Resin sheet for forming insulating layer of semiconductor package substrate

Abstract

The present invention addresses the problem of providing a resin sheet for forming an insulating layer of a semiconductor package substrate, the resin sheet exhibiting excellent stain removal properties and excellent heat resistance (glass transition temperature), and also exhibiting high adhesion strength (CZ copper peel strength) even when exposed to a high-temperature, high-humidity environment, and a cured product (insulating layer) having the three characteristics can be provided. [Solution] A resin sheet for forming an insulating layer of a semiconductor package substrate, the resin sheet having a support and a resin composition layer provided on the support, the resin composition layer containing (1A) a maleimide compound having a specific structure, (B) an epoxy resin, and (C) a polycarbodiimide compound.

Description

Technical Field

[0001] This invention relates to a resin sheet for forming an insulating layer on a semiconductor packaging substrate. Furthermore, it relates to a semiconductor packaging substrate and a semiconductor device obtained using the resin sheet. Background Technology

[0002] Resin compositions containing epoxy resin are widely used as insulating layers for circuit boards such as semiconductor packaging substrates because they produce cured products with excellent insulation properties. This insulating layer can be formed, for example, by using a resin sheet containing a resin composition layer and laminating the resin composition layer onto the circuit board such as a semiconductor packaging substrate, followed by curing the resin composition layer.

[0003] On the other hand, with the increasing speed of communication in recent years, materials for insulating layers of circuit boards such as semiconductor packaging substrates need to have excellent dielectric properties (low dielectric loss tangent) in order to reduce transmission loss when operating in high-frequency environments. As insulating layer materials with excellent dielectric properties, materials using specific curing agents such as reactive ester resins that can reduce / suppress the generation of polar groups such as secondary hydroxyl groups during the curing reaction of epoxy resins have been reported (e.g., Patent Documents 1 and 2).

[0004] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2019-157027 Patent Document 2: Japanese Patent Application Publication No. 2020-094213 Summary of the Invention

[0005] The technical problem to be solved by the invention However, as mentioned above, in order to obtain a cured product with a low dielectric loss tangent, if an active ester resin or the like is used as a curing agent, a problem may arise where contamination residue is easily left during via formation. Furthermore, when manufacturing circuit boards such as semiconductor packaging substrates by alternating layers of insulating and conductive layers in a build-up manner, high adhesion strength (CZ copper peel strength) between the conductive and insulating layers is required. In particular, the inventors have found that even when high adhesion strength is exhibited immediately after manufacturing, the adhesion strength may decrease if the circuit board is exposed to a high-temperature and high-humidity environment. Moreover, when operating in high-frequency environments, there is a tendency for increased heat generation from electronic components, necessitating further improvements in the heat resistance of insulating materials used in high-speed communication applications.

[0006] The present invention was made in view of the above-mentioned problems, and its object is to provide a resin sheet for forming an insulating layer of a semiconductor packaging substrate. The resin sheet exhibits excellent contamination removal properties and excellent heat resistance (glass transition temperature), and also exhibits high adhesion strength (CZ copper peel strength) even when exposed to high temperature and high humidity environments, and can produce a cured product (insulating layer) that has all three of these properties.

[0007] means for solving technical problems The inventors conducted in-depth research and found that the above-mentioned problems can be solved by a resin sheet having a resin composition layer containing a maleimide compound, an epoxy resin, and a polycarbodiimide compound having a specific structure, thereby completing the present invention.

[0008] That is, the present invention includes the following contents. [1] A resin sheet for forming an insulating layer of a semiconductor packaging substrate, the resin sheet having a support and a resin composition layer disposed on the support, the resin composition layer comprising: (1A) a maleimide compound having a partial structure shown in formula (1), a partial structure shown in formula (T-1) chemically bonded to the partial structure shown in formula (1), and a partial structure shown in formula (T-2) chemically bonded to the partial structure shown in formula (1), (B) an epoxy resin, and (C) a polycarbodiimide compound, [Chemical Formula 1] (In equation (1), R) a1 R a2 R a3 and R a4 Each can independently represent a hydrogen atom or a hydrocarbon group with 1 to 18 carbon atoms. R 13 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. 2 Each represents an integer from 0 to 4 independently, n 1 Indicates the number of repeating units. The two "*" symbols represent connecting keys, indicating that a connecting key is in equation (T-1) below. 13 or L 14 The two bonds are chemically bonded at one position, and the other linking bond is in the L position of the following formula (T-2). 11 or L 12 Chemical bonding occurs at the positions of [chemical formula 2]. (In the above equations (T-1) and (T-2), R) 11 and R 15 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. R 12 and R 14 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. L 11 L 12 L13 and L 14 Each represents a connection key independently. Specifically, in L... 11 or L 12 The position is chemically bonded to part of the structure shown in equation (1), and in L 13 or L 14 The position is chemically bonded to the partial structure shown in formula (1). m 1 and m 3 Each can independently represent an integer from 0 to 2. [2] The resin sheet for forming the insulating layer of the semiconductor packaging substrate according to [1], wherein, in formulas (T-1) and (T-2), L is not chemically bonded to the partial structure shown in formula (1). 11 L 12 L 13 and L 14 Bonded to a hydrogen atom or a monovalent group as shown in formula (4) below, [Chemical Formula 3] (In equation (4), R) a5 and R a6 Each can independently represent a hydrogen atom or a hydrocarbon group with 1 to 18 carbon atoms. R 16 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. 4 Represents integers from 0 to 5, * represents a hyphen. [3] A resin sheet for forming an insulating layer of a semiconductor packaging substrate, the resin sheet having a support and a resin composition layer disposed on the support, the resin composition layer comprising: (2A) a maleimide compound having a structural unit shown in formula (2), (B) an epoxy resin, and (C) a polycarbodiimide compound, [Chemical Formula 4] (In equation (2), R) a1 R a2 R a3 R a4 R a5 and R a6 Each can independently represent a hydrogen atom or a hydrocarbon group with 1 to 18 carbon atoms. R 11 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. R 12 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. R 13 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. R 16 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. 1 Each represents an integer from 0 to 2 independently, m 6 Each element independently represents an integer from 0 to 2, and satisfies m 1 +m 6 ≤2. m 2 Each represents an integer from 0 to 4 independently, m4 Each represents an integer from 0 to 5 independently, n 1 Each element independently represents the number of repeating units. [4] The resin sheet for forming the insulating layer of the semiconductor packaging substrate according to [3], wherein component (2A) is a maleimide compound having the structure shown in formula (3) below, [Chemical Formula 5] [Chemical Formula 6] In equations (3), (4), and (5), R a1 R a2 R a3 R a4 R a5 and R a6 Each can independently represent a hydrogen atom or a hydrocarbon group with 1 to 18 carbon atoms. R 11 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. R 12 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. R 13 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. R 16 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. 1 Each represents an integer from 0 to 2 independently, m 6 Each represents an integer from 0 to 2 independently, m 5 Each element independently represents an integer from 0 to 3, and satisfies m 1 +m 6 ≤2 and m 1 +m 5 ≤3. m 2 Each represents an integer from 0 to 4 independently, m 4 Each of the n integers from 0 to 5 can be represented independently. 1 Each element independently represents the number of repeating units, and each of n independently represents an integer greater than 1. X M1 X represents a hydrogen atom or a monovalent group as shown in formula (4). M2 * Represents a hydrogen atom or a monovalent group as shown in formula (5). * Represents a linking bond. [5] A resin sheet for forming an insulating layer of a semiconductor packaging substrate according to any one of [1] to [4], wherein R 13 Each is an alkyl group having 1 to 18 carbon atoms. [6] A resin sheet for forming an insulating layer of a semiconductor packaging substrate according to any one of [1], [2], and [5], wherein the mass ratio of component (1A) to component (C) in the resin composition layer [(1A) component / (C) component] is 0.1 to 50. [7] A resin sheet for forming an insulating layer of a semiconductor packaging substrate according to any one of [3] to [5], wherein the mass ratio of component (2A) to component (C) in the resin composition layer [(2A) component / (C) component] is 0.1 to 50. [8] A resin sheet for forming an insulating layer of a semiconductor packaging substrate according to any one of [1] to [7], wherein the resin composition layer further contains a (D) curing agent. [9] The resin sheet for forming the insulating layer of the semiconductor packaging substrate according to [8], wherein the ratio of the number of moles of the active groups of the curing agent (D) to the number of moles of the epoxy groups of the epoxy resin (B) in the resin composition layer (number of moles of the active groups of the curing agent / number of moles of the epoxy groups of the epoxy resin) is 1 or more.

