the following formulas (V-1) to (V-9).

[0030] In the above formula (V-2), R Ｘ１ each independently represent a hydrogen atom, an alkyl group or a halogenated alkyl group. Further, in the above formula (V-3), R Ｘ２ and R Ｘ３ each independently represent a hydrogen atom or a substituent, and R Ｘ２ and R Ｘ３ may be bonded to form a ring structure. Further, in the above formula (V-7), two R Ｘ５ each independently represent a hydrogen atom, an alkyl group or a halogenated alkyl group.

[0031] In the above formula (V-2), R Ｘ１ is preferably each 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 still more preferably a methyl group or a trifluoromethyl group. A halogenated alkyl group refers to a group in which at least one hydrogen atom of an alkyl group is substituted with a halogen atom. As the halogen atom, F or Cl is preferable, and F is more preferable. In the above formula (V-3), R Ｘ２ and R Ｘ３ are preferably each independently a hydrogen atom. When R Ｘ２ and R Ｘ３ are bonded to form a ring structure, the structure formed by bonding R Ｘ２ and R Ｘ３ is preferably a single bond, -O- or -CR ２ -, more preferably -O- or -CR ２ -, and still 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. R in the above formula (V-7) Ｘ５ , specific examples and preferred embodiments correspond to those of R in the above formula (V-2) Ｘ１It is the same as the above. Note that the two R Ｘ５ These may be the same or different.

[0032] If X in formula (1) above is a group that includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-1) above, it is preferable that X is a group represented by the following formula (V-1-1). In the following formula, * represents the bonding sites with the four carbonyl groups to which X in formula (1) is bonded, and n1 represents an integer from 0 to 5, and is preferably an integer from 1 to 5. Furthermore, the hydrogen atoms in the following structure may be further substituted with known substituents such as hydroxyl groups and hydrocarbon groups. Also, if n in formula (1) above is an integer of 1 or more, it is preferable that n hydrogen atoms are substituted with R in formula (1).

[0033] In formula (1) above, if X is a group that includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-2) above, X is preferably a group represented by the following formula (V-2-1) or formula (V-2-2), and from the viewpoint of lowering the amine value in the resin, it is preferably a group represented by formula (V-2-2). In this specification, a bond intersecting the edge of a ring structure means that one of the hydrogen atoms in that ring structure is substituted. In the following formula, L Ｘ１ represents a single bond or -O-, and * represents the bonding sites with the four carbonyl groups to which X in formula (1) is bonded. Also, R Ｘ１ The definition and preferred embodiments are as described above. Furthermore, the hydrogen atoms in these structures may be further substituted with known substituents such as hydroxyl groups and hydrocarbon groups. In addition, when n in formula (1) above is an integer of 1 or more, it is preferable that n hydrogen atoms are substituted with R in formula (1).

[0034] If X in formula (1) above is a group that includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-3) above, then X is preferably a group represented by the following formula (V-3-1) or formula (V-3-2), and from the viewpoint of reducing the dielectric constant, etc., it is preferably a group represented by formula (V-3-2). In the following formula, * represents the bonding sites with the four carbonyl groups to which X in formula (1) is bonded. Also, R Ｘ２ and R Ｘ３ The definition and preferred embodiments are as described above. Furthermore, the hydrogen atoms in these structures may be further substituted with known substituents such as hydroxyl groups and hydrocarbon groups. In addition, when n in formula (1) above is an integer of 1 or more, it is preferable that n hydrogen atoms are substituted with R in formula (1).

[0035] If X in formula (1) above is a group that includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-4) above, it is preferable that X is a group represented by the following formula (V-4-1). In the following formula, * represents the bonding sites with the four carbonyl groups to which X in formula (1) is bonded, and n1 represents an integer from 0 to 5. Furthermore, the hydrogen atoms in the following structure may be further substituted with known substituents such as hydroxyl groups and hydrocarbon groups. Also, if n in formula (1) above is an integer of 1 or more, it is preferable that n hydrogen atoms are substituted with R in formula (1).

[0036] -Y- In formula (1) above, Y represents an organic group having 4 or more carbon atoms. Here, the organic group having 4 or more carbon atoms preferably includes a structure obtained by removing 2 or more hydrogen atoms from any of the structures represented by formulas (V-1) to (V-4) above.

[0037] If Y in formula (1) above is a group that includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-1) above, then Y is preferably a group represented by the following formula (V-1-2). In the following formula, * represents the bonding sites with the two nitrogen atoms to which Y in formula (1) is bonded, and n1 represents an integer from 1 to 5. In the following structure, m hydrogen atoms are substituted by R in formula (1). m is synonymous with m in formula (1). Furthermore, the hydrogen atoms in the following structure may be further substituted by known substituents such as hydroxyl groups and hydrocarbon groups.

[0038] In formula (1) above, if Y is a group that includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-2) above, Y is preferably a group represented by the following formula (V-2-3) or formula (V-2-4), and from the viewpoint of reducing the dielectric constant, it is preferable that Y is a group represented by formula (V-2-4). In the following formula, L Ｘ１ represents a single bond or -O-, and * represents the bonding site between Y and the two nitrogen atoms to which Y is bonded in formula (1). Also, R Ｘ１ The preferred embodiments are as described above. In the following structures, m hydrogen atoms are substituted with R in formula (1). m is synonymous with m in formula (1). Furthermore, the hydrogen atoms in these structures may be further substituted with known substituents such as hydroxyl groups and hydrocarbon groups.

[0039] If Y in formula (1) above is a group that includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-3) above, Y is preferably a group represented by the following formula (V-3-3) or formula (V-3-4), and from the viewpoint of reducing the dielectric constant, etc., it is preferable that Y is a group represented by formula (V-3-3). In the following formula, * represents the bonding site with the two nitrogen atoms to which Y in formula (1) is bonded. Also, R Ｘ２ and R Ｘ３ The preferred embodiments are as described above. In the following structures, m hydrogen atoms are substituted with R in formula (1). m is synonymous with m in formula (1). Furthermore, the hydrogen atoms in these structures may be further substituted with known substituents such as hydroxyl groups and hydrocarbon groups.

[0040] If Y in formula (1) above is a group that includes a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-4) above, then Y is preferably a group represented by the following formula (V-4-2) or formula (V-4-3). In the following formulas, * represents the bonding sites with the two nitrogen atoms to which Y in formula (1) is bonded, and n1 represents an integer from 0 to 5. The embodiment in which n1 is 0 is also one of the preferred embodiments of the present invention. In the following structure, m hydrogen atoms are substituted by R in formula (1). m is synonymous with m in formula (1). Furthermore, the hydrogen atoms in the following structure may be further substituted by known substituents such as hydroxyl groups and hydrocarbon groups.

[0041] Among these, it is preferable that X and Y in formula (1) each include a structure obtained by removing two or more hydrogen atoms from the structure represented by any of the above formulas (V-1) to (V-4).

[0042] Polyimide resins are preferably made to contain an alicyclic structure (aliphatic ring structure) for the following reasons: they exhibit superior flatness and can form cured products with superior adhesion and mechanical strength even after exposure to high temperature and high humidity environments (hereinafter also referred to as "the reasons for the superior effects of the present invention"). Specific examples and preferred embodiments of the alicyclic structure are the same as those described above for cyclic aliphatic hydrocarbons (alicyclic compounds).

[0043] In the present invention, the weight-average molecular weight (Mw) of the polyimide resin is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. By setting the weight-average molecular weight to 5,000 or more, the flexural 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 15,000 or more. Furthermore, the number-average molecular weight (Mn) of the polyimide resin is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. Furthermore, the degree of dispersion of the molecular weight of the polyimide resin is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no specific upper limit for the degree of dispersion of the molecular weight of polyimide, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. The degree of dispersion of molecular weight is calculated as the weight-average molecular weight / number-average molecular weight. When the resin composition of the present invention contains multiple types of polyimide resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polyimide resins are within the above range. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated when the above multiple types of polyimide resins are treated as a single resin are each within the above range.

[0044] A preferred embodiment of the method for producing polyimide resin is a method for synthesizing polyimide from at least one acid anhydride and at least one diamine (hereinafter also referred to as "the production method of the present invention"). The production method of the present invention will be further described below.

[0045] [1] Polymerization step and imidation step The manufacturing method of the present invention preferably comprises a polymerization step and an imidation step. In the polymerization step, an acid anhydride and a diamine react to produce a polyimide precursor, and in the imidation step, the produced polyimide precursor is imidized to produce a polyimide.

[0046] <Acid Anhydride> The acid anhydride is preferably a carboxylic acid anhydride (carboxylic acid anhydride), and more preferably a tetracarboxylic acid dianhydride (tetracarboxylic acid dianhydride). Examples of tetracarboxylic acid dianhydrides include the dianhydride of an aromatic compound having four carboxyl groups (aromatic tetracarboxylic acid dianhydride), and the dianhydride of an aliphatic compound (especially an alicyclic compound) having four carboxyl groups (aliphatic tetracarboxylic acid dianhydride). Among these, aromatic tetracarboxylic acid dihydrates are preferred because they provide superior effects in the present invention.

[0047] Specific examples of aromatic tetracarboxylic dianhydrides include 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2-dicarboxylic anhydride, pyromellitic dianhydride (PMDA), 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA), 2,2′,3,3′-benzophenonetetracarboxylic dianhydride, and 3,3′,4,4′-biphenyltetracarboxylic dianhydride. Acidic dianhydride (sBPDA), 3,3′,4,4′-diphenylsulfontetracarboxylic acid dianhydride (DSDA), 2,2′,3,3′-biphenyltetracarboxylic acid dianhydride, methylene-4,4′-diphthalic acid dianhydride, 1,1-ethylidene-4,4′-diphthalic acid dianhydride, 2,2-propyridene-4,4′-diphthalic acid dianhydride, 1,2-ethylene-4,4′-diphthalic acid dianhydride, 1,3-trimethylene-4,4′-diphthalic acid dianhydride, 1,4-tetramethylene-4,4′-diphthalic acid dianhydride, 1,5-pentamethylene-4,4′-diphthalic acid dianhydride Dianhydride taric acid, 4,4'-oxydiphthalic acid dianhydride (ODPA), thio-4,4'-diphthalic acid dianhydride, sulfonyl-4,4'-diphthalic acid dianhydride, 1,3-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,3-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride Anhydride, bis[3-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA), bis(3,4-dicarboxyphenoxy)dimethylsilane dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,Examples include 7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, and 1,2,7,8-phenanthrenetetracarboxylic dianhydride. Among these, BPADA, DSDA, and ODPA are preferred, BPADA and DSDA are more preferred, and BPADA is even more preferred, due to the superior effects of the present invention.

[0048] Specific examples of aliphatic tetracarboxylic dianhydrides include ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), and cyclopentanetetracarboxylic dianhydride. 1,2,3,4-cyclohexanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride (CHDA), 3,3′,4,4′-bicyclohexyltetracarboxylic acid dianhydride, carbonyl-4,4′-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4′-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4′-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylidene-4,4′-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylidene-4,4′-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4′-bis(cyclohex Examples include 1,2-dicarboxylic acid dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo[2,2,2]octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, rel-[1S,5R,6R]-3-oxabicyclo[3,2,1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, and ethylene glycol-bis-(3,4-dicarboxylic acid anhydride phenyl) ether. Among these, CHDA is preferred because it exhibits superior effects compared to the present invention.

[0049] One type of acid anhydride may be used, or two or more types may be used, but it is preferable to use two or more types because the effects of the present invention are superior.

[0050] <Diamines> Diamines are compounds having two or more amino groups. Examples of diamines include aromatic diamines and aliphatic diamines (especially alicyclic diamines). Among these, aromatic diamines are preferred because they exhibit superior effects compared to the present invention.