[10] A resin sheet for forming an insulating layer of a semiconductor packaging substrate according to any one of [1] to [9], wherein the resin composition layer further contains (E) an inorganic filler material.

[11] The resin sheet for forming the insulating layer of the semiconductor packaging substrate according to

[10] , wherein when the non-volatile component in the resin composition layer is set to 100% by mass, the content of the (E) component in the resin composition layer is 80% by mass or less.

[12] The resin sheet for forming the insulating layer of the semiconductor packaging substrate according to any one of [1], [2], [5], [6], [8] to

[11] , wherein the resin composition layer further contains maleimide compounds other than component (1A) (hereinafter referred to as "(1F) other maleimide compounds").

[13] A resin sheet for forming an insulating layer of a semiconductor packaging substrate according to any one of [3] to [5] and [7] to

[11] , wherein the resin composition layer further contains maleimide compounds other than component (2A) (hereinafter referred to as "(2F) other maleimide compounds").

[14] A resin sheet for forming an insulating layer of a semiconductor packaging substrate according to any one of [1] to

[13] , wherein the resin composition layer further contains (G) free radical polymerizable resin.

[15] A resin sheet for forming an insulating layer of a semiconductor packaging substrate according to any one of [1] to

[14] , wherein the resin composition layer further contains an organic filler material (H).

[16] A resin sheet for forming an insulating layer of a semiconductor packaging substrate according to any one of [1] to

[15] , wherein the resin composition layer further contains (I) a curing accelerator.

[17] A resin sheet for forming an insulating layer of a semiconductor packaging substrate according to any one of [1] to

[16] , wherein the support is a thermoplastic resin film or a metal foil.

[18] A semiconductor packaging substrate having an insulating layer comprising a cured resin composition layer of a resin sheet used for forming an insulating layer of the semiconductor packaging substrate as described in any one of [1] to

[17] .

[19] A semiconductor device comprising the semiconductor packaging substrate described in

[18] . Effects of the Invention

[0009] According to the present invention, a resin sheet for forming an insulating layer of a semiconductor packaging substrate, a semiconductor packaging substrate and a semiconductor device obtained using the resin sheet can be provided. The resin sheet exhibits excellent contamination removal properties and excellent heat resistance (glass transition temperature), and also exhibits high adhesion strength (CZ copper peel strength) even when exposed to high temperature and high humidity environments, and can produce a cured product (insulating layer) that combines these three properties. Attached Figure Description

[0010] Figure 1 This is a schematic top view of a glass cloth substrate epoxy resin double-sided copper-clad laminate with inner layer circuitry used in reflow soldering tests. Detailed Implementation

[0011] The present invention will now be described in detail with reference to the embodiments and examples shown below. However, the present invention is not limited to the embodiments and examples listed below, and may be implemented in any way without departing from the scope of the claims and their equivalents.

[0012] [Explanation of Terminology] In the following explanation, the descriptions of numerical ranges as "above XX and below YY" or "XX to YY" refer to the numerical range including both the lower and upper limits as endpoints, unless otherwise specified. When the numerical range is described in stages, the upper and lower limits of each numerical range can be combined arbitrarily.

[0013] In the following description, unless otherwise stated, “dielectric constant” means “relative dielectric constant”.

[0014] In the following description, "non-volatile component" refers to the component constituting the resin composition layer other than the organic solvents described later. Additionally, "resin component" refers to the non-volatile component constituting the resin composition layer after removing the inorganic filler materials described later.

[0015] In the following description, the term "optionally having substituents" used to refer to compounds or groups, unless otherwise stated, refers to two cases: either the hydrogen atoms of the compound or group are not substituted by substituents, or some or all of the hydrogen atoms of the compound or group are substituted by substituents. Furthermore, when the number of constituent atoms and carbon atoms of the compound or group is stated, unless otherwise specified, this number of constituent atoms and carbon atoms does not include the number of constituent atoms and carbon atoms of substituents.

[0016] In the following description, "aromatic ring" refers to a ring that follows Hückel's rule, where the number of electrons in the π-electron system of the ring is 4r+2 (r is a natural number), including monocyclic aromatic rings and fused aromatic rings formed by the fusion of two or more monocyclic aromatic rings. Unless otherwise specified, monocyclic aromatic rings are preferred as aromatic rings. The aromatic ring can be an aromatic carbon ring having only carbon atoms as cyclic atoms, or an aromatic heterocycle having, in addition to carbon atoms, heteroatoms such as oxygen, nitrogen, and sulfur atoms as cyclic atoms. Unless otherwise specified, aromatic carbon rings are preferred as aromatic rings. Unless otherwise specified, the number of carbon atoms in the aromatic ring is preferably 3 or more, more preferably 4 or more or 5 or more, further preferably 6 or more, and preferably up to 24 or less, more preferably 18 or less or 14 or less, and further preferably 10 or less. This number of carbon atoms does not include the number of carbon atoms without substituents.

[0017] Examples of monocyclic aromatic rings include benzene rings, furan rings, thiophene rings, pyrrole rings, pyrazole rings, oxazole rings, isoxazole rings, furazine rings, thiazole rings, isothiazole rings, thiadiazole rings, imidazole rings, triazole rings, tetraazole rings, pyridine rings, pyridazine rings, pyrimidine rings, and pyridazine rings. Examples of fused aromatic rings, formed by the fusion of two or more monocyclic aromatic rings, include naphthyl rings, anthracene rings, phenanthrene rings, benzofuran rings, isobenzofuran rings, indole rings, isoindole rings, benzothiophene rings, benzimidazole rings, indazole rings, benzoxazole rings, benzoisoxazole rings, benzothiazole rings, quinoline rings, isoquinoline rings, quinoxaline rings, acridine rings, quinazoline rings, terpinen rings, phthalazine rings, pyridothiazole rings, benzotriazole rings, imidazole-pyridine rings, triazole-pyridine rings, and purine rings. Unless otherwise specified, the aromatic ring is preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring.

[0018] In the following description, "alkyl" can be any of straight-chain, branched, or cyclic forms, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, 1,2-dimethylpropyl, n-hexyl, isohexyl, (n)heptyl, (n)octyl, (n)nonyl, (n)decyl, (n)undecyl, (n)dodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornyl, adamantyl, etc.

[0019] In the following description, components (1A) and (2A) are sometimes collectively referred to as "(A) component". Additionally, components (1F) and (2F) are sometimes collectively referred to as "(F) component". The resin sheet for forming the insulating layer of the semiconductor packaging substrate according to the first embodiment and the resin sheet for forming the insulating layer of the semiconductor packaging substrate according to the second embodiment are sometimes collectively referred to as "resin sheet for forming the insulating layer of the semiconductor packaging substrate".

[0020] [Resin sheet for forming the insulating layer of a semiconductor packaging substrate according to the first embodiment] The resin sheet for forming the insulating layer of a semiconductor packaging substrate according to the first embodiment of the present invention has a support and a resin composition layer disposed on the support. The resin composition layer contains (1A) a maleimide compound having a first specific structure, (B) an epoxy resin, and (C) a polycarbodiimide compound. The first specific structure is described below. According to such a resin sheet, excellent contamination removal properties and excellent heat resistance (glass transition temperature) are exhibited, and high adhesion strength (CZ copper peel strength) is also exhibited even when exposed to high temperature and high humidity environments, resulting in a cured product (insulating layer) that possesses all three characteristics. In the present invention, "adhesion strength" refers to the adhesion strength between the insulating layer and the conductor layer of the cured product containing the resin composition layer of the resin sheet for forming the insulating layer of the semiconductor packaging substrate of the present invention. The inventors have confirmed that the adhesion strength is particularly excellent when the conductor layer is copper. Examples of adhesion strength between the insulating layer and copper include "CZ copper peel strength" and "plating peel strength". "CZ copper peel strength" refers to the adhesion strength between the insulating layer and the conductor layer (copper) when they are bonded together by lamination. "Platinum peel strength" refers to the adhesion strength between the insulating layer and the conductor layer (copper) when a conductor layer (copper) is formed by plating on the insulating layer. According to the present invention, a cured product (insulating layer) exhibits excellent CZ copper peel strength and plating peel strength, especially a cured product (insulating layer) exhibiting excellent CZ copper peel strength. The inventors have also confirmed that the cured product (insulating layer) obtained by the present invention also exhibits excellent dielectric properties (low dielectric constant, low dielectric loss tangent) and excellent reflow solderability, low coefficient of linear thermal expansion (CTE), suppressed warpage, and low arithmetic mean roughness Ra of the surface of the roughened insulating layer.