[0051] Specific examples of aromatic diamines include p-phenylenediamine (PDA), m-phenylenediamine, 2,4-diaminotoluene, benzidine, 3,3'-dihydroxy-4,4'-diaminobiphenyl (HAB), 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP), 3,3'-dimethyl-4,4'-diaminobiphenyl (o-tolidine), 2,2'-dimethyl-4,4'-diaminobiphenyl (m-tolidine), 3,3'-diethyl-4,4'-diaminobiphenyl, and 2,2'-diethyl-4,4'-diaminobiphenyl 4,4′-diamino-2,2′-bis(trifluoromethyl)biphenyl, 3,3-dimethoxy-4,4-diaminobiphenyl, 2,2′-dichloro-4,4′-diamino-5,5′-dimethoxybiphenyl, 2,2′,5,5′-tetrachloro-4,4′-diaminobiphenyl, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether (ODA), 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,7-diamino-dimethyldibenzothiophen-5,5-dioxide, 4,4′-diaminodiphenyl Minobenzophenone, 3,3′-diaminobenzophenone, 4,4′-bis(4-aminophenyl)sulfide, 4,4′-diaminodiphenylsulfone, 4,4′-diaminobenzanilide, 1,n-bis(4-aminophenoxy)alkane, 1,3-bis[2-(4-aminophenoxyethoxy)]ethane, 9,9-bis(4-aminophenyl)fluorene, 9,9-bis(4-aminophenoxyphenyl)fluorene, 5(6)-amino-1-(4-aminomethyl)-1,3,3-trimethylindan, 1,4-bis(4-aminophenoxy ) benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 2,5-bis(4-aminophenoxy)biphenyl, 4,4′-bis(4-aminophenoxy)biphenyl, 4,4′-bis(3-aminophenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxyphenyl)]propane, 2,2-bis(4-aminophenoxyphenyl)hexafluoropropane, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,Examples include 2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 4,4'-methylene-bis(2-chloroaniline), 9,10-bis(4-aminophenyl)anthracene, o-tolidine sulfone, etc. Among these, HAB, BAP, m-tolidine, and ODA are preferred.

[0052] Specific examples of aliphatic diamines include 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-3,3′-dimethylcyclohexylmethane, 4,4′-diamino-3,3′,5,5′-tetramethylcyclohexylmethane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 2,2-bis(4,4′-diaminocyclohexyl)propane, 1,3-bisaminomethylcyclohexane, and 1,4-bisaminomethylcyclohexane. Examples include 2,3-diaminobicyclo[2.2.1]heptane, 2,5-diaminobicyclo[2.2.1]heptane, 2,6-diaminobicyclo[2.2.1]heptane, 2,7-diaminobicyclo[2.2.1]heptane, 2,5-bis(aminomethyl)-bicyclo[2.2.1]heptane, 2,6-bis(aminomethyl)-bicyclo[2.2.1]heptane, 2,3-bis(aminomethyl)-bicyclo[2.2.1]heptane, and 3(4),8(9)-bis(aminomethyl)-tricyclo[5.2.1.02,6]decane.

[0053] One type of diamine may be used, or two or more types may be used, but it is preferable to use two or more types because the effects of the present invention are superior.

[0054] <Other Monomers> In the production method of the present invention, in addition to acid anhydrides and diamines, other monomers (other monomers) may also be used. Examples of such monomers include monoamines. Monoamines function as end-capturing agents. Specific examples of monoamines include aromatic monoamines such as aniline and 4-aminophenol (PAP), and aliphatic monoamines such as hexylamine, octylamine, and hexadecylamine.

[0055] <Temperature> The temperature (reaction temperature) of the polymerization and imidization steps is preferably 50 to 300°C, and more preferably 100 to 180°C, for better performance of the present invention.

[0056] [2] Step to introduce radical polymerizable group-containing group The manufacturing method of the present invention may include steps other than the polymerization step and the imidation step. For example, such a step is the step to introduce a radical polymerizable group-containing group. The step to introduce a radical polymerizable group-containing group is a step to introduce a radical polymerizable group-containing group to the side chains and / or terminals of the polyimide obtained in the polymerization step and the imidation step. The radical polymerizable group-containing group is as described above. When the polyimide obtained in the polymerization step and the imidation step has hydroxyl groups, suitable radical polymerizable group-containing group introducing agents (side chain introducing agents, terminal introducing agents) include, for example, chloromethylstyrene and 2-methacryloyloxyethyl isocyanate. It is also preferable to add a reaction accelerator during the radical polymerizable group-containing group introduction reaction. Examples of reaction accelerators include organic bases such as triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undeca-7-ene, N,N-dimethyl-4-aminopyridine, and imidazole, as well as salt compounds such as potassium iodide, sodium iodide, tetrabutylammonium iodide, potassium carbonate, lithium carbonate, and cesium carbonate.

[0057] [3] Purification step The manufacturing method of the present invention may include a step of precipitating the polyimide resin as a solid. Specifically, after filtering off the water-absorbing by-products of the dehydrating condensing agent present in the reaction solution as needed, the obtained polymer component is added to a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof, and the polymer component is precipitated to precipitate as a solid, which is then dried to obtain the polyimide resin. To improve the degree of purity, the polyimide resin may be redissolved, re-precipitation, and dried. Furthermore, a step of removing ionic impurities using an ion exchange resin may be included. In addition, a reslurry step may be included in which the obtained solid polyimide resin is immersed in a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof and stirred.

[0058] [Compounds Having Radical Polymerizable Groups] The resin composition of the present invention contains compounds having radical polymerizable groups (hereinafter also referred to as "polymerizable compounds"). Note that polyimide resin and polymerizable compounds are different compounds, so polyimide resin having radical polymerizable groups does not fall under the category of polymerizable compounds.

[0059] Examples of polymerizable compounds include radical crosslinking agents. Here, a radical crosslinking agent is a compound having a radical polymerizable group. Examples of radical polymerizable groups include those described above in relation to polyimide resins.

[0060] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, but more preferably a compound having two or more. The radical crosslinking agent may also have three or more ethylenically unsaturated bonds. As for the compound having two or more ethylenically unsaturated bonds, it is preferable to have a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and even more preferably a compound having 2 to 6.

[0061] 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.

[0062] Specific examples of radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably esters of unsaturated carboxylic acids with polyhydric alcohol compounds, and amides of unsaturated carboxylic acids with polyhydric amine compounds. Addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, or sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxys, and dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids are also suitably used. Addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having leaving substituents such as halogeno groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also suitable. As another example, it is also possible to use a group of compounds in which the above-mentioned unsaturated carboxylic acids are replaced with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc. For specific examples, refer to paragraphs

[0113] to

[0122] of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0063] The radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples of compounds having a boiling point of 100°C or higher under normal pressure include the compounds described in paragraph

[0203] of International Publication No. 2021 / 112189. This information is incorporated herein by reference.

[0064] Other preferred radical crosslinking agents include the radical polymerizable compounds described in paragraphs

[0204] to

[0208] of International Publication No. 2021 / 112189. This information is incorporated herein by reference.

[0065] Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), and structures in which the (meth)acryloyl groups of these are linked via ethylene glycol residues or propylene glycol residues. These oligomer types can also be used.

[0066] Examples of commercially available radical crosslinking agents include SR-494, a tetrafunctional acrylate with four ethylene oxy chains; SR-209, 231, and 239, difunctional methacrylates with four ethylene oxy chains (all manufactured by Sartomer Co., Ltd.); DPCA-60, a hexafunctional acrylate with six pentylene oxy chains; and TPA-330, a trifunctional acrylate with three isobutylene oxy chains (both manufactured by Nippon Kayaku Co., Ltd.); and urethane oligomers. Examples include UAS-10, UAB-140 (both manufactured by Nippon Paper Industries), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (all manufactured by Kyoeisha Chemical Co., Ltd.), and Bremmer PME400 (manufactured by NOF Corporation).

[0067] Suitable radical crosslinking agents include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Unexamined Patent Publication No. 51-037193, Japanese Unexamined Patent Publication No. 02-032293, and Japanese Unexamined Patent Publication No. 02-016765, as well as urethane compounds having an ethylene oxide-based skeleton as described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418. Compounds having an amino or sulfide structure within the molecule, as described in Japanese Unexamined Patent Publication No. 63-277653, Japanese Unexamined Patent Publication No. 63-260909, and Japanese Unexamined Patent Publication No. 01-105238, can also be used as radical crosslinking agents.

[0068] The radical crosslinking agent may be a radical crosslinking agent having an acidic group such as a carboxyl group or a phosphate group. The radical crosslinking agent having an acidic group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent obtained by reacting the unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group. Particularly preferred is a radical crosslinking agent obtained by reacting the unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group, wherein the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include M-510 and M-520, which are polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

[0069] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mg KOH / g, and more preferably 1 to 100 mg KOH / g. When the acid value of the radical crosslinking agent is within the above range, it exhibits excellent handling properties during manufacturing and excellent developability. It also exhibits good polymerizability. The above acid value is measured in accordance with the description in JIS K 0070:1992. As a radical crosslinking agent, a radical crosslinking agent having at least one selected from the group consisting of urea bonds and urethane bonds (hereinafter also referred to as "crosslinking agent U") is also preferred. Examples of crosslinking agent U include compounds described in paragraphs

[0133] to

[0143] of International Publication No. 2023 / 190064. This content is incorporated herein by reference.

[0070] The resin composition of the present invention preferably uses a bifunctional methacrylate or acrylate from the viewpoint of pattern resolution and film stretchability. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6- Hexanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, ethylene oxide (EO) adduct diacrylate of bisphenol A, ethylene oxide (EO) adduct dimethacrylate of bisphenol A, propylene oxide (PO) adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, and other difunctional acrylates and difunctional methacrylates having urethane bonds can be used. Two or more of these can be mixed and used as needed. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate in which the molecular weight of the polyethylene glycol chain is about 200.

[0071] From the viewpoint of suppressing warping of the pattern (cured product), the resin composition of the present invention preferably uses a monofunctional radical crosslinking agent. Preferred monofunctional radical crosslinking agents include (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate, as well as N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl glycidyl ether. As a monofunctional radical crosslinking agent, compounds with a boiling point of 100°C or higher under normal pressure are also preferred in order to suppress volatilization before exposure. Other examples of bifunctional or more radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0072] The polymerizable compound content is preferably greater than 0% by mass and 60% by mass or less, relative to the total mass of the total solids in the resin composition. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less. The resin composition of the present invention may contain only one polymerizable compound or two or more. When two or more are contained, the total amount is preferably within the above range.

[0073] [Solvent] The resin composition of the present invention preferably contains a solvent. Any known solvent can be used. An organic solvent is preferred. Examples of organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0074] Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl esters of 3-alkyloxypropionates (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), and 2-alkyloxy Suitable examples include alkyl cypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.).

[0075] Suitable ethers include, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0076] Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucocenone, and dihydrolevoglucocenone.

[0077] Suitable cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0078] As an example of a sulfoxide, dimethyl sulfoxide is a suitable choice.

[0079] Suitable amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0080] Suitable ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0081] Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenylcarbinol, n-amyl alcohol, methylamyl alcohol, and diacetone alcohol.

[0082] From the viewpoint of improving the properties of the coated surface, it is also preferable to use a mixture of two or more solvents.

[0083] In the present invention, one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, γ-valerolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, levoglucocenone, and dihydrolevoglucocenone, or a mixed solvent composed of two or more of these, is preferred. The combined use of dimethyl sulfoxide and γ-butyrolactone, or the combined use of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred.

[0084] Furthermore, the boiling point of the solvent is preferably between 80°C and 300°C. Specific examples of solvent boiling points include 150°C, 190°C, and 200°C. The upper limit of the solvent's explosion is preferably between 5 vol% and 50 vol%, and the lower limit is preferably between 0.5 vol% and 15 vol%.

[0085] When the resin composition of the present invention contains a solvent, the amount of solvent is preferably such that the total solid content concentration of the resin composition is 5 to 80% by mass, more preferably 5 to 75% by mass, even more preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass, from the viewpoint of coatability. The amount of solvent can be adjusted according to the desired thickness of the coating film and the application method. When two or more solvents are included, it is preferable that their total amount is within the above range.

[0086] [Polymerization Initiator] The resin composition of the present invention preferably contains a polymerization initiator, and more preferably contains at least one of a photopolymerization initiator and a thermal polymerization initiator.

[0087] <Photopolymerization Initiator> The photopolymerization initiator is not particularly limited and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible region is preferred. Alternatively, an activator that acts with a photoexcited sensitizer to generate active radicals may also be used.

[0088] The photoradical polymerization initiator is present in an amount of at least about 50 L / mol with a wavelength in the range of about 240 to 800 nm (preferably 330 to 500 nm). －１ ・cm －１ It is preferable that the compound contains at least one compound having a molar extinction coefficient. The molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure it using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0089] Any known compound can be used as a photoradical polymerization initiator. Examples include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron arene complexes, etc. For further details, refer to paragraphs

[0165] to

[0182] of Japanese Patent Application Publication No. 2016-027357 and paragraphs

[0138] to

[0151] of International Publication No. 2015 / 199219, which are incorporated herein by reference. Furthermore, examples include paragraphs

[0065] to

[0111] of Japanese Patent Publication No. 2014-130173, the compounds described in Japanese Patent No. 6301489, the peroxide-based photopolymerization initiators described in MATERIAL STAGE 37-60p, vol. 19, No. 3, 2019, the photopolymerization initiators described in International Publication No. 2018 / 221177, the photopolymerization initiators described in International Publication No. 2018 / 110179, the photopolymerization initiators described in Japanese Patent Publication No. 2019-043864, the photopolymerization initiators described in Japanese Patent Publication No. 2019-044030, and the peroxide-based initiators described in Japanese Patent Publication No. 2019-167313, the contents of which are incorporated herein by reference.

[0090] Examples of ketone compounds include the compounds described in paragraph

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

[0091] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used as photoradical polymerization initiators. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Application Publication No. 10-291969 and an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, and this is incorporated herein by reference.

[0092] As α-hydroxyketone initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF) can be used.

[0093] As α-aminoketone initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.

[0094] As aminoacetophenone initiators, acylphosphine oxide initiators, and metallocene compounds, for example, compounds described in paragraphs

[0161] to

[0163] of International Publication No. 2021 / 112189 can also be suitably used. This is incorporated herein by reference.

[0095] More preferably, oxime compounds are used as photoradical polymerization initiators. Using oxime compounds makes it possible to more effectively improve the exposure latitude. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.

[0096] Specific examples of oxime compounds include the compounds described in Japanese Patent Publication No. 2001-233842, Japanese Patent Publication No. 2000-080068, Japanese Patent Publication No. 2006-342166, the compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), the compounds described in J. C. S. Perkin II (1979, pp. 156-162), and Journal of Photopolymer Science and Examples include compounds described in Technology (1995, pp. 202-232), compounds described in Japanese Patent Publication No. 2000-066385, compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Publication No. 2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, compounds described in Japanese Patent Publication No. 2017-198865, compounds described in paragraphs 0025-0038 of International Publication No. 2017 / 164127, compounds described in International Publication No. 2013 / 167515, and the like, which are incorporated herein by reference.

[0097] Preferred oxime compounds include, for example, compounds with the following structures, as well as 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropane-1-one, 2-(benzoyloxy(imino))-1-phenylpropane-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropane-1-one. In resin compositions, it is particularly preferable to use oxime compounds as photoradical polymerization initiators. Oxime compounds used as photoradical polymerization initiators have a >C=N-O-C(=O)- linking group in their molecule.

[0098]

[0099] Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (all manufactured by BASF), ADEKA optomer N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in Japanese Patent Publication No. 2012-014052), TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA Arclus NCI-730, NCI-831, and ADEKA Arclus NCI-930 (manufactured by ADEKA Corporation), DFI-091 (manufactured by Daito Chemix Co., Ltd.), and SpeedCure PDO (SARTOMER Examples include those manufactured by ARKEMA. Additionally, oxime compounds with the following structures can also be used.

[0100] As photoradical polymerization initiators, for example, oxime compounds having a fluorene ring as described in paragraphs

[0169] to

[0171] of International Publication No. 2021 / 112189, oxime compounds having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring, and oxime compounds having a fluorine atom can also be used. In addition, oxime compounds having a nitro group as described in paragraphs

[0208] to

[0210] of International Publication No. 2021 / 020359, oxime compounds having a benzofuran skeleton, and oxime compounds in which a substituent having a hydroxyl group is attached to the carbazole skeleton can also be used. These contents are incorporated herein by reference. Furthermore, as photoradical polymerization initiators, compounds described in paragraphs

[0113] to

[0117] of Japanese Patent Application Publication No. 2023-058585 can also be used. This description is incorporated herein by reference.

[0101] When the resin composition of the present invention contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass, based on the total solid content of the resin composition. The resin composition of the present invention may contain only one type of photopolymerization initiator or may contain two or more types. When two or more types are contained, it is preferable that the total amount is within the above range.

[0102] <Thermal polymerization initiator> The thermal polymerization initiator is not particularly limited and can be appropriately selected from known thermal polymerization initiators. Examples of thermal polymerization initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, and perbutyl P (α,α'-di(t-butylperoxy)diisopropylbenzene; manufactured by NOF Corporation), among which azobisisobutyronitrile and perbutyl P (manufactured by NOF Corporation) are preferred.

[0103] When the resin composition of the present invention contains a thermal polymerization initiator, the content of the thermal polymerization initiator is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, and even more preferably 0.1 to 3% by mass, based on the total solid content of the resin composition. The resin composition of the present invention may contain only one type of thermal polymerization initiator or may contain two or more types. When two or more types are contained, it is preferable that the total amount is within the above range.

[0104] [Migration Inhibitor] The resin composition of the present invention preferably further contains a migration inhibitor. By including a migration inhibitor, for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, the migration of metal ions originating from the metal layer (or metal wiring) into the film can be effectively suppressed.

[0105] There are no particular restrictions on the migration inhibitors, but examples include compounds having heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, and 6H-pyran ring, triazine ring), thioureas and compounds having sulfanyl groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. Of these, nitrogen-containing heterocyclic compounds are preferred, and triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole are more preferred.

[0106] As a migration inhibitor, an ion trapping agent that captures anions such as halogen ions can also be used.

[0107] Other migration inhibitors that can be used include the rust inhibitor described in paragraph

[0094] of Japanese Patent Publication No. 2013-015701, the compounds described in paragraphs

[0073] to

[0076] of Japanese Patent Publication No. 2009-283711, the compounds described in paragraph

[0052] of Japanese Patent Publication No. 2011-059656, the compounds described in paragraphs

[0114] ,

[0116] and

[0118] of Japanese Patent Publication No. 2012-194520, the compounds described in paragraph

[0166] of International Publication No. 2015 / 199219, and the like, which are incorporated herein by reference.

[0108] Specific examples of migration inhibitors include the following compounds.

[0109] When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass, based on the total solid content of the resin composition. The resin composition of the present invention may contain only one type of migration inhibitor, or it may contain two or more types. When two or more types are used, it is preferable that their total is within the above range.

[0110] [Organometallic Complex] The resin composition of the present invention preferably contains an organometallic complex. Here, the organometallic complex may be any organic complex compound containing a metal atom, but it is preferably a complex compound containing a metal atom and an organic group, more preferably a compound in which an organic group is coordinated to a metal atom, and even more preferably a metallocene compound. In the present invention, the metallocene compound refers to an organometallic complex having two cyclic pentadienyl anion derivatives, which may have substituents, as η5-ligands. The above organic group is not particularly limited, but a hydrocarbon group or a group consisting of a hydrocarbon group and a heteroatom is preferred. As heteroatoms, oxygen atoms, sulfur atoms, and nitrogen atoms are preferred. In the present invention, at least one of the organic groups is preferably a cyclic group, and at least two are preferably cyclic groups. The above cyclic group is preferably selected from a five-membered ring cyclic group and a six-membered ring cyclic group, and more preferably selected from a five-membered ring cyclic group. The above cyclic group may be a hydrocarbon ring or a heterocycle, but a hydrocarbon ring is preferred. As a five-membered ring cyclic group, a cyclopentadienyl group is preferred. Furthermore, it is preferable that the organometallic complex contains 2 to 4 cyclic groups in one molecule.

[0111] The metal included in the organometallic complex is not particularly limited, but it is preferably a metal belonging to Group 4 elements, more preferably at least one metal selected from the group consisting of titanium, zirconium, and hafnium, even more preferably at least one metal selected from the group consisting of titanium and zirconium, and particularly preferably titanium.

[0112] Organometallic complexes may contain two or more metal atoms, or only one metal atom, but it is preferable that they contain only one metal atom. When organometallic complexes contain two or more metal atoms, they may contain only one type of metal atom, or two or more types of metal atoms.

[0113] The organometallic complex is preferably a titanocene compound, a zirconocene compound, or a hafnocene compound, more preferably a titanocene compound or a zirconocene compound, and even more preferably a titanocene compound.

[0114] When the resin composition of the present invention contains an organometallic complex, the content of the organometallic complex is preferably 0.1 to 30% by mass relative to the total solid content of the resin composition. The lower limit is more preferably 1.0% by mass or more, even more preferably 1.5% by mass or more, and particularly preferably 3.0% by mass or more. The upper limit is more preferably 25% by mass or less. The resin composition of the present invention may contain only one organometallic complex or two or more. When two or more are used, it is preferable that their total is within the above range.

[0115] [Metal Adhesion Modifying Agent] The resin composition of the present invention preferably contains a metal adhesion modifying agent from the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc. Examples of metal adhesion modifying agents include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, amino compounds, and the like.

[0116] <Silane Coupling Agents> Examples of silane coupling agents include the compounds described in paragraph

[0316] of International Publication No. 2021 / 112189 and the compounds described in paragraphs

[0067] to

[0078] of Japanese Patent Application Publication No. 2018-173573, the contents of which are incorporated herein by reference. It is also preferable to use two or more different silane coupling agents, as described in paragraphs

[0050] to

[0058] of Japanese Patent Application Publication No. 2011-128358. The following compounds are also preferable as silane coupling agents. In the following formulas, Me represents a methyl group and Et represents an ethyl group. In addition, R below represents a structure derived from a blocking agent in a blocked isocyanate group. The blocking agent can be selected according to the elimination temperature, but examples include alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, and active methylene compounds. For example, from the viewpoint of wanting to set the elimination temperature to 160 to 180°C, caprolactam is preferred. Examples of commercially available products of this type of compound include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0117]

[0118] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- Examples include (aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, and 3-trimethoxysilylpropyl succinic anhydride. These can be used individually or in combination of two or more. Furthermore, oligomeric compounds having multiple alkoxysilyl groups can also be used as silane coupling agents. Examples of such oligomeric compounds include compounds containing repeating units represented by the following formula (S-1).

[0119]

[0120] In formula (S-1), R Ｓ１ represents a monovalent organic group, R Ｓ２ R represents a hydrogen atom, a hydroxyl group, or an alkoxy group, and n represents an integer between 0 and 2. Ｓ１It is preferable that the structure includes polymerizable groups. Examples of polymerizable groups include groups having ethylenically unsaturated bonds, epoxy groups, oxetanyl groups, benzoxazolyl groups, blocked isocyanate groups, amino groups, etc. Examples of groups having ethylenically unsaturated bonds include vinyl groups, allyl groups, isoallyl groups, 2-methylallyl groups, groups having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl group), (meth)acrylamide groups, (meth)acryloyloxy groups, etc., with vinylphenyl groups, (meth)acrylamide groups, or (meth)acryloyloxy groups being preferred, vinylphenyl groups or (meth)acryloyloxy groups being more preferred, and (meth)acryloyloxy groups being even more preferred. Ｓ２ n is preferably an alkoxy group, and more preferably a methoxy group or an ethoxy group. n represents an integer from 0 to 2, and is preferably 1. Here, the structures of the multiple repeating units represented by formula (S-1) contained in the oligomer-type compound may all be the same. Here, it is preferable that n is 1 or 2 in at least one of the multiple repeating units represented by formula (S-1) contained in the oligomer-type compound, more preferably that n is 1 or 2 in at least two, and even more preferably that n is 1 in at least two. Commercially available products can be used as such oligomer-type compounds, and an example of a commercially available product is KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0121] <Aluminum-based adhesive aids> Examples of aluminum-based adhesive aids include aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), and ethyl acetate aluminum diisopropylate.