[0021] The resin sheet for forming the insulating layer of the semiconductor packaging substrate according to the first embodiment of the present invention is useful as an insulating layer for the semiconductor packaging substrate. Examples of semiconductor packaging substrates include FC-BGA, FC-CSP, MIS-BGA package, ETS-BGA package, Fan-out type WLP (Wafer Level Package), Fan-in type WLP, Fan-out type PLP (Panel Level Package), and Fan-in type PLP. Hereinafter, "resin sheet for forming the insulating layer of the semiconductor packaging substrate" will sometimes be simply referred to as "resin sheet".

[0022] <Support Body> The resin sheet according to the first embodiment of the present invention has a support body, which is bonded to one side of the resin composition layer. Examples of support bodies include thermoplastic resin films, metal foils, and release paper, with thermoplastic resin films or metal foils being preferred, and thermoplastic resin films being more preferred.

[0023] When a thermoplastic resin film is used as a support, examples of thermoplastic resins include polyester resins such as polyethylene terephthalate (hereinafter, sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter, sometimes abbreviated as "PEN"); polycarbonate (hereinafter, sometimes abbreviated as "PC"); acrylic resins such as polymethyl methacrylate (PMMA); cyclic polyolefins; triacetyl cellulose (TAC); polyether sulfide (PES); polyether ketone; and polyimide. Among these, polyester resins are preferred, polyethylene terephthalate and polyethylene naphthalate are more preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0024] When metal foil is used as a support, examples of metal foil include copper foil and aluminum foil. Copper foil is preferred. As copper foil, foil containing a single metal such as copper can be used, or foil containing an alloy of copper and other metals (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can be used.

[0025] For the support, matte finish, corona treatment, and antistatic treatment can be applied to the surface that bonds with the resin composition layer.

[0026] Furthermore, as a support, a support with a release layer can be used on the surface that bonds to the resin composition layer. Examples of release agents for the release layer of a support with a release layer include, for example, one or more release agents selected from alkyd resins, polyolefin resins, polyurethane resins, and silicone resins. Commercially available release agents include "SK-1," "AL-5," and "AL-7" manufactured by Lintec Corporation. Additionally, commercially available products can be used as supports with release layers, such as "Purex" manufactured by Toyobo Corporation and "Unipeel" manufactured by Unitech Corporation, which are PET films having a release layer with an alkyd resin-based release agent or a polyolefin resin-based release agent as the main component.

[0027] The thickness of the support is not particularly limited, but is preferably 1 μm or more, more preferably 5 μm or more, even more preferably 10 μm or more, preferably 75 μm or less, more preferably 60 μm or less, and even more preferably 50 μm or less. When using a support with a release layer, the overall thickness of the support with the release layer is preferably within the above range.

[0028] <Resin Composition Layer> The resin sheet according to the first embodiment of the present invention has a resin composition layer disposed on a support. An insulating layer can be formed by thermally curing the resin composition layer. Typically, the insulating layer comprises a cured product of the resin composition layer, preferably only comprising a cured product of the resin composition layer. As described above, the resin composition layer contains (1A) a maleimide compound having a first specific structure, (B) an epoxy resin, and (C) a polycarbodiimide compound.

[0029] From the viewpoint of achieving thinner semiconductor packaging substrates and providing a cured product with excellent insulation properties even when the cured resin composition layer is a thin film, the thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, and even more preferably 55 μm or less. The lower limit of the resin composition layer thickness is not particularly limited, and is typically 5 μm or more, 10 μm or more, etc.

[0030] The resin composition layer may further contain any components in combination with components (1A) to (C). Examples of such components include (D) a curing agent, (E) an inorganic filler, (1F) other maleimide compounds, (G) a free radical polymerizable resin, (H) an organic filler, (I) a curing accelerator, (J) an organic solvent, and (K) other additives. Hereinafter, each component contained in the resin composition layer of the resin sheet according to the first embodiment will be described in detail.

[0031] <(1A) Maleimide compounds having a first specific structure> The resin composition layer of the resin sheet according to the first embodiment of the present invention comprises: (1A) a maleimide compound having a partial structure shown in formula (1), a partial structure shown in formula (T-1) chemically bonded to the partial structure shown in formula (1), and a maleimide compound having a partial structure shown in formula (T-2) chemically bonded to the partial structure shown in formula (1). Component (1A) may be used alone or in combination of two or more. [Chemical Formula 7] (In equation (1), R) a1 R a2 R a3 and R a4 Each can independently represent a hydrogen atom or a hydrocarbon group with 1 to 18 carbon atoms. R 13 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. 2 Each represents an integer from 0 to 4 independently, n 1 Indicates the number of repeating units. The two "*" symbols represent connecting keys, indicating that a connecting key is in equation (T-1) below.13 or L 14 The two bonds are chemically bonded at one position, and the other linking bond is in the L position of the following formula (T-2). 11 or L 12 Chemical bonding occurs at specific positions. [Chemical Formula 8] (In the above equations (T-1) and (T-2), R) 11 and R 15 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. R 12 and R 14 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. L 11 L 12 L 13 and L 14 Each represents a connection key independently. Specifically, in L... 11 or L 12 The position is chemically bonded to part of the structure shown in equation (1), and in L 13 or L 14 The position is chemically bonded to the partial structure shown in formula (1). m 1 and m 3 Each can independently represent an integer from 0 to 2.

[0032] In equation (1), the two asterisks represent connecting keys. Furthermore, one of the two connecting keys is represented by L in equation (T-1) above. 13 or L 14 Chemical bonding occurs at the position of [position missing]. Additionally, another linking bond is located at L in the above formula (T-2). 11 or L 12 Chemical bonding occurs at the position. Therefore, component (1A) has a structural unit formed by connecting the partial structure shown in formula (T-1) and the partial structure shown in formula (T-2) through the partial structure shown in formula (1), and the partial structure shown in formula (1) is chemically bonded at the para or ortho position relative to the maleimide group on the benzene ring in formula (T-1) and formula (T-2).

[0033] In equation (1), R a1 R a2 R a3 and R a4 Each group independently represents a hydrocarbon group having 1 to 18 hydrogen or carbon atoms. Examples of hydrocarbon groups include alkyl, alkenyl, and aromatic hydrocarbon groups, with alkyl being preferred. The upper limit for the number of carbon atoms in the hydrocarbon group is preferably 12 or less or 10 or less, more preferably 6 or less, and even more preferably 5 or less, 4 or less, 3 or less, or 2 or less. In one embodiment, R... a1 R a2 Ra3 and R a4 The number of carbon atoms in the hydrocarbon group is particularly preferably 1.

[0034] R a1 R a2 R a3 and R a4 The alkyl group is a chain (straight-chain or branched) alkyl group or a cyclic alkyl group. The alkyl group has 1 to 18 carbon atoms, preferably 1 to 12 or 1 to 10, more preferably 1 to 6, further preferably 1 to 5, 1 to 4, 1 to 3 or 1 to 2, and particularly preferably 1. Examples of chain alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, hexyl, 2-ethylhexyl, octyl, decyl, etc., preferably methyl, ethyl, n-propyl, isopropyl or tert-butyl, more preferably methyl or ethyl, and further preferably methyl. Examples of cyclic alkyl groups include cyclopentyl, cyclohexyl, cyclooctyl, etc., preferably cyclohexyl.

[0035] R a1 R a2 R a3 and R a4 The alkenyl group is a straight-chain, branched, and / or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one non-aromatic carbon-carbon double bond. The alkenyl group has 2 to 18 carbon atoms, preferably 2 to 12 or 2 to 10, more preferably 2 to 6, further preferably 2 to 5, 2 to 4, or 2 to 3, and particularly preferably 2. Examples of alkenyl groups include vinyl, propenyl (allyl, 1-propenyl, isopropenyl), butenyl (1-butenyl, crotonyl, methylallyl, isocrotonyl, etc.), pentenyl (1-pentenyl, etc.), hexenyl (1-hexenyl, etc.), heptenyl (1-heptenyl, etc.), octenyl (1-octenyl, etc.), cyclopentenyl (2-cyclopentenyl, etc.), and cyclohexenyl (3-cyclohexenyl), etc.