[0122] Other metal adhesion modifiers that can be used include the compounds described in paragraphs

[0046] to

[0049] of Japanese Patent Application Publication No. 2014-186186 and the sulfide compounds described in paragraphs

[0032] to

[0043] of Japanese Patent Application Publication No. 2013-072935, the details of which are incorporated herein by reference.

[0123] When the resin composition of the present invention contains a metal adhesion improver, the content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the polyimide resin described above. A content above the lower limit provides good adhesion between the pattern and the metal layer, while a content below the upper limit provides good heat resistance and mechanical properties of the pattern. The resin composition of the present invention may contain only one type of metal adhesion improver, or it may contain two or more types. When two or more types are used, it is preferable that their total content is within the above range.

[0124] [Polymerization Inhibitor] The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

[0125] Specific polymerization inhibitor compounds include those described in paragraph

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

[0126] If the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass, based on the total solid content of the resin composition. The resin composition of the present invention may contain only one polymerization inhibitor or two or more. If there are two or more polymerization inhibitors, it is preferable that their total is within the above range.

[0127] [Antioxidant] The resin composition of the present invention preferably contains an antioxidant. By including an antioxidant as an additive, the elongation properties of the cured film and the adhesion to metal materials can be further improved. Examples of antioxidants include phenol compounds, phosphite ester compounds, and thioether compounds. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. A preferred phenol compound is a hindered phenol compound. Compounds having a substituent at the ortho position adjacent to the phenolic hydroxyl group are preferred. As the substituents mentioned above, substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms are preferred. Furthermore, compounds having both a phenol group and a phosphite ester group in the same molecule are also preferred as antioxidants. In addition, phosphorus-based antioxidants can also be suitably used as antioxidants. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosfepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosfepin-2-yl)oxy]ethyl]amine, and ethylbis(2,4-di-tert-butyl-6-methylphenyl) phosphate. Examples of commercially available antioxidants include ADEKA stab AO-20, ADEKA stab AO-30, ADEKA stab AO-40, ADEKA stab AO-50, ADEKA stab AO-50F, ADEKA stab AO-60, ADEKA stab AO-60G, ADEKA stab AO-80, and ADEKA stab AO-330 (all manufactured by ADEKA Corporation). Furthermore, compounds described in paragraphs

[0023] to

[0048] of Japanese Patent No. 6268967 may also be used as antioxidants, and this information is incorporated herein. Additionally, the resin composition of the present invention may optionally contain a latent antioxidant. Examples of latent antioxidants include compounds in which the antioxidant portion is protected by a protecting group, and which function as antioxidants when heated at 100 to 250°C or when heated at 80 to 200°C in the presence of an acid / base catalyst, thereby removing the protecting group.Examples of latent antioxidants include compounds described in International Publication No. 2014 / 021023, International Publication No. 2017 / 030005, and Japanese Patent Publication No. 2017-008219, the contents of which are incorporated herein by reference. Examples of commercially available latent antioxidants include ADEKA Arclus GPA-5001 (manufactured by ADEKA Corporation). Examples of preferred antioxidants include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, and compounds represented by the following formula (3).

[0128]

[0129] In the above formula (3), R ５ R represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), ６ R represents an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). ７ k represents a 1-4 valent organic group containing at least one of an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), an oxygen atom, and a nitrogen atom. k represents an integer from 1 to 4.

[0130] The compound represented by formula (3) above suppresses the oxidative degradation of aliphatic groups and phenolic hydroxyl groups in resins. Furthermore, it can suppress metal oxidation by providing rust prevention to metal materials.

[0131] Since it can act on both resin and metal materials simultaneously, k is more preferably an integer between 2 and 4. ７ Examples of alkyl groups include alkyl groups, cycloalkyl groups, alkoxy groups, alkyl ether groups, alkylsilyl groups, alkoxysilyl groups, aryl groups, aryl ether groups, carboxyl groups, carbonyl groups, allyl groups, vinyl groups, heterocyclic groups, -O-, -NH-, -NHNH-, and combinations thereof, and may further have substituents. Among these, alkyl ether groups and -NH- are preferred from the viewpoint of solubility in the developer and metal adhesion, and -NH- is more preferred from the viewpoint of interaction with the resin and metal adhesion due to metal complex formation.

[0132] Examples of compounds represented by formula (3) above include the following, but are not limited to the structures shown below.

[0133]

[0134]

[0135]

[0136]

[0137] When the resin composition of the present invention contains an antioxidant, the antioxidant content is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of polyimide resin. By adding 0.1 parts by mass or more, it is easier to obtain the effect of improving elongation characteristics and adhesion to metal materials even in high temperature and high humidity environments, and by adding 10 parts by mass or less, the sensitivity of the resin composition is improved, for example, through interaction with a photosensitive agent. The resin composition of the present invention may contain only one type of antioxidant or two or more types. If there are two or more polymerization inhibitors, it is preferable that their total is within the above range.

[0138] [Surfactants] The resin composition of the present invention preferably contains a surfactant. Various surfactants can be used as surfactants, such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0139] By incorporating a surfactant into the resin composition of the present invention, the liquid properties (especially fluidity) of the prepared resin composition are further improved, the uniformity of the coating thickness and the liquid-saving properties are further improved, and the ability of the resin composition to follow steps is increased. Specifically, when forming a film using a coating solution containing a surfactant, the interfacial tension between the surface to be coated and the coating solution is reduced, improving the wettability to the surface to be coated and improving the coatability to the surface to be coated. As a result, air bubbles and other particles are less likely to be included in the stepped areas, and a more uniform film with less thickness variation can be formed more favorably.

[0140] Examples of silicone-based surfactants, hydrocarbon-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants include the compounds described in paragraphs

[0329] to

[0334] of International Publication No. 2021 / 112189, respectively, which are incorporated herein by reference.

[0141] When the resin composition of the present invention contains a surfactant, the surfactant content is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, based on the total solid content of the resin composition. The resin composition of the present invention may contain only one type of surfactant, or it may contain two or more types. When two or more types are used, it is preferable that their total is within the above range.

[0142] [Light Absorber] The resin composition of the present invention may also preferably contain a compound (light absorber) whose absorbance at the exposure wavelength decreases upon exposure. Examples of light absorbers include the compounds described in paragraphs

[0159] to

[0183] of International Publication No. 2022 / 202647 and the compounds described in paragraphs

[0088] to

[0108] of Japanese Patent Application Publication No. 2019-206689. These contents are incorporated herein by reference.

[0143] When the resin composition of the present invention contains a light absorber, the content of the light absorber is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 5% by mass, based on the total solid content of the resin composition. The resin composition of the present invention may contain only one type of light absorber or may contain two or more types. When two or more types of light absorbers are contained, it is preferable that their total is within the above range.

[0144] [Base Generator] The resin composition of the present invention may contain a base generator. Here, a base generator is a compound that can generate a base by physical or chemical action. Preferred base generators include thermal base generators and photo-based base generators. The base generator may be an ionic base generator or a nonionic base generator. Examples of bases generated from the base generator include secondary amines and tertiary amines. The base generator is not particularly limited, and known base generators can be used. Known base-generating agents include, for example, carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, amineimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, α-lactone ring derivative compounds, amineimide compounds, phthalimide derivative compounds, and acyloxyimino compounds. Specific examples of nonionic base-generating agents include the compounds described in paragraphs

[0249] to

[0275] of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0145] Examples of base-generating agents include, but are not limited to, the following compounds.

[0146]

[0147] The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

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

[0149] Specific examples of ammonium salts include, but are not limited to, the following compounds.

[0150] Specific examples of iminium salts include, but are not limited to, the following compounds.

[0151] When the resin composition of the present invention contains a base generating agent, the amount of base generating agent is preferably 0.1 to 50 parts by mass per 100 parts by mass of the polyimide resin described above. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less. The resin composition of the present invention may contain only one type of base generating agent, or it may contain two or more types. When two or more types are used, it is preferable that their total is within the above range.

[0152] [Other Additives] The resin composition of the present invention may optionally contain various additives, such as higher fatty acid derivatives, inorganic particles, ultraviolet absorbers, photoacid generators, anti-aggregation agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliary agents (e.g., defoamers, flame retardants, etc.), to the extent that the effects of the present invention are obtained. By appropriately including these components, properties such as film properties can be adjusted. These components can be described, for example, in paragraphs

[0183] onwards of Japanese Patent Application Publication No. 2012-003225 (paragraph

[0237] of the corresponding U.S. Patent Application Publication No. 2013 / 0034812), paragraphs

[0101] to

[0104] ,

[0107] to

[0109] of Japanese Patent Application Publication No. 2008-250074, and the contents of these are incorporated herein. When these additives are included, their total content is preferably 3% by mass or less of the solid content of the composition.

[0153] [Characteristics of the resin composition of the present invention] The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of coating film thickness, 1,000 mm ２ / s~12,000mm ２ / s is preferred, and 2,000 mm ２ / s~10,000mm ２ / s is more preferable, 2,500 mm２ / s~8,000mm ２ / s is even more preferable. Within the above range, it becomes easier to obtain a highly uniform coating film. 1,000 mm ２ If the temperature is 1 / s or higher, it is easy to coat the film with the required thickness, for example, as an insulating film for rewiring, and 12,000 mm ２ If the rate is less than or equal to / s, a coating with excellent properties can be obtained on the coated surface.

[0154] The flash point of the resin composition of the present invention is preferably 25°C to 150°C. Specific examples of flash points of the resin composition include 60°C, 90°C, and 100°C.

[0155] The number of particles with a diameter of 0.5 to 20 μm that may be contained in the resin composition of the present invention is preferably 100 or less, and more preferably 50 or less. There is no particular lower limit to the number of particles, and it may be 0. From a practical standpoint such as manufacturing costs, the number of particles is, for example, 0.1 or more, specifically 1 or more. Furthermore, the number of particles with a diameter of 0.1 to 0.5 μm that may be contained in the resin composition of the present invention is preferably 100 or less, and more preferably 50 or less. There is no particular lower limit to the number of particles, and it may be 0. From a practical standpoint such as manufacturing costs, the number of particles is, for example, 0.1 or more, specifically 1 or more.

[0156] In this invention, when the number of particles in the resin composition is small, the resulting cured film tends to have good tensile elongation properties. This is merely a hypothesis, but can be explained as follows: If particles are present in the cured film, the location of those particles is thought to act as a "trigger" for fracture. Therefore, by reducing the number of particles in the resin composition used to form the cured film, the "trigger" for fracture in the cured film can be reduced, and as a result, good tensile elongation properties can be obtained.

[0157] Furthermore, in this invention, a lower number of particles in the resin composition tends to improve the adhesion of the resulting cured film to various substrates. This is presumed to be because fewer particles reduce the "triggers for delamination."

[0158] <Restrictions on the substances contained in the resin composition> The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the stability of the resin composition over time is improved. Furthermore, the lower limit of the water content of the resin composition of the present invention is preferably 0.001% by mass or more, can be 0.05% by mass or more, and can be 0.5% by mass or more, from the viewpoint of reducing the effort required to manage storage conditions, imparting adhesion, and imparting developability. Specific examples of the water content of the composition of the present invention include, for example, 0.05% by mass, 0.2% by mass, and 1.4% by mass. Methods for maintaining the water content include adjusting the humidity in the storage conditions and reducing the porosity of the storage container during storage.