[0036] R a1 R a2 R a3 and R a4 The aromatic hydrocarbon group is a group formed by removing one hydrogen atom from an aromatic carbon ring. The aromatic hydrocarbon group has 6 to 18 carbon atoms, preferably 6 to 12 or 6 to 10, and more preferably 6. Examples of aromatic hydrocarbon groups include phenyl, naphthyl, anthracene, etc., preferably phenyl or naphthyl, and more preferably phenyl.

[0037] In one implementation, R a1 R a2 R a3 and R a4 Hydrogen atoms are preferred.

[0038] In another embodiment, R is preferred. a1 and R a2 One of them is a hydrogen atom and the other is a hydrocarbon group with 1 to 18 carbon atoms, more preferably R. a1 and R a2 One of them is a hydrogen atom and the other is an alkyl group having 1 to 18 carbon atoms, with R being more preferred. a1 and R a2 One of them is a hydrogen atom and the other is an alkyl group having 1 to 6 carbon atoms, with R being particularly preferred. a1 and R a2 One of them is a hydrogen atom, and the other is a methyl group. Similarly, R is preferred. a3 and R a4 One of them is a hydrogen atom and the other is a hydrocarbon group with 1 to 18 carbon atoms, more preferably R. a3 and R a4 One of them is a hydrogen atom and the other is an alkyl group having 1 to 18 carbon atoms, with R being more preferred. a3 and R a4 One of them is a hydrogen atom and the other is an alkyl group having 1 to 6 carbon atoms, with R being particularly preferred. a3 and R a4 One of them is a hydrogen atom and the other is a methyl group.

[0039] In equation (1), R 13 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. 2 or n 1 When the integer is greater than or equal to 2, multiple existing R 13 They can be the same or different, but being the same is preferred. Examples of hydrocarbon groups include alkyl, alkenyl, and aromatic hydrocarbon groups, with alkyl being preferred. That is, R 13 Preferably, it is an alkyl group having 1 to 18 carbon atoms. The upper limit for the number of carbon atoms in the hydrocarbon group is preferably 12 or less or 10 or less, more preferably 6 or less, and even more preferably 5 or less, 4 or less, 3 or less, or 2 or less. In one embodiment, R 13 The number of carbon atoms in the hydrocarbon group is particularly preferably 1.

[0040] R 13The alkyl group is a chain (straight-chain or branched) alkyl or a cyclic alkyl group, preferably a chain alkyl group, more preferably a straight-chain alkyl group. The alkyl group has 1 to 18 carbon atoms, preferably 1 to 12 or 1 to 10, more preferably 1 to 6, further preferably 1 to 5, 1 to 4, 1 to 3 or 1 to 2, and particularly preferably 1. Examples of chain alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, hexyl, 2-ethylhexyl, octyl, decyl, etc., preferably methyl, ethyl, n-propyl, isopropyl or tert-butyl, more preferably methyl or ethyl, and further preferably methyl. In addition, examples of cyclic alkyl groups include cyclopentyl, cyclohexyl, cyclooctyl, etc., preferably cyclohexyl.

[0041] R 13 The alkenyl group is a straight-chain, branched, and / or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one non-aromatic carbon-carbon double bond. The alkenyl group has 2 to 18 carbon atoms, preferably 2 to 12 or 2 to 10, more preferably 2 to 6, further preferably 2 to 5, 2 to 4, or 2 to 3, and particularly preferably 2. Examples of alkenyl groups include vinyl, propenyl (allyl, 1-propenyl, isopropenyl), butenyl (1-butenyl, crotonyl, methylallyl, isocrotonyl, etc.), pentenyl (1-pentenyl, etc.), hexenyl (1-hexenyl, etc.), heptenyl (1-heptenyl, etc.), octenyl (1-octenyl, etc.), cyclopentenyl (2-cyclopentenyl, etc.), and cyclohexenyl (3-cyclohexenyl), etc.

[0042] R 13 The aromatic hydrocarbon group is a group formed by removing one hydrogen atom from an aromatic carbon ring. The aromatic hydrocarbon group has 6 to 18 carbon atoms, preferably 6 to 12 or 6 to 10, and more preferably 6. Examples of aromatic hydrocarbon groups include phenyl, naphthyl, anthracene, etc., preferably phenyl or naphthyl, and more preferably phenyl.

[0043] It should be noted that R in equation (1) 13 The benzene ring that is bonded can be the benzene ring of compound (b) with a benzyl ether skeleton, which will be described later.

[0044] In equation (1), m 2 Each element independently represents an integer from 0 to 4. In n 1 When the integer is greater than or equal to 2, multiple existing m 2 They can be the same or different, but it is preferred that they are the same. In one embodiment, m 2 The lower limit is preferably 1 or higher. 2 The upper limit is preferably 3 or less, more preferably 2 or less. Furthermore, m is even more preferably... 2 The value is 2. In another implementation, m 2It can also be 0.

[0045] In equation (1), n 1 Indicates the number of repeating units. From the viewpoint of adjusting the viscosity of the resin composition used in the manufacture of resin sheets, n 1 The upper limit is preferably 50 or less, more preferably 30 or less, and even more preferably 15 or less. 1 The lower limit is preferably 1 or more. Furthermore, in one embodiment, n 1 It can also be 1. The number of repeating units n 1 It can be calculated based on the feed ratio, NMR, etc.

[0046] In equations (T-1) and (T-2), R 11 and R 15 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. 1 When the value is 2, there are 2 R's. 11 They can be the same or different, but it is preferable that they are the same. 3 When the value is 2, there are 2 R's. 15 They can be the same or different, but being the same is preferred. R 11 and R 15 The preferred method and R 13 same.

[0047] In equations (T-1) and (T-2), m 1 and m 3 Each represents an integer from 0 to 2 independently. m 1 and m 3 They can be the same or different, but it is preferable that they are the same. 1 and m 3 Preferably 0 or 1, more preferably 0.

[0048] In equations (T-1) and (T-2), R 12 and R 14 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. R 12 and R 14 They can be the same as or different from each other, but are preferably the same. Examples of hydrocarbon groups include alkyl, alkenyl, and aromatic hydrocarbon groups, with alkyl being preferred. The upper limit of the number of carbon atoms in the hydrocarbon group is preferably 12 or less or 10 or less, more preferably 6 or less, and even more preferably 5 or less, 4 or less, or 3 or less. The lower limit of the number of carbon atoms in the hydrocarbon group is preferably 2 or more. In one embodiment, R... 12 and R 14 The number of carbon atoms in the hydrocarbon group is particularly preferred to be 2.

[0049] R 12 and R 14The alkyl group is a chain (straight-chain or branched) alkyl or a cyclic alkyl group, preferably a chain alkyl group, more preferably a straight-chain alkyl group. The upper limit for the number of carbon atoms in the alkyl group is 18 or less, preferably 12 or less or 10 or less, more preferably 6 or less, and even more preferably 5 or less, 4 or less or 3 or less. The lower limit for the number of carbon atoms in the alkyl group is preferably 2 or more. In one embodiment, R 12 and R 14 The alkyl group in the compound preferably has 2 carbon atoms. Examples of chain alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, hexyl, 2-ethylhexyl, octyl, and decyl, with methyl, ethyl, n-propyl, isopropyl, or tert-butyl being preferred, methyl or ethyl being more preferred, and ethyl being even more preferred. Additionally, examples of cyclic alkyl groups include cyclopentyl, cyclohexyl, and cyclooctyl, with cyclohexyl being preferred.

[0050] R 12 and R 14 The alkenyl group is a straight-chain, branched, and / or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one non-aromatic carbon-carbon double bond. The alkenyl group has 2 to 18 carbon atoms, preferably 2 to 12 or 2 to 10, more preferably 2 to 6, further preferably 2 to 5, 2 to 4, or 2 to 3, and particularly preferably 2. Examples of alkenyl groups include vinyl, propenyl (allyl, 1-propenyl, isopropenyl), butenyl (1-butenyl, crotonyl, methylallyl, isocrotonyl, etc.), pentenyl (1-pentenyl, etc.), hexenyl (1-hexenyl, etc.), heptenyl (1-heptenyl, etc.), octenyl (1-octenyl, etc.), cyclopentenyl (2-cyclopentenyl, etc.), and cyclohexenyl (3-cyclohexenyl), etc.