[0159] From the viewpoint of insulation, reliability, etc., the metal content of the resin composition of the present invention is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Furthermore, from the viewpoint of reducing the effort required to reduce the metal content, mechanical properties, adhesion, etc., the lower limit of the metal content in the resin composition of the present invention can be 0.001 ppm by mass or more, and can also be 0.01 ppm by mass or more. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, manganese, aluminum, titanium, cobalt, zinc, tin, etc., but excludes metals included as complexes of organic compounds and metals. If multiple metals are included, it is preferable that the sum of these metals is within the above range. Specific examples of the metal content in the resin composition of the present invention include, for example, 0.002 ppm by mass, 0.05 ppm by mass, 0.3 ppm by mass, etc.

[0160] Furthermore, methods for reducing metal impurities unintentionally included in the resin composition of the present invention include selecting raw materials with a low metal content as the raw materials constituting the resin composition, performing filter filtration on the raw materials constituting the resin composition, and performing distillation under conditions where contamination is suppressed as much as possible by lining the inside of the apparatus with polytetrafluoroethylene or the like.

[0161] In the resin composition of the present invention, the content of the following substances is preferably 1 ppm by mass or less, more preferably 0.1 ppm by mass or less, and preferably substantially absent (below the detection limit). <Substances> NMP, benzene, toluene, xylene, formaldehyde, trichloroethylene, ethylene oxide, dichloromethane, trichloromethane, tetrachloromethane, 1,2-dichloroethane, vinylidene chloride, vinyl chloride, 1,4-dioxane, acrylonitrile, PCB (polychlorinated biphenyl), PFOA (perfluorooctanoic acid), PFAS

[0162] Furthermore, in the resin composition of the present invention, the content of compounds that serve as raw materials for polyimide resin and compounds that serve as raw materials for compounds having radical polymerizable groups (so-called residual monomers) is preferably 10 ppm by mass or less, more preferably 5 ppm by mass or less, and even more preferably 1 ppm by mass or less. The lower limit of the content may be 0 ppm by mass. Also, from the viewpoint of reducing the effort required to reduce residual monomers and improving adhesion, the lower limit of the residual monomer content in the resin composition can be 0.001 ppm by mass or more, or 0.01 ppm by mass or more. Specific examples of residual monomer content include, for example, 0.002 ppm by mass, 0.05 ppm by mass, 0.3 ppm by mass, etc. Examples of such residual monomers include 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride, 4,4'-oxydiphthalic anhydride, 3,3'-dihydroxybenzidine, 2,2'-dimethylbenzidine, 4,4'-diaminodiphenyl ether, etc. Furthermore, if multiple residual monomers are present, it is preferable that the total amount of these residual monomers falls within the numerical range described above.

[0163] Conventional containers can be used as containers for the resin composition of the present invention. To suppress the incorporation of impurities into the raw materials and resin composition, it is also preferable to use multilayer bottles with an inner wall constructed of six types of resin in six layers, or bottles with a seven-layer structure of six types of resin. Examples of such containers include the container described in Japanese Patent Application Publication No. 2015-123351.

[0164] [Preparation of the resin composition of the present invention] The resin composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited and can be carried out by conventionally known methods. Examples of mixing methods include mixing with a stirring blade, mixing with a ball mill, and mixing by rotating a tank. The temperature during mixing is preferably 10 to 30°C, and more preferably 15 to 25°C.

[0165] When preparing the resin composition of the present invention, it is preferable that containers, pipes, etc., be made of stainless steel. It is preferable that the containers, pipes, etc., are cleaned with a solvent and free of residue. Furthermore, it is preferable that the preparation of the resin composition of the present invention be carried out in a cleanroom of class 10 to 10000. Moreover, when handling the resin composition of the present invention, such as when preparing it, it is preferable to use gloves with excellent solvent resistance. Excellent solvent resistance means, for example, conforming to ISO 374-1.

[0166] [Storage and Transportation of the Present Invention] When storing and transporting the resin composition of the present invention, a temperature range of -25°C to 15°C is preferred, and if it falls outside this range, the storage period is preferably less than 48 hours.

[0167] To remove foreign matter such as dust and fine particles from the resin composition of the present invention, filtration using a filter is preferable. The filter may be described in paragraph

[0287] of International Publication No. 2023 / 190064, and these descriptions are incorporated herein by reference. The filtration of the resin composition of the present invention is preferably carried out in a cleanroom of class 10 to 10000.

[0168] [Transfer Film] The resin composition of the present invention can also be applied to a method in which the resin composition is applied to a temporary support, a transfer film having a composition layer containing the resin composition is formed on the temporary support, and the composition layer is transferred onto a substrate. That is, the transfer film of the present invention is a transfer film having a temporary support and a composition layer containing the resin composition of the present invention as described above. The transfer film of the present invention may further include a cover film. Furthermore, the transfer film of the present invention may include layers other than the temporary support, the composition layer, and the cover film. Examples of layers other than the temporary support, the composition layer, and the cover film include a water-soluble resin layer containing a water-soluble resin such as PVA and / or PVP, a thermoplastic resin layer containing a thermoplastic resin, and an adhesion layer for providing adhesion.

[0169] [Temporary Support] The transfer film includes a temporary support. The temporary support is a component that supports the composition layer and is ultimately removed by a peeling process.

[0170] The temporary support may have either a single-layer or multi-layer structure. A film is preferred for the temporary support, and a resin film is more preferred. A film that is flexible and does not undergo significant deformation, shrinkage, or elongation under pressure, or under pressure and heat, is also preferred as the temporary support. Examples of the above films include polyethylene terephthalate film (e.g., biaxially oriented polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, polycycloolefin film, and polycarbonate film, with polyethylene terephthalate film being preferred. It is also preferable that the temporary support does not have deformations such as wrinkles or scratches.

[0171] [Composition Layer] The composition layer is a layer containing the curable resin composition of the present disclosure described above. The various components that may be included in the composition layer are, for example, the same as the various components that may be included in the curable resin composition of the present disclosure, and the preferred embodiments are the same except in terms of the solvent content. From the viewpoint of embedding properties, film handling properties, etc., the solvent content in the composition layer is preferably 0.0001% to 10% by mass, more preferably 0.0005% to 8% by mass, even more preferably 0.001% to 5% by mass, and particularly preferably 0.01% to 4% by mass, relative to the entire composition layer. The composition layer may consist of multiple layers with different components.

[0172] <Thickness> The average thickness of the composition layer is preferably 0.5 μm to 40 μm, more preferably 0.5 μm to 25 μm, and even more preferably 3 μm to 20 μm. An average thickness of 40 μm or less of the composition layer is preferable in that it provides excellent pattern resolution, and an average thickness of 0.5 μm or more of the composition layer is preferable in that it provides excellent embeddability and device reliability.

[0173] The transfer can be carried out using a known laminator. Roll type, diaphragm type, press type, vacuum pressure type, etc., can be used. Examples of commercially available laminators include vacuum pressure laminators manufactured by Meiki Seisakusho Co., Ltd., vacuum applicators manufactured by Nikko Materials Co., Ltd., and batch type vacuum pressure laminators. Regarding the transfer method, the manufacturing methods described in paragraphs 0108 to 0111 of Japanese Patent Application Publication No. 2022-39763, paragraphs 0023, 0036 to 0051 of Japanese Patent Application Publication No. 2006-023696, and paragraphs 0096 to 0108 of Japanese Patent Application Publication No. 2006-047592 can be suitably used.

[0174] [Cured product] The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention described above.

[0175] Furthermore, the cured product of the present invention may be a cured product obtained by curing a resin composition containing a polyimide resin, a compound having a radical polymerizable group, and a halogen element, wherein the content of the halogen element may be 0.001 to 300 ppm relative to the mass of the cured product. That is, even if the content of the halogen element in the resin composition is unknown, if the content of the halogen element in the cured product is within the above range, it is the cured product of the present invention. Here, the polyimide resin, the compound having a radical polymerizable group, and the halogen element contained in the resin composition in the above embodiment are the same as those described in the resin composition of the present invention described above. Furthermore, the content of the halogen element in the cured product in the above embodiment refers to the value measured by the same measurement method as described in the resin composition of the present invention described above.

[0176] [Method for Manufacturing Cured Products] The method for manufacturing cured products of the present invention preferably includes a film-forming step of applying the resin composition of the present invention onto a substrate to form a film. The method for manufacturing cured products more preferably includes the film-forming step, an exposure step of selectively exposing the film formed in the film-forming step, and a developing step of developing the film exposed in the exposure step using a developer to form a pattern. The method for manufacturing cured products particularly preferably includes the film-forming step, the exposure step, the developing step, and at least one of a heating step of heating the pattern obtained in the developing step and a post-development exposure step of exposing the pattern obtained in the developing step. Furthermore, the method for manufacturing cured products may also preferably include the film-forming step and a step of heating the film. Details of each step will be described below.

[0177] [Film Formation Process] The resin composition of the present invention can be used in a film formation process in which it is applied to a substrate to form a film. The method for producing a cured product of the present invention preferably includes a film formation process in which the resin composition is applied to a substrate to form a film.

[0178] <Substrate> The type of substrate can be appropriately determined according to the application and is not particularly limited. Examples of substrates include semiconductor manufacturing substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon; quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, reflective films; metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metal, and substrates in which a metal layer is formed by, for example, plating or vapor deposition); paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, molded substrates, and electrode plates for plasma display panels (PDPs). Semiconductor manufacturing substrates are particularly preferred, and silicon substrates, Cu substrates, and molded substrates are more preferred. These substrates may have layers such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) on their surface. The shape of the substrate is not particularly limited and may be circular or rectangular. If the substrate is circular, for example, a diameter of 100 to 450 mm is preferred, and 200 to 450 mm is more preferred. If it is rectangular, for example, the length of the shorter side is preferred to be 100 to 1000 mm, and 200 to 700 mm is more preferred. As the substrate, for example, a plate-shaped, preferably panel-shaped, substrate (substrate) is used.

[0179] When a resin composition is applied to the surface of a resin layer (for example, a layer made of cured material) or a metal layer to form a film, the resin layer or metal layer serves as the substrate.

[0180] Coating is a preferred method for applying the resin composition onto a substrate. Specific application methods include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating, or inkjet coating are preferred, and from the viewpoint of both uniformity of film thickness and productivity, spin coating and slit coating are more preferred. By adjusting the solid content concentration of the resin composition and the coating conditions according to the application method, a film of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected depending on the shape of the substrate; for circular substrates such as wafers, spin coating, spray coating, and inkjet coating are preferred, while for rectangular substrates, slit coating, spray coating, and inkjet coating are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. Furthermore, a method can be applied in which a coating film formed in advance on a temporary support by the above application method is transferred onto the substrate. Regarding the transfer method, the manufacturing methods described in paragraphs

[0023] ,

[0036] to

[0051] of Japanese Patent Application Publication No. 2006-023696 and paragraphs

[0096] to

[0108] of Japanese Patent Application Publication No. 2006-047592 can be suitably used. In addition, a step of removing excess film at the edges of the substrate may be performed. Examples of such steps include edge bead rinsing (EBR) and back rinsing. A pre-wetting step may be adopted in which the substrate is coated with various solvents to improve the wettability of the substrate before applying the resin composition to the substrate, and then the resin composition is applied.

[0181] [Drying Process] After the film formation process (layer formation process), the film may be subjected to a drying process (soft bake) to remove the solvent from the formed film (layer). That is, the method for producing a cured product of the present invention may include a drying process for drying the film formed in the film formation process. The drying process is preferably performed after the film formation process and before the exposure process. The drying temperature of the film in the drying process is preferably 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. Drying may also be performed under reduced pressure. The drying time is exemplified as 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.