[0051] R 12 and R 14 The aromatic hydrocarbon group is a group formed by removing one hydrogen atom from an aromatic carbon ring. The aromatic hydrocarbon group has 6 to 18 carbon atoms, preferably 6 to 12 or 6 to 10, and more preferably 6. Examples of aromatic hydrocarbon groups include phenyl, naphthyl, anthracene, etc., preferably phenyl or naphthyl, and more preferably phenyl.

[0052] In equation (T-1), L 13 and L 14 Each represents a connection key independently. Specifically, in L... 13 or L 14 At least one of the positions, the partial structure shown in formula (1) is chemically bonded to the partial structure shown in formula (T-1). Additionally, the partial structure shown in formula (1) can also be chemically bonded to L. 13 and L 14 These two locations are chemically bonded.

[0053] In equation (T-2), L 11 and L 12 Each represents a connection key independently. Specifically, in L... 11 or L 12 At least one of the positions, the partial structure shown in formula (1) is chemically bonded to the partial structure shown in formula (T-2). Additionally, the partial structure shown in formula (1) can also be chemically bonded to L. 11 and L 12 These two locations are chemically bonded.

[0054] The ortho (6-position) position of the benzene ring relative to the maleimide group in formulas (T-1) and (T-2) allows for bonding with a partial structure shown in formula (1), resulting in higher solubility in organic solvents and exhibiting superior low dielectric loss tangent and high heat resistance upon curing. It should be noted that R in formula (T-1) 14 The combined benzene ring, and R in formula (T-2) 12 The benzene ring that is bonded can be the benzene ring of the aromatic amine compound (a) described later.

[0055] In equations (T-1) and (T-2), L that is not chemically bonded to the partial structure shown in equation (1) 11 L 12 L 13 and L 14 Preferably bonded to a hydrogen atom or a monovalent group as shown in formula (4) below, more preferably bonded to a hydrogen atom. [Chemical Formula 9] (In equation (4), R) a5 and R a6 Each can independently represent a hydrogen atom or a hydrocarbon group with 1 to 18 carbon atoms. R 16 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. 4 Represents an integer from 0 to 5. * indicates a hyphen.

[0056] In equation (4), R a5 and R a6 Each of the following independently represents a hydrocarbon group with 1 to 18 hydrogen atoms or carbon atoms, and is related to R in formula (1). a1 R a2 R a3 and R a4 Same. That is, in one implementation, R a5 and R a6 Preferably, it is a hydrogen atom. In another embodiment, R is preferred. a5 and R a6 One of them is a hydrogen atom and the other is a hydrocarbon group with 1 to 18 carbon atoms, more preferably R.a5 and R a6 One of them is a hydrogen atom and the other is an alkyl group having 1 to 18 carbon atoms, with R being more preferred. a5 and R a6 One of them is a hydrogen atom and the other is an alkyl group having 1 to 6 carbon atoms, with R being particularly preferred. a5 and R a6 One of them is a hydrogen atom and the other is a methyl group.

[0057] In equation (4), R 16 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. In m 4 When the integer is greater than or equal to 2, multiple existing R 16 They can be the same or different, but are preferably the same. Examples of hydrocarbon groups include alkyl, alkenyl, and aromatic hydrocarbon groups, with alkyl being preferred. The upper limit of the number of carbon atoms in the hydrocarbon group is preferably 12 or less or 10 or less, more preferably 6 or less, and even more preferably 5 or less, 4 or less, or 3 or less. The lower limit of the number of carbon atoms in the hydrocarbon group is preferably 2 or more. In one embodiment, R... 12 and R 14 The number of carbon atoms in the hydrocarbon group is particularly preferred to be 2.

[0058] R 16 The alkyl group is a chain (straight-chain or branched) alkyl or a cyclic alkyl group, preferably a chain alkyl group, more preferably a straight-chain alkyl group. The upper limit for the number of carbon atoms in the alkyl group is 18 or less, preferably 12 or less or 10 or less, more preferably 6 or less, and even more preferably 5 or less, 4 or less or 3 or less. The lower limit for the number of carbon atoms in the alkyl group is preferably 2 or more. In one embodiment, R 16 The alkyl group in the compound preferably has 2 carbon atoms. Examples of chain alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, hexyl, 2-ethylhexyl, octyl, and decyl, with methyl, ethyl, n-propyl, isopropyl, or tert-butyl being preferred, methyl or ethyl being more preferred, and ethyl being even more preferred. Additionally, examples of cyclic alkyl groups include cyclopentyl, cyclohexyl, and cyclooctyl, with cyclohexyl being preferred.

[0059] R 16The alkenyl group is a straight-chain, branched, and / or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one non-aromatic carbon-carbon double bond. The alkenyl group has 2 to 18 carbon atoms, preferably 2 to 12 or 2 to 10, more preferably 2 to 6, further preferably 2 to 5, 2 to 4, or 2 to 3, and particularly preferably 2. Examples of alkenyl groups include vinyl, propenyl (allyl, 1-propenyl, isopropenyl), butenyl (1-butenyl, crotonyl, methylallyl, isocrotonyl, etc.), pentenyl (1-pentenyl, etc.), hexenyl (1-hexenyl, etc.), heptenyl (1-heptenyl, etc.), octenyl (1-octenyl, etc.), cyclopentenyl (2-cyclopentenyl, etc.), and cyclohexenyl (3-cyclohexenyl), etc.

[0060] R 16 The aromatic hydrocarbon group is a group formed by removing one hydrogen atom from an aromatic carbon ring. The aromatic hydrocarbon group has 6 to 18 carbon atoms, preferably 6 to 12 or 6 to 10, and more preferably 6. Examples of aromatic hydrocarbon groups include phenyl, naphthyl, anthracene, etc., preferably phenyl or naphthyl, and more preferably phenyl.

[0061] In equation (4), m 4 Represents integers from 0 to 5. m 4 The upper limit is preferably 4 or less, more preferably 3 or less, further preferably 2 or less, and particularly preferably 1 or less. In one embodiment, m 4 It can be 0 or 1.

[0062] In component (1A), relative to the total amount (100% by mass) of component (1A), it is preferable to contain 1 to 99% by mass of the partial structure shown in formula (T-1), more preferably 3 to 97% by mass of the partial structure shown in formula (T-1), and even more preferably 5 to 95% by mass of the partial structure shown in formula (T-1).

[0063] In component (1A), relative to the total amount (100% by mass) of component (1A), it is preferable to contain 1 to 99% by mass of the partial structure shown in formula (T-2), more preferably 3 to 97% by mass of the partial structure shown in formula (T-2), and even more preferably 5 to 95% by mass of the partial structure shown in formula (T-2).

[0064] Specific examples of component (1A) include, for example, maleimide compounds as shown in formulas (3-1) to (3-4) below. [Chemical Formula 10]

[0065] The number-average molecular weight (Mn) of component (1A) is preferably in the range of 200 to 1500, more preferably in the range of 300 to 800. In addition, the weight-average molecular weight (Mw) of component (1A) is preferably in the range of 280 to 2000, more preferably in the range of 330 to 1200.

[0066] For component (1A), from the viewpoint of excellent solvent solubility, heat resistance, and low dielectric loss tangent, the molecular weight distribution (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) calculated by gel permeation chromatography (GPC) is preferably in the range of 1.01 to 4.0, more preferably 1.05 to 2.0, and even more preferably 1.10 to 1.8. It should be noted that, according to the GPC chromatogram obtained by GPC, when the molecular weight distribution range is wide and the high molecular weight component is abundant, the proportion of high molecular weight components contributing to flexibility increases. Therefore, compared with cured products using conventional maleimide, brittleness can be suppressed, resulting in cured products with excellent flexibility or suppleness, which is a preferred method.

[0067] It should be noted that the number-average molecular weight (Mn), weight-average molecular weight (Mw), and molecular weight distribution (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) of component (1A) can be determined using gel permeation chromatography (hereinafter referred to as "GPC").

[0068] From the viewpoint of significantly obtaining the effects of the present invention, when the resin component in the resin composition layer is set to 100% by mass, the content of component (1A) in the resin composition layer is preferably 0.1% by mass or more, more preferably 1% by mass or more or 2% by mass or more, further preferably 3% by mass or more or 4% by mass or more, and particularly preferably 5% by mass or more or 6% by mass or more. In one embodiment, it can be 7% by mass or more, 8% by mass or more, etc. The upper limit is preferably 50% by mass or less or 45% by mass or less, more preferably 40% by mass or less or 35% by mass or less, further preferably 30% by mass or less or 25% by mass or less, and particularly preferably 20% by mass or less, 15% by mass or less or 14% by mass or less. In another embodiment, it can be 13% by mass or less, 12% by mass or less, 11% by mass or less, 10% by mass or less, etc.

[0069] When the non-volatile component in the resin composition layer is set to 100% by mass, from the viewpoint of significantly obtaining the effects of the present invention, the content of component (1A) in the resin composition layer is preferably 0.01% by mass or more or 0.1% by mass or more, more preferably 0.2% by mass or more or 0.5% by mass or more, further preferably 0.8% by mass or more or 1% by mass or more, and particularly preferably 1.2% by mass or more or 1.5% by mass or more. In one embodiment, it can be 1.8% by mass or more, 2% by mass or more, 2.2% by mass or more, 2.5% by mass or more, etc. The upper limit is preferably 20% by mass or less or 18% by mass or less, more preferably 15% by mass or less or 12% by mass or less, further preferably 10% by mass or less or 8% by mass or less, and particularly preferably 5% by mass or less or 4% by mass or less. In another embodiment, it can be 3.8% by mass or less, 3.5% by mass or less, 3.2% by mass or less, 3% by mass or less, etc.

[0070] <(1A) First manufacturing method relating to maleimide compounds having a first specific structure> There are no limitations on the method of manufacturing component (1A). In one embodiment, component (1A) may be manufactured, for example, by using an aromatic amine compound (a) of formula (a1) (hereinafter also referred to as "aromatic amine compound (a)"), a compound (b) having a benzyl ether skeleton, and maleic anhydride as reactants (1). [Chemical Formula 11] (In formula (a1), R) a7 and R a8 Each independently represents an alkyl group having 1 to 6 hydrogen atoms or carbon atoms, R 1 R represents a hydrocarbon group with 1 to 18 carbon atoms. 2 and R 3 Each can independently represent a hydrogen atom or a hydrocarbon group with 1 to 18 carbon atoms.

[0071] Furthermore, for component (1A), it is preferable to use an intermediate amine compound (c) formed by linking aromatic amine compounds (a) through structural units from a compound (b) having a benzyl ether skeleton, and maleic anhydride as reactants (2). Moreover, the intermediate amine compound (c) is preferably a compound in which aromatic amine compound (a) and compound (b) having a benzyl ether skeleton are used as reactants (3).

[0072] In other words, the intermediate amine compound (c) in this embodiment preferably has a structural unit formed by chemically bonding a structural unit of an aromatic amine compound (a) having an aromatic ring with an amino group and a structural unit from a compound (b) having a benzyl ether skeleton. Furthermore, component (1A) has a structure in which the amino group bonded to the aromatic ring of the intermediate amine compound (c) is replaced with an N-substituted maleimide ring. It should be noted that "amino" in this specification also includes substituted amino groups in which the hydrogen atom of -NH2 is further replaced by an alkyl group having 1 to 6 carbon atoms.

[0073] Therefore, the component (1A) of the "maleimide compound" and the "intermediate amine compound (c)" of the precursor of the "maleimide compound" are different polymer compounds in that the amino group bonded to the aromatic ring is replaced with an N-substituted maleimide ring. It should be noted that the structural unit of the aforementioned aromatic amine compound (a) refers to the group after removing at least one hydrogen atom from the aromatic ring of the aromatic amine compound (a). For example, when the aromatic amine compound (a) is represented by formula (a1) as described below, the group after removing at least one hydrogen atom from the benzene ring of formula (a1) is called the structural unit of the aromatic amine compound (a). Furthermore, the structural unit from the compound (b) having a benzyl ether skeleton refers to the -(CH2O)- group in the compound (b) having a benzyl ether skeleton, where the -(CH2O)- group (excluding the terminal group) is replaced with -(CH2)- and directly bonded to the benzene ring, forming the -(CH2O)-R group. b All groups were replaced with -(CH2)- groups. It should be noted that the above R... b A hydrocarbon group representing 1 to 18 hydrogen or carbon atoms.

[0074] In this embodiment, since an aromatic amine compound (a) with a substituent at a specific position and an aromatic ring structure is used as a reaction raw material, the reaction site with the compound (b) with a benzyl ether skeleton described later is easily controlled, so a homogeneous chemical structure and a chain-like maleimide compound can be easily obtained. As a result, a maleimide compound ((1A) component) exhibiting excellent solubility in solvents, high heat resistance during curing, and low dielectric loss tangent can be provided.

[0075] Hereinafter, the aromatic amine compound (a), compound (b) having a benzyl ether skeleton, and maleic anhydride shown in formula (a1), which are constituents of the reaction raw material (1) of the maleimide compound ((1A) component), will be described.

[0076] <Aromatic amine compound (a) shown in formula (a1)> The aromatic amine compound (a) in this embodiment is shown by the following formula (a1), having an aromatic ring with an amino group attached, and having a structure in which a hydrocarbon group with 1 to 18 carbon atoms is attached at one of the adjacent positions of the aromatic ring. [Chemical Formula 12] (In formula (a1), R) a7 and R a8 Each independently represents an alkyl group having 1 to 6 hydrogen atoms or carbon atoms, R 1 R represents a hydrocarbon group with 1 to 18 carbon atoms. 2 and R 3 Each can independently represent a hydrogen atom or a hydrocarbon group with 1 to 18 carbon atoms.

[0077] In the aromatic amine compound (a) of this embodiment, the hydrocarbon group (R) that can be substituted with one or more but no more than two hydrogen atoms in the aromatic ring of the aromatic amine compound (a) is... 2 R 3 Examples of hydrocarbon groups with 1 to 18 carbon atoms, whether linear, branched, or cyclic, are preferred, with 1 to 12 linear or branched hydrocarbon groups, and more preferably with 1 to 6 linear or branched alkyl groups. As described in formula (a1) above, the aromatic ring has one bonding site with the compound (b) having a benzyl ether skeleton at both the ortho and para positions.

[0078] In the above formula (a1), R 1 The hydrocarbon group represents a hydrocarbon group having 1 to 18 carbon atoms, preferably a hydrocarbon group having 1 to 12 carbon atoms, and more preferably a hydrocarbon group having 1 to 6 carbon atoms.

[0079] In the above equation (a1), R 2 The hydrocarbon group represents 1 to 18 hydrogen atoms or carbon atoms, preferably a hydrocarbon group with 1 to 12 carbon atoms, and more preferably a hydrocarbon group with 1 to 6 carbon atoms.

[0080] In the above equation (a1), R 3 The hydrocarbon group represents 1 to 18 hydrogen atoms or carbon atoms, preferably a hydrocarbon group with 1 to 12 carbon atoms, and more preferably a hydrocarbon group with 1 to 6 carbon atoms.

[0081] Furthermore, by ensuring that the number of hydrocarbon groups (e.g., alkyl groups) substituted in the aromatic ring of the aromatic amine compound (a) is one or more, the reaction site with the compound (b) having a benzyl ether skeleton (described later) can be easily controlled, thus readily obtaining a maleimide compound (component (1A)) with a specific chemical structure. As a result, in the cured resin composition layer, solvent solubility, heat resistance, and excellent high-frequency electrical properties are readily exhibited. In particular, due to the introduction of substituents (R groups) into the ortho (proximal) position of the aromatic amine compound (a), 1Therefore, after maleimidizing the amino group from the aromatic amine compound (a), the dihedral angle formed by the aromatic ring plane of the aniline skeleton and the nitrogen-containing five-membered ring plane of the maleimide becomes larger. It is believed that the crystallinity of the maleimide group is easily destroyed and the solubility is improved.