[0182] [Exposure Process] The above film may be subjected to an exposure process in which the film is selectively exposed. The method for manufacturing the cured product may include an exposure process in which the film formed by the film formation process is selectively exposed. Selective exposure means exposing a part of the film. By selective exposure, exposed areas (exposed parts) and unexposed areas (unexposed parts) are formed in the film. The amount of exposure is not particularly limited as long as the resin composition of the present invention can be cured, but for example, it may be 50 to 10,000 mJ / cm in terms of exposure energy at a wavelength of 365 nm. ２ Preferably, 200 to 8,000 mJ / cm² ２ This is preferable.

[0183] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, with 240 to 550 nm being preferred.

[0184] In relation to the light source, the exposure wavelength can be (1) semiconductor lasers (e.g., wavelengths 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-line (wavelength 436nm), h-line (wavelength 405nm), i-line (wavelength 365nm), broad (three wavelengths of g, h, and i), (4) excimer lasers, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F ２Examples of exposure methods include (5) excimer laser (wavelength 157 nm), (6) extreme ultraviolet light; EUV (wavelength 13.6 nm), (7) YAG laser with second harmonic 532 nm and third harmonic 355 nm. For the resin composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferred, and exposure with the i-line is more preferred from the viewpoint of exposure sensitivity. The exposure method is not particularly limited, and any method in which at least a part of the film made of the resin composition of the present invention is exposed is acceptable, but examples include exposure using a photomask and exposure by laser direct imaging.

[0185] [Post-exposure heating step] The above film may be subjected to a heating step after exposure (post-exposure heating step (post-exposure bake)). That is, the method for producing a cured product of the present invention may include a post-exposure heating step in which the film exposed in the exposure step is heated. The post-exposure heating step can be performed after the exposure step and before the development step. The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, and more preferably 60°C to 120°C. The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, and more preferably 1 minute to 10 minutes. The heating rate in the post-exposure heating step is preferably 1 to 12°C / min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. The heating rate may also be changed as appropriate during heating. The heating means in the post-exposure heating step is not particularly limited, and known hot plates, ovens, infrared heaters, etc., can be used. Furthermore, it is preferable to carry out the heating process in a low-oxygen atmosphere by flowing inert gases such as nitrogen, helium, or argon through the system.

[0186] [Development Process] The film after exposure may be subjected to a development process in which a pattern is formed by developing it with a developer. That is, the method for manufacturing a cured product of the present invention may include a development process in which a pattern is formed by developing the film exposed in the exposure process with a developer. By developing, one of the exposed and unexposed parts of the film is removed, and a pattern is formed. Here, development in which the unexposed part of the film is removed by the development process is called negative development, and development in which the exposed part of the film is removed by the development process is called positive development.

[0187] <Developer> Developers used in the developing process include alkaline aqueous solutions or developers containing organic solvents.

[0188] When the developer is an alkaline aqueous solution, the basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts, preferably those described in paragraph

[0300] of International Publication No. 2023 / 190064, and more preferably tetramethylammonium hydroxide (TMAH). The content of the basic compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass, based on the total mass of the developer.

[0189] If the developer contains an organic solvent, the organic solvent may be one of the compounds described in paragraph

[0387] of International Publication No. 2021 / 112189. This is incorporated herein by reference. Suitable alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutylcarbinol, triethylene glycol, etc., and suitable amides include N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc.

[0190] When the developer contains an organic solvent, one or more organic solvents can be used in mixture form. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide is more preferred, and a developer containing cyclopentanone is particularly preferred.

[0191] When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Alternatively, the above content may be 100% by mass.

[0192] The developing solution may further contain other components. Examples of other components include known surfactants and known defoamers.

[0193] In the development process, after processing with the developer solution, the pattern may be further washed (rinsed) with a rinsing solution. Alternatively, methods such as supplying the rinsing solution before the developer solution in contact with the pattern dries completely may be employed.

[0194] The resin composition of the present invention preferably does not solidify at a concentration of 0.5 to 99.5% by mass when mixed with a developer. Furthermore, it is preferable that the resin composition of the present invention can be separated into developer components and resin composition components by methods such as distillation after mixing with a developer.

[0195] <Rinsing Solution> If the developer is an alkaline aqueous solution, water can be used as the rinsing solution. If the developer contains an organic solvent, a solvent different from the solvent contained in the developer (for example, water, or an organic solvent different from the organic solvent contained in the developer) can be used as the rinsing solution.

[0196] When the rinsing solution contains an organic solvent, the organic solvent can be the same as the organic solvent exemplified above when the developer contains an organic solvent. Preferably, the organic solvent in the rinsing solution is different from the organic solvent in the developer, and more preferably, it is an organic solvent with lower pattern solubility than the organic solvent in the developer.

[0197] If the rinsing solution contains an organic solvent, one or more organic solvents may be used in mixture form. Preferred organic solvents are cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA (propylene glycol monomethyl ether acetate), and PGME (propylene glycol monomethyl ether). More preferred are cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME, with cyclohexanone and PGMEA being even more preferred.

[0198] When the rinsing solution contains an organic solvent, the amount of the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, relative to the total mass of the rinsing solution. Alternatively, the amount of the organic solvent may be 100% by mass, relative to the total mass of the rinsing solution.

[0199] The rinse solution may further contain other components. Examples of other components include known surfactants and known defoaming agents. When the resin composition of the present invention is mixed with the rinse solution, it is preferable that it does not solidify at a concentration of 40 to 90% by mass.

[0200] <Method of supplying rinsing solution> There are no particular restrictions on the method of supplying the rinsing solution as long as a desired pattern can be formed. These include immersing the substrate in the rinsing solution, supplying the rinsing solution to the substrate by pouring the solution, supplying the rinsing solution to the substrate with a shower, and continuously supplying the rinsing solution onto the substrate using means such as a straight nozzle. From the viewpoint of the penetration of the rinsing solution, the removal of non-image areas, and manufacturing efficiency, there are methods of supplying the rinsing solution with a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuous supply with a spray nozzle is preferred, and from the viewpoint of the penetration of the rinsing solution into the image area, the method of supplying with a spray nozzle is more preferred. There are no particular restrictions on the type of nozzle, and examples include straight nozzles, shower nozzles, spray nozzles, etc. That is, the rinsing process is preferably a process of supplying the rinsing solution to the film after exposure using a straight nozzle or continuously supplying it, and it is more preferable to supply the rinsing solution using a spray nozzle. Possible methods for supplying the rinsing solution in the rinsing process include a process in which the rinsing solution is continuously supplied to the substrate, a process in which the rinsing solution is kept in a nearly stationary state on the substrate, a process in which the rinsing solution is vibrated on the substrate using ultrasound or the like, and a process that combines these methods.

[0201] The rinsing time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the rinsing solution during rinsing is not particularly specified, but is preferably 10 to 45°C, and more preferably 18 to 30°C.

[0202] [Heating Step] The pattern obtained by the developing step (or the pattern after rinsing, if a rinsing step is performed) may be subjected to a heating step (post-bake) in which the pattern obtained by the developing step is heated. That is, the method for producing a cured product of the present invention may include a heating step in which the pattern obtained by the developing step is heated. Furthermore, the method for producing a cured product of the present invention may include a heating step in which a pattern obtained by another method without performing a developing step, or a film obtained by a film formation step is heated. The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, and even more preferably 150 to 250°C. In particular, the reason why the effects of the present invention become apparent, in other words, because problems tend to occur when conventionally known resin compositions are cured at low temperatures, in the present invention, the heating temperature (maximum heating temperature) in the heating step is preferably 150°C or more and 200°C or less, more preferably 150°C or more and less than 200°C, and even more preferably 150°C or more and 190°C or less. Furthermore, in the heating process, the amount of volatilization of components with a boiling point of 150°C or higher is preferably 5000 ppm or less, and more preferably 500 ppm or less, relative to the gas flow rate in the heating process. The heating process can be described in paragraphs

[0326] to

[0332] of International Publication No. 2023 / 190064, and these descriptions are incorporated herein by reference.

[0203] [Metal layer formation step] The pattern obtained by the development step (preferably one that has been subjected to at least one of the heating step and the post-development exposure step) may be subjected to a metal layer formation step in which a metal layer is formed on the pattern. That is, the method for producing a cured product of the present invention preferably includes a metal layer formation step in which a metal layer is formed on the pattern obtained by the development step (preferably one that has been subjected to at least one of the heating step and the post-development exposure step).

[0204] The metal layer is not particularly limited, and existing metal species can be used, with examples including copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals, with copper and aluminum being more preferred, and copper being even more preferred.

[0205] The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, methods described in Japanese Patent Publication No. 2007-157879, Japanese Patent Publication No. 2001-521288, Japanese Patent Publication No. 2004-214501, Japanese Patent Publication No. 2004-101850, U.S. Patent No. 7888181B2, and U.S. Patent No. 9177926B2 can be used. For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and methods combining these can be considered. More specifically, patterning methods combining sputtering, photolithography and etching, and patterning methods combining photolithography and electroplating can be mentioned. Preferred embodiments of plating include electroplating using copper sulfate or copper cyanide plating solutions.

[0206] The thickness of the metal layer is preferably 0.01 to 50 μm at the thickest part, and more preferably 1 to 10 μm.

[0207] [Applications] The resin composition, cured product, and method for manufacturing the cured product of the present invention can be applied to fields such as insulating films for electronic devices, interlayer insulating films for redistribution layers, and stress buffer films. Other applications include etching patterns for sealing films, substrate materials (base films, coverlays, and interlayer insulating films for flexible printed circuit boards), or insulating films for the above-mentioned mounting applications. For more information on these applications, see, for example, Science & Technology Co., Ltd., "High-Functionality and Application Technologies of Polyimides," April 2008, supervised by Masaaki Kakimoto; CMC Technical Library, "Fundamentals and Development of Polyimide Materials," November 2011; and the Japan Polyimide and Aromatic Polymer Research Association, ed., "Latest Fundamentals and Applications of Polyimides," NTS, August 2010.

[0208] The resin composition, cured product, and method for manufacturing the cured product of the present invention can also be used for manufacturing printing plates such as offset or screen printing plates, etching molded parts, and manufacturing protective lacquers and dielectric layers in electronics, particularly microelectronics.

[0209] [Laminate and Method for Manufacturing a Laminate] The laminate of the present invention refers to a structure having multiple layers made of the cured product of the present invention. The laminate is a laminate containing two or more layers made of the cured product, and may be a laminate with three or more layers. Of the two or more layers made of the cured product included in the above laminate, at least one is made of the cured product of the present invention, and from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product due to the above shrinkage, it is also preferable that all layers made of the cured product included in the above laminate are made of the cured product of the present invention.

[0210] In other words, the method for manufacturing the laminate of the present invention preferably includes a method for manufacturing the cured product of the present invention, and more preferably includes repeating the method for manufacturing the cured product of the present invention multiple times.

[0211] The laminate of the present invention preferably comprises two or more layers made of cured material, with a metal layer preferably included between any of the layers made of cured material. The metal layer is preferably formed by the metal layer formation step described above. That is, the method for manufacturing the laminate of the present invention preferably further includes a metal layer formation step in which a metal layer is formed on the layers made of cured material, between multiple cured material manufacturing steps. The preferred embodiment of the metal layer formation step is as described above. As the laminate, for example, a laminate is preferred that includes at least three layers in which a first layer made of cured material, a metal layer, and a second layer made of cured material are laminated in this order. It is preferable that both the first layer made of cured material and the second layer made of cured material are layers made of cured material of the present invention. The resin composition of the present invention used to form the first layer made of cured material and the resin composition of the present invention used to form the second layer made of cured material may have the same composition or may have different compositions. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.

[0212] [Lamination Process] The method for manufacturing a laminate of the present invention preferably includes a lamination process. The lamination process is a series of steps that include performing, in this order, at least one of the following on the surface of a pattern (resin layer) or metal layer: (a) film formation process (layer formation process), (b) exposure process, (c) development process, (d) heating process, and post-development exposure process. However, the process may also involve repeating at least one of the following: (a) film formation process and (d) heating process and post-development exposure process. Furthermore, at least one of the following: (d) heating process and post-development exposure process may be followed by (e) metal layer formation process. Needless to say, the lamination process may also appropriately include the above-mentioned drying process, etc.