[0082] In this embodiment, among the carbon atoms in the benzene ring constituting the aromatic amine compound (a), preferably one or more carbon atoms having the highest HOMO electron density (Hückel coefficient) are unsubstituted (substituted with hydrogen atoms). Therefore, as the aromatic amine compound (a) represented by formula (a1), it is preferable that any two of the 2, 4, and 6 positions are substituted with hydrogen atoms. As a particularly preferred embodiment of the aromatic amine compound (a) represented by formula (a1), the 2 position is substituted with an alkyl group, and the 4 and 6 positions are hydrogen atoms. This makes it easier to control ArS caused by the cationic reagent formed by the compound (b) having the benzyl ether skeleton described later. E Reaction and molecular design. As a result, the cured resin composition layer readily exhibits solvent solubility, heat resistance, and excellent high-frequency electrical properties. In particular, by substituting hydrogen atoms at positions 4 and 6 of the benzene ring in formula (a1), maleimide compounds (or intermediate amine compounds) with linearly extended molecules can be obtained.

[0083] As a specific example of the aromatic amine compound (a) in this embodiment, for example, o-toluidine, 2-ethylaniline, 2-propylaniline, 2-butylaniline, 2-cyclobutylaniline, 2-cyclopentylaniline, 2-cyclohexylaniline, dimethylaniline (2,3-dimethylaniline, 2,4-dimethylaniline or 2,5-dimethylaniline), diethylaniline (2,3-diethylaniline, 2,4-diethylaniline or 2,5-diethylaniline), diisopropylaniline (2,3-diisopropylaniline) Amines, such as 2,4-diisopropylaniline or 2,5-diisopropylaniline, ethyl methylaniline (e.g., ethyl methylaniline with methyl at any one of the 2,3, 2,4, or 2,5 positions and the others being ethyl), methyl isopropylaniline (e.g., methyl isopropylaniline with methyl at any one of the 2,3, 2,4, or 2,5 positions and the others being isopropyl), or ethyl butylaniline (e.g., ethyl butylaniline with ethyl at any one of the 2,3, 2,4, or 2,5 positions and the others being butyl), etc. The butyl group further includes n-butyl, tert-butyl, and sec-butyl. It should be noted that the aromatic amine compound (a) in this embodiment can be used alone or in combination of two or more.

[0084] For example, in the case of a chemical structure where the maleimide group is directly bonded to an unsubstituted benzene ring, such as N-phenylmaleimide, the state in which the benzene ring and the 5-membered ring of the maleimide are arranged in the same plane is stable, and therefore easy to stack, exhibiting high crystallinity. This results in poor solvent solubility. In contrast, in the case of this disclosure, for example, where an alkyl group (e.g., ethyl) is used as a substituent for the benzene ring, such as 2-ethylaniline, the steric hindrance of the ethyl group causes the benzene ring and the 5-membered ring of the maleimide to form a distorted conformation, making stacking difficult. Therefore, crystallinity decreases and solvent solubility increases, making this a preferred approach. However, depending on excessive steric hindrance or the substitution position of the alkyl group, the reactivity during the synthesis of maleimide may be hindered, or the curability of the maleimide group may deteriorate when producing a cured product. Therefore, it is preferable to use, for example, an aromatic amine compound having a hydrocarbon group having 1 to 6 carbon atoms (a). It should be noted that in this embodiment, the aromatic amine compound (a) shown in the above formula (a1) can be used alone or in combination of two or more.

[0085] <<Compounds with a benzyl ether skeleton (b)>> The compound (b) having a benzyl ether skeleton in this embodiment can be a monomer or a mixture. When the compound (b) having a benzyl ether skeleton in this embodiment is a monomer, it is preferably a compound having a partial structure shown in formula (b) as described later, more preferably a compound shown in formula (b1) as described later, and even more preferably a compound shown in formula (b2) as described later.

[0086] On the other hand, when the compound (b) having a benzyl ether skeleton in this embodiment is a mixture, it is preferable that it is not only a mixture containing not only compounds having a partial structure shown in formula (b) below and / or compounds having a benzyl ether skeleton shown in formula (b1) below, but also a mixture in which the component having a partial structure shown in formula (b3) below accounts for 95% or more and 100% or less of the total. The compound (b) having a benzyl ether skeleton in this embodiment is preferably a compound having a benzyl ether skeleton shown in formula (b). [Chemical Formula 13] (In equation (b), R) b3 Each independently represents an alkyl group having 1 to 18 carbon atoms, m b2 j represents an integer greater than 0 and less than 4. 1 and j 2 Each is an independent integer greater than 0 and less than 4, j 1 +j 2 ≥1, k1 and k 2 Each atom is either 0 or 1, and * indicates a bond with another atom.

[0087] In this embodiment, the compound (b) having a benzyl ether skeleton is preferably the product obtained by reacting alkylbenzene with formaldehyde under an acid catalyst.

[0088] The compound (b) having a benzyl ether skeleton in this embodiment preferably has the benzyl ether skeleton shown in formula (b) above, and satisfies at least one of the following physical property values. Thus, a resin exhibiting superior solvent solubility, heat resistance, and dielectric properties can be synthesized.

[0089] In this embodiment, the upper limit of the number-average molecular weight (Mn) of the compound (b) having a benzyl ether skeleton is preferably 1200 or less, more preferably 800 or less, and even more preferably 500 or less. The lower limit of the number-average molecular weight (Mn) of the compound (b) having a benzyl ether skeleton is preferably 200 or more, more preferably 240 or more, and even more preferably 250 or more.

[0090] The upper limit of the oxygen content of the compound (b) having a benzyl ether skeleton in this embodiment is preferably 15% by mass or less, more preferably 13% by mass or less, and even more preferably 12% by mass or less. The lower limit of the oxygen content of the compound (b) having a benzyl ether skeleton is preferably 4% by mass or more, more preferably 5% by mass or more, and even more preferably 7% by mass or more.

[0091] In this embodiment, the upper limit of the specific gravity of the compound (b) having a benzyl ether skeleton is preferably less than 1.2, more preferably less than 1.15, and even more preferably less than 1.10. The lower limit of the specific gravity of the compound (b) having a benzyl ether skeleton is preferably 1.0 or more, more preferably 1.01 or more, and even more preferably 1.02 or more.

[0092] The upper limit of the viscosity (75°C) of the compound (b) having a benzyl ether skeleton in this embodiment is preferably 1500 mPa·s or less, more preferably 1000 mPa·s or less, and even more preferably 900 mPa·s or less. The lower limit of the viscosity (75°C) of the compound (b) having a benzyl ether skeleton is preferably 30 mPa·s or more, more preferably 50 mPa·s or more, and even more preferably 70 mPa·s or more.

[0093] The upper limit of the indirect viscosity (at 20°C) of the compound (b) having a benzyl ether skeleton in this embodiment is preferably 1000 mPa·s or less, more preferably 800 mPa·s or less, and even more preferably 500 mPa·s or less. The lower limit of the indirect viscosity (at 20°C) of the compound (b) having a benzyl ether skeleton is preferably 10 mPa·s or more, more preferably 20 mPa·s or more, and even more preferably 30 mPa·s or more. The hydroxyl value of the compound (b) having a benzyl ether skeleton in this embodiment is preferably 16 to 50 (mgKOH / g), more preferably 18 to 40 (mgKOH / g), and even more preferably 22 to 35 (mgKOH / g).

[0094] An example of a compound (b) having a benzyl ether skeleton that is a reactant (1) that is a component of (1A) is preferably a compound having the structural unit shown in the following formula (b1). [Chemical Formula 14] (In the above formula (b1), R) b1 Each can independently represent an alkyl group having 1 to 11 hydrogen atoms or carbon atoms, wherein one or more -CH2- atoms in the alkyl group may be replaced by -O- or -C(=O)- in a non-adjacent manner. R b2 and R b3 Each can independently represent a hydrocarbon group with 1 to 18 carbon atoms. L 1 Each can independently represent an alkylene group having 1 to 11 carbon atoms, wherein one or more -CH2- atoms in the alkylene group can be replaced with -O- atoms in a non-adjacent manner. L 2 This indicates a single bond or an alkylene group having 1 to 11 carbon atoms, wherein one or more -CH2- atoms in the alkylene group may be replaced by -O- or -(C=O)- in a non-adjacent manner. Z 1 Each can independently represent a hydrocarbon group with 1 to 11 hydrogen or carbon atoms. k represents an integer greater than 0 and less than 20. m b1 and m b2 Each can independently represent an integer greater than 0 and less than 4. R b1 or L 2 At least one of them has a -CH2O- group.