[0213] If a further lamination process is performed after the lamination process, a surface activation treatment process may be performed after the exposure process, the heating process, or the metal layer formation process. Plasma treatment is an example of a surface activation treatment. Details of the surface activation treatment will be described later.

[0214] The above lamination process is preferably performed 2 to 20 times, and more preferably 2 to 9 times. For example, a configuration with 2 to 20 resin layers, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferred, and a configuration with 2 to 9 resin layers is even more preferred. Each of the above layers may have the same composition, shape, film thickness, etc., or they may be different.

[0215] In the present invention, it is particularly preferable to form a cured product (resin layer) of the resin composition of the present invention so as to cover the metal layer after providing the metal layer. Specifically, examples include repeating the steps in the order of (a) film formation, (b) exposure, (c) development, (d) heating and post-development exposure, and (e) metal layer formation, or repeating the steps in the order of (a) film formation, (d) heating and post-development exposure, and (e) metal layer formation. By alternately performing the lamination step of stacking the resin composition layer (resin layer) of the present invention and the metal layer formation step, the resin composition layer (resin layer) and the metal layer of the present invention can be alternately stacked.

[0216] [Surface Activation Treatment Step] The manufacturing method of the laminate of the present invention preferably includes a surface activation treatment step in which at least a portion of the metal layer and the resin composition layer is surface activated. The surface activation treatment step is usually performed after the metal layer formation step, but after the development step (preferably after at least one of the heating step and the post-development exposure step), the surface activation treatment step may be performed on the resin composition layer before the metal layer formation step. The surface activation treatment may be performed only on at least a portion of the metal layer, or only on at least a portion of the resin composition layer after exposure, or on at least a portion of both the metal layer and the post-exposure resin composition layer. It is preferable to perform the surface activation treatment on at least a portion of the metal layer, and it is preferable to perform the surface activation treatment on a portion or all of the area on the surface of the metal layer where the resin composition layer is formed. By performing the surface activation treatment on the surface of the metal layer in this way, the adhesion to the resin composition layer (film) provided on its surface can be improved. It is also preferable to perform the surface activation treatment on a portion or all of the post-exposure resin composition layer (resin layer). By performing the surface activation treatment on the surface of the resin composition layer in this way, the adhesion to the metal layer and resin layer provided on the surface-activated surface can be improved. In particular, when the resin composition layer is cured, such as when developing negative film, it is less susceptible to damage from surface treatment and adhesion is easily improved. Surface activation treatment can be carried out, for example, by the method described in paragraph

[0415] of International Publication No. 2021 / 112189. This is incorporated herein by reference.

[0217] [Semiconductor Device and Method for Manufacturing the Same] The present invention also discloses a semiconductor device including a cured product or a laminate of the present invention. Furthermore, the present invention also discloses a method for manufacturing a semiconductor device including a method for manufacturing a cured product or a laminate of the present invention. Specific examples of semiconductor devices in which the resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer can be found in paragraphs

[0213] to

[0218] and Figure 1 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0218] The present invention will be described in more detail below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

[0219] [Synthesis of Polyimide Resin] [Synthesis Example 1: Synthesis of Polyimide Resin A-1] As an acidic dianhydride, 20.80 g (40 mmol) of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride is dissolved in 70 g of N-methylpyrrolidone (NMP). Subsequently, as diamines, 3.81 g (17.6 mmol) of 3,3'-dihydroxybenzidine and 3.74 g (17.6 mmol) of 2,2'-dimethylbenzidine are dissolved in 50 g of NMP, and this is added dropwise to the previously prepared NMP solution of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride over 1 hour at a temperature of 10°C to 25°C, and the mixture is stirred at 25°C for 30 minutes. Then, 10 g of toluene is added, and the mixture is reacted at 200°C for 4 hours while flowing nitrogen, and then cooled to 25°C. Next, 13.8 g (45 mmol) of 4-(chloromethyl)styrene, 16.6 g (120 mmol) of potassium carbonate, 1.38 g (10 mmol) of potassium iodide, and 0.08 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical are added as compounds that introduce radical polymerizable groups (hereinafter also called "polymerizable group introducing agents"), and the mixture is reacted at 95°C for 15 hours, cooled to 25°C, and diluted with 120 g of tetrahydrofuran. Subsequently, the reaction mixture is added dropwise to a mixture of 1.8 L of methanol and 0.6 L of water, stirred for 15 minutes, and then the polyimide resin is filtered. Next, the resin is re-slurred with 1 L of water, filtered, re-slurred again with 1 L of methanol, filtered, and dried under reduced pressure at 40°C for 8 hours. Next, the dried resin is dissolved in 250 g of tetrahydrofuran, 40 g of ion exchange resin (MB-1: manufactured by Organo), and the mixture is stirred for 4 hours. After removing the ion exchange resin by filtration, the polyimide resin is precipitated in 2 L of methanol and stirred for 15 minutes. The polyimide resin is obtained by filtration, and after re-slurring three times with 1 L of methanol, it is dried under reduced pressure at 45°C for 1 day to obtain polyimide resin A-1 represented by the structural formula described below. The weight-average molecular weight (Mw) of polyimide resin A-1 is 28,000.

[0220] Polyimide resin A-1

[0221] [Synthesis Examples 2-14: Synthesis of Polyimide Resins A-2 to A-14] Polyimide resins A-2 to A-14 are synthesized in the same manner as in Synthesis Example 1, except that the types and amounts of raw materials such as acid dianhydrides, diamines, and polymerizable group introducers, as well as the presence and number of times reslurry purification after resin filtration are changed as shown in Table 1 below.

[0222] [Synthesis Examples 15-17, 19-21, 25: Synthesis of Polyimide Resins A-15-17, 19-21, 25] Polyimide resins A-15-17, 19-21, 25 are synthesized in the same manner as in Synthesis Example 1, except that the types and amounts of raw materials such as acidic dianhydrides, diamines, monoamines, and polymerizable group introducers, the reaction time at 200°C is 24 hours, and the presence and number of times reslurry purification after resin filtration are changed as shown in Table 1 below.

[0223] [Synthesis Examples 18, 22-24: Synthesis of Polyimide Resins A-18, 22-24] Polyimide resins A-18, 22-24 are synthesized in the same manner as in Synthesis Example 1, except that the types and amounts of raw materials such as acid dianhydrides, diamines, monoamines, and polymerizable group introducers are changed to 24 hours at 200°C, potassium carbonate is replaced with 1,8-diazabicyclo[5.4.0]undeca-7-ene, and the presence and number of times reslurry purification after resin filtration are changed as shown in Table 1 below.

[0224] [Synthesis Examples H1-H4: Synthesis of Polyimide Resins HA-1-HA-4] Polyimide resins HA-1-HA-4 are synthesized in the same manner as in Synthesis Example 1, except that the types and amounts of raw materials such as acid dianhydrides, diamines, and polymerizable group introducers, as well as the presence and number of times reslurry purification after resin filtration are changed as shown in Table 1 below.

[0225]

[0226] The structural formula of the polyimide resin synthesized above is shown below. The subscripts in parentheses in the following formulas indicate the molar ratio of each repeating unit. The structure of the repeating unit is as follows: １ It is determined from the H-NMR (Nuclear Magnetic Resonance) spectrum.

[0227] Polyimide resin A-1 to A-3

[0228] Polyimide resin A-4

[0229] Polyimide resin A-5 to A-9

[0230] Polyimide resin A-10

[0231] Polyimide resin A-11

[0232] Polyimide resin A-12

[0233] Polyimide resin A-13

[0234] Polyimide resin A-14

[0235] Polyimide resin A-15

[0236] Polyimide resin A-16

[0237] Polyimide resin A-17

[0238] Polyimide resin A-18

[0239] Polyimide resin A-19

[0240] Polyimide resin A-20

[0241] Polyimide resin A-21

[0242] Polyimide resin A-22

[0243] Polyimide resin A-23

[0244] Polyimide resin A-24

[0245] Polyimide resin A-25

[0246] Polyimide resins HA-1 to HA-2

[0247] Polyimide resins HA-3 to HA-4

[0248] [Examples 1-114 and Comparative Examples 1-4: Preparation of Resin Compositions] A solution was prepared by mixing each component shown in Table 2 in the parts by mass shown in the same table. The resulting solution was then filtered through a polyethylene filter having a pore size of 0.1 μm to obtain the resin compositions of Examples 1-73 and Comparative Examples 1-4. The halogen element content of each obtained resin composition was measured using the method described above. The results are shown in Table 2 below.

[0249] [Comparative Example 5] A resin composition similar to that of Example 1 in Japanese Patent Publication No. 2021-117442 is prepared. The halogen element content of the obtained resin composition is measured using the method described above. The results are shown in Table 2 below. The resin composition prepared in Comparative Example 5 is a composition that is cured at 200°C for 2 hours, as will be described later.

[0250] [Comparative Example 6] A resin composition similar to that of Example 1 in Japanese Patent Publication No. 2021-117442 is prepared. The halogen element content of the obtained resin composition is measured using the method described above. The results are shown in Table 2 below. The resin composition prepared in Comparative Example 6 is a composition that is cured at 170°C for 2 hours, as will be described later.

[0251] [Comparative Example 7] A resin composition similar to that of Example 1 in Japanese Patent Publication No. 2019-066754 is prepared. The halogen element content of the obtained resin composition is measured using the method described above. The results are shown in Table 2 below.

[0252] [Comparative Example 8] A resin composition similar to that of Example 13 in International Publication No. 2019 / 189110 is prepared. The halogen element content of the obtained resin composition is measured using the method described above. The results are shown in Table 2 below.

[0253] [Evaluation] (1) Thermal shrinkage rate (as an index of flatness) For each example and comparative example, the resin composition is applied to a silicon wafer by spin coating to form a resin composition layer. The silicon wafer to which the obtained resin composition layer is applied is heated on a hot plate under the conditions shown in "Soft bake conditions" in Table 2 below to obtain a resin composition layer with a uniform thickness of approximately 15 μm after film formation on the silicon wafer. The obtained resin composition layer is subjected to a Ushio exposure machine (light source: 500 W / m²). ２ 600 mJ / cm² due to ultra-high pressure mercury lamp ２ The entire surface is exposed using the i-line with the specified exposure energy. The resin composition layer (resin layer) after exposure is spray-developed with cyclopentanone for 30 seconds, overlapped with cyclopentanone / PGMEA for 5 seconds, and rinsed with PGMEA for 30 seconds to remove unexposed areas. Furthermore, the layer is heated under a nitrogen atmosphere at a heating rate of 10°C / min, under the conditions shown in "Curing Conditions" in Table 2 below. A clean oven (Koyo, CLH-21) is used as the curing oven. The film thickness after curing is measured, and the thermal shrinkage rate is calculated as follows and evaluated according to the following criteria. The results are shown in Table 2 below. Note that A or B is preferred, and A is particularly preferred. Thermal shrinkage rate = 100 × (film thickness after soft bake - film thickness after cure) / (film thickness after soft bake) [%] <Evaluation criteria> A: Thermal shrinkage rate less than 10% B: Thermal shrinkage rate 10% or more and less than 20% C: Thermal shrinkage rate 20% or more

[0254] (2) As an adhesion test to the copper wiring after the high temperature and high humidity test, a test similar to the HAST (High Accelerated Stress Test) evaluation is performed using the test vehicle 100 shown in Figure 1. This is a schematic cross-sectional view. The test vehicle 100 has SiO on a Si wafer (silicon wafer) 102. ２ Layer 104, a patterned Ti layer 106, and patterned 10 μm L / S (line and space) comb-shaped Cu wiring 108 are stacked in this order, and the wiring is covered with cured products 110 of each composition. In Figure 1, d1 and d2 are 5 μm. SiO contained in the test vehicle ２The resin compositions of each example and comparative example are applied to layer 104 and Cu wiring 108, and soft baked under the conditions shown in Table 2 below to form a coated film. The obtained resin composition layer is exposed using a Ushio exposure machine (light source: 500 W / m²). ２ 600 mJ / cm² due to ultra-high pressure mercury lamp ２ Exposure is performed with the following exposure energy. Subsequently, spray development is performed with cyclopentanone for 30 seconds, overlap with cyclopentanone / PGMEA for 5 seconds, and rinse with PGMEA for 30 seconds to remove unexposed areas. Furthermore, heating is performed under a nitrogen atmosphere at a heating rate of 10°C / min, and heated under the conditions shown in "Curing Conditions" in Table 2 below. A clean oven (Koyo, CLH-21) is used as the curing oven. The HAST-like test is performed using a Hirayama oven at 130°C / 98% RH (relative humidity) for 96 hours. After the test, the cross section of test vehicle 100 is cut open, and 20 wires are observed using an SEM (scanning electron microscope) to check for voids or delamination between the copper wiring and the resin composition layer, and evaluated according to the following criteria. The results are shown in Table 2 below. <Evaluation Criteria> A: No voids or delamination are observed in any of the 20 wires. B: Of the 20 wires, gaps are observed in 1 to 4 wires, and no delamination is observed. C: Of the 20 wires, gaps are observed in 5 or more wires, or delamination is observed in 1 or more wires, or gaps are observed in 5 or more wires and delamination is observed in 1 or more wires.

[0255] (3) Mechanical strength after high temperature and high humidity test The resin compositions of each example and comparative example are applied to a silicon wafer by spin coating to form a resin composition layer. The silicon wafer to which the obtained resin composition layer is applied is heated on a hot plate under the conditions shown in "Soft bake conditions" in Table 2 below to obtain a resin composition layer with a uniform thickness of approximately 15 μm after film formation on the silicon wafer. The obtained resin composition layer is subjected to a Ushio exposure (light source: 500 W / m²). ２ 600 mJ / cm² due to ultra-high pressure mercury lamp ２Exposure is performed using a dumbbell-shaped mask with i-ray exposure energy. The dumbbell shape is the No. 7 dumbbell shape described in JIS K 6251:2017. The resin composition layer (resin layer) after exposure is spray-developed with cyclopentanone for 30 seconds and rinsed with PGMEA for 30 seconds to remove unexposed areas. Furthermore, the temperature is increased at a rate of 10°C / min under a nitrogen atmosphere and heated under the conditions shown in "Curing Conditions" in Table 2 below. A clean oven (Koyo, CLH-21) is used as the curing oven. Subsequently, the silicon wafer is cut in half, and one half is stored in a Hirayama oven at 130°C / 85% RH (relative humidity) for one week. After that, the resin layer (cured product) of both wafers is immersed in a 4.9 mass% hydrofluoric acid aqueous solution, and the dumbbell-shaped cured product (test piece) is peeled off from the silicon wafer (sample width 2 mm, sample length 35 mm). The resulting dumbbell-shaped test specimens were subjected to a tensile test using an Instron 34SC-2 machine at a grip strength of 1 kN, a chuck distance of 2 mm, and a speed of 5 mm / min to break. The elongation at break was calculated from the chuck distance at the time of breakage. The elongation at break was measured before and after storage in an oven at 130°C / 85% RH (relative humidity) for one week, and evaluated according to the following criteria. The results are shown in Table 2 below. <Evaluation Criteria> A: Change in elongation at break is less than 10% B: Change in elongation at break is 10% or more but less than 25% C: Change in elongation at break is 25% or more

[0256]

[0257] The components other than polyimide resin in Table 2 are listed below.

[0258] [Polymerizable Compounds] ・B-1: SR-209 (manufactured by Sartomer Co., Ltd.) ・B-2: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) ・B-3: Light Acrylate 3EG-A (manufactured by Kyoeisha Chemical Co., Ltd.) ・B-4: NOD-N (manufactured by Shin Nakamura Chemical Industry Co., Ltd.) ・B-5: A-9300 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.) ・B-6: Light Acrylate 4EG-A (manufactured by Kyoeisha Chemical Co., Ltd.) ・B-7: M-350 (manufactured by Toagosei Co., Ltd.)

[0259] [Solvents] D-1: γ-Butyrolactone, D-2: Dimethyl sulfoxide, D-3: γ-Valerolactone, D-4: Cyclohexanone, D-5: Anisole, D-6: N-Methylpyrrolidone, D-7: N-Ethylpyrrolidone

[0260] [Photopolymerization Initiators] ・E-1: Irgacure OXE01 (BASF) ・E-2: TR-PBG-304 (Tronly) ・E-3: Irgacure OXE02 (BASF)

[0261] [Thermal polymerization initiator] ・F-1: Perbutyl P (manufactured by NOF Corporation)

[0262] [Migration Inhibitors] ・G-1: 1H-tetrazole ・G-2: 5-aminotetrazole ・G-3: benzotriazole ・G-4: 4-azabenzotriazole ・G-5: 8-azaadenine ・G-6: ADEKA stab CDA-1M (manufactured by ADEKA Corporation) ・G-7: Compound with the following structure ・G-8: 5-methylbenzotriazole ・G-9: Compound with the following structure ・G-10: Compound with the following structure

[0263] [Organometallic Complex] • H-1: Compound with the structure shown below • H-2: Orgatic TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd.)

[0264] [Silane coupling agent] • I-1: KBM-5803 (manufactured by Shin-Etsu Chemical Co., Ltd.) • I-2: Compound with the structure shown below • I-3: KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0265] [Polymerization Initiators / Antioxidants] ・J-1: p-Methoxyphenol (manufactured by Kanto Chemical Co., Ltd.) ・J-2: Benzoquinone ・J-3: 4-HydroxyTEMPO ・J-4: Irganox 1010 (manufactured by ADEKA Corporation) ・J-5: 1-Nitroso-2-Naphthol

[0266] [Surfactants] ・K-1: BYK-333 (manufactured by BYK) ・K-2: DOWSIL ＴＭSH 8400 (NL) Fluid (Dow-made) • K-3: Compound with the following structure • K-4: Compound with the following structure • K-5: Compound with the following structure • K-6: Compound with the following structure • K-7: Compound with the following structure

[0267] The results shown in Table 2 indicate that when the halogen element content is outside the range of 0.001 to 300 ppm relative to the total mass of all solids in the resin composition, the resulting cured product exhibits poor adhesion after exposure to a high-temperature, high-humidity environment (Comparative Examples 1-4, 7, and 8). In particular, Comparative Examples 7 and 8, corresponding to Patent Documents 1 and 2, show that the resulting cured product exhibits poor flatness and poor mechanical strength after exposure to a high-temperature, high-humidity environment. Furthermore, even when the halogen element content is within a predetermined range, when a polyimide precursor is used as the resin, the resulting cured product exhibits poor flatness (Comparative Examples 5 and 6). In contrast, in resin compositions containing polyimide resin and polymerizable compounds, where the halogen element content is 0.001 to 300 ppm relative to the total mass of all solids in the resin composition, the resulting cured product exhibits good flatness, as well as excellent adhesion and mechanical strength even after exposure to a high-temperature, high-humidity environment (Examples 1-114).

[0268] [Example 101] The resin composition used in Example 1 was applied in layers to the surface of a copper thin layer formed on a resin substrate by spin coating, and dried at 100°C for 4 minutes to form a resin composition layer with a thickness of 20 μm. After that, it was exposed using a stepper (Nikon Corporation, NSR1505 i6). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-and-space pattern and a line width of 10 μm). After exposure, it was heated at 100°C for 4 minutes, developed with cyclohexanone for 2 minutes, and rinsed with PGMEA for 30 seconds to obtain the layer pattern. Next, under a nitrogen atmosphere, the temperature was increased at a rate of 10°C / min until it reached 230°C, and then maintained at 230°C for 3 hours to form an interlayer insulating film for redistribution layers. When semiconductor devices were manufactured using these interlayer insulating films for redistribution layers, they operated without problems.

[0269] [Examples 102-214] In Example 101, the resin composition is changed from the one used in Example 1 to the one used in Examples 2-114; otherwise, the evaluation is the same as in Example 101. In all of the examples, the semiconductor device operates without problems.

[0270] [Film Formation using Transfer Film] In the evaluation of Examples 1 to 114, the reliability and resolution evaluation was performed in the same manner as above, except that the formation of the resin composition layer on a substrate with a copper thin layer formed on its surface or on a silicon wafer was changed as follows, and it was confirmed that the same results were obtained. <Formation of Resin Composition Layer> The resin composition prepared in Examples 1 to 114 after pressure filtration was applied to a temporary support (QS62, manufactured by Toray Industries, Inc., 16 μm thick PET (polyethylene terephthalate) film), and heated under the conditions shown in "Soft Bake Conditions" in Table 2 above to form a composition layer. The thickness of the composition layer was to be 15 μm after drying. A transfer film was obtained in this way. The composition layer of the transfer film was laminated so that it faced the substrate. Lamination was performed using an MCK vacuum laminator under the conditions of substrate temperature: 60°C, rubber roller temperature: 90°C, linear pressure: 2.5 N / cm, and transport speed: 1.6 m / min.

[0271] [Exposure using a direct writing exposure apparatus] In the evaluation of Examples 1 to 114, the evaluation was carried out in the same manner as above, except that the exposure method was changed as follows, and it was confirmed that the same results were obtained. <Exposure method> The obtained composition layer was exposed using a direct writing exposure apparatus (manufactured by SCREEN Semiconductor Solutions Co., Ltd.: DW-3100, wavelength 375 nm).

[0272] 100 Test vehicle 102 Silicon wafer 104 SiO ２ Layer 106 Patterned Ti layer 108 Comb-shaped Cu wiring 110 Cured resin composition

Claims

1. A resin composition comprising a polyimide resin, a compound having a radical polymerizable group, and a halogen element, wherein the content of the halogen element is 0.001 to 300 ppm relative to the total mass of the total solids of the resin composition.

2. The resin composition according to claim 1, wherein the content of the halogen element is 0.001 to 500 ppm relative to the mass of the polyimide resin.

3. The resin composition according to claim 1, wherein the polyimide resin is a polyimide resin having radical polymerizable groups.

4. The resin composition according to claim 1, wherein the polyimide resin has repeating units represented by the following formula (1). Here, in formula (1), R independently represents an organic group having a radical polymerizable group. n and m independently represent integers from 0 to 4, where n + m represents an integer of 1 or more. X represents an organic group having 4 or more carbon atoms. Y represents an organic group having 4 or more carbon atoms.

5. The resin composition according to claim 4, wherein R in formula (1) is an organic group having an aromatic group.

6. The resin composition according to claim 1, wherein the halogen element is at least one element selected from the group consisting of fluorine, chlorine, bromine, and iodine.

7. The resin composition according to claim 1, further comprising at least one of a photopolymerization initiator and a thermal polymerization initiator.

8. The resin composition according to claim 1, further comprising a migration inhibitor.

9. The resin composition according to claim 1, further comprising an organometallic complex.

10. The resin composition according to claim 1, used for forming an interlayer insulating film for a redistribution layer.

11. A transfer film comprising a temporary support and a composition layer containing the resin composition described in any one of claims 1 to 10.

12. A cured product obtained by curing the resin composition according to any one of claims 1 to 10.

13. A cured product obtained by curing a resin composition containing a polyimide resin, a compound having a radical polymerizable group, and a halogen element, wherein the content of the halogen element is 0.001 to 300 ppm relative to the mass of the cured product.

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

15. A method for producing a cured product, comprising a film-forming step of applying a resin composition according to any one of claims 1 to 10 onto a substrate to form a film.

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

17. A method for producing a cured product according to claim 15, comprising a heating step of heating the film to 50 to 450°C.

18. A method for manufacturing a laminate, comprising the method for manufacturing a cured product described in claim 15.

19. A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured product according to claim 15.

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

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