[0095] R in the above formula (b1) b1Preferably, it represents a hydrocarbon group having 1 to 11 hydrogen atoms or carbon atoms; more preferably, it represents a hydrocarbon group having 1 to 9 hydrogen atoms or carbon atoms. One or more -CH2- atoms in this hydrocarbon group may also be replaced with -O- atoms in a non-adjacent manner. Preferred R b1 Preferably, it is selected from hydrogen atom, alkyl group having 1 to 9 carbon atoms, alkoxy group having 1 to 9 carbon atoms, hydroxyalkyl group having 1 to 9 carbon atoms, and -(CH2O). p1 -C(=O)-R b4 -(CH2O) p1 -R b4 -(CH2O) p1 -(CH2) p2 -R b4 -(CH2) p3 -(CH2O) p1 -(CH2) p2 -R b4 -(OCH2) q1 -R b4 -(OCH2) q1 -(CH2) q2 -R b4 and -(CH2) q3 -(OCH2) q1 -(CH2) q2 -R b4 One of them. Here, the aforementioned R... b4 It represents an alkyl group having 1 to 5 hydrogen atoms or carbon atoms. In addition, p1 to p3 and q1 to q3 above preferably each independently represent an integer from 1 to 11, more preferably an integer from 1 to 6, even more preferably an integer from 1 to 3, and particularly preferably an integer from 1 to 2.

[0096] Furthermore, R is preferred. b1 or L 2 At least one of them has a -CH2O- group, more preferably R b1 and L 2 Both have the -CH2O- group.

[0097] R in equation (b1) b2 and R b3 Each can independently correspond to R in equation (1) above. 13 Therefore, R in equation (b1) above b2 and R b3 Each alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, and even more preferably an alkyl group having 1 to 6 carbon atoms. Additionally, in m... b1 When the integer is 2 or more, there are more than 2 R's. b2They can be the same as each other, or they can be different groups. Similarly, in m b2 When the integer is 2 or more, there are more than 2 R's. b3 They can be the same as each other, or they can be different groups.

[0098] In the above formula (b1), L 1 Each alkylene group is preferably represented by an alkylene group having 1 to 11 carbon atoms, and more preferably by an alkylene group having 1 to 9 carbon atoms. One or more of the -CH2- atoms in this alkylene group may also be replaced with -O- atoms in a non-adjacent manner. Specifically, L 1 Preferably, it is selected from alkylene groups having 1 to 11 carbon atoms, alkylene oxide groups having 1 to 11 carbon atoms, and -(CH2O). p1 -C(=O)-R b4 -(CH2O) p1 -R b4 -(CH2O) p1 -(CH2) p2 -、-(CH2) p3 -(CH2O) p1 -(CH2) p2 -、-(OCH2) q1 -、-(OCH2) q1 -(CH2) q2 -and-(CH2) q3 -(OCH2) q1 -(CH2) q2 - One of them. In addition, p1 to p3 and q1 to q3 above each preferably represent an integer from 1 to 11, more preferably an integer from 1 to 6, even more preferably an integer from 1 to 3, and particularly preferably an integer from 1 to 2.

[0099] In the above equation (b1), L 2 Preferably, each alkylene group independently represents a single bond or has 1 to 11 carbon atoms; more preferably, it represents a single bond or has 1 to 9 carbon atoms, wherein one or more -CH2- atoms in the alkylene group can be replaced with -O- atoms in a non-adjacent manner. Specifically, L 2 Preferably, it is selected from single bonds, alkylene groups having 1 to 11 carbon atoms, alkylene oxide groups having 1 to 11 carbon atoms, and -(CH2O). p1 -C(=O)-、-(CH2O) p1 -、-(CH2O) p1 -(CH2) p2 -、-(CH2) p3 -(CH2O) p1 -(CH2) p2 -、-(OCH2) q1-、-(OCH2) q1 -(CH2) q2 -and-(CH2) q3 -(OCH2) q1 -(CH2) q2 - One of them. In addition, p1 to p3 and q1 to q3 mentioned above preferably each independently represent an integer from 1 to 11, more preferably an integer from 1 to 6, even more preferably an integer from 1 to 3, and particularly preferably an integer from 1 to 2.

[0100] Furthermore, R is preferred. b1 or L 2 At least one of them has a -CH2O- group, more preferably R b1 and L 2 Both have the -CH2O- group.

[0101] Z in the above formula (b1) 1 Preferably, it represents an alkyl group having 1 to 11 hydrogen atoms or carbon atoms; more preferably, it represents an alkyl group having 1 to 9 hydrogen atoms or carbon atoms.

[0102] In the above formula (b1), k is preferably an integer from 0 to 20, more preferably an integer from 0 to 15, and even more preferably an integer from 0 to 10. It should be noted that when k is 2 or more, multiple existing L... 1 They can be the same groups or different groups.

[0103] As a preferred embodiment of the compound (b) having a benzyl ether skeleton, it may be a compound having the structural unit shown in formula (b2). [Chemical Formula 15] (In equation (b2), R) b1 Each can independently represent an alkyl group having 1 to 11 hydrogen atoms or carbon atoms, wherein one or more -CH2- atoms in the alkyl group may be replaced by -O- or -C(=O)- in a non-adjacent manner. R b2 and R b3 Each can independently represent an alkyl group having 1 to 18 carbon atoms. L 1 Each can independently represent an alkylene group having 1 to 11 carbon atoms, wherein one or more -CH2- atoms in the alkylene group can be replaced with -O- atoms in a non-adjacent manner. L 2 This indicates a single bond or an alkylene group having 1 to 11 carbon atoms, wherein one or more -CH2- atoms in the alkylene group may be replaced by -O- or -(C=O)- in a non-adjacent manner. Z 1Each can independently represent an alkyl group having 1 to 11 hydrogen atoms or carbon atoms. k represents an integer greater than 0 and less than 20. m b1 and m b2 Each can independently represent an integer greater than 0 and less than 4. R b1 or L 2 At least one of them has a -CH2O- group.

[0104] In the above equation (b2), R b1 R b2 and R b3 L 1 L 2 Z 1 , k and m b1 and m b2 The preferred method is the same as that in equation (b1) above.

[0105] The compound (b) having a benzyl ether skeleton in this embodiment can be used alone, or in combination of two or more compounds. Alternatively, it can be a mixture containing two or more compounds (b) having different benzyl ether skeletons. It should be noted that, for ease of explanation, in this specification, the term "compound (b) having a benzyl ether skeleton" refers to a mixture containing two or more compounds (b) having different benzyl ether skeletons as a mixture (b) having a benzyl ether skeleton. Therefore, "compound (b) having a benzyl ether skeleton" can refer not only to a single compound but also to a mixture (b) having a benzyl ether skeleton.

[0106] For the mixture (b) having a benzyl ether skeleton in this embodiment, it is preferable that the component having the partial structure shown in the following formula (b3) accounts for more than 95% by mass and less than 100% by mass of the mixture (b) having a benzyl ether skeleton. [Chemical Formula 16] (In formula (b3), L) 3 and L 4 Each of the following groups is a linking group, and each group is independently selected from -CH2-, -CH2O-CH2-, -(CH2O)2-CH2-, and -(CH2O)3-CH2-. * indicates a bond with other atoms.

[0107] The mixture (b) having a benzyl ether skeleton in this embodiment preferably has a component having a partial structure shown in the above formula (b3) accounting for 95% or more and 100% or less of the total mixture (b) having a benzyl ether skeleton, and satisfies the following requirements (I) or (II). (I) The number of linking groups (L) per molecule of the component having the partial structure shown in formula (b3) above. 3 and L 4 The total (of which) is between 1.1 and 2.4. (II) The number of terminal groups attached to the ends of molecules constituting the components having the partial structure shown in formula (b3) above is 0.5 or more and 1.5 or less for each of the above molecules.

[0108] In this embodiment, the linking group (L) of the molecule constituting a component having a partial structure as shown in formula (b3) above... 3 and L 4 One group selected from -CH2-, -CH2O-CH2-, -(CH2O)2-CH2- and -(CH2O)3-CH2- can be cited as an example.

[0109] In the mixture (b) as a whole having a benzyl ether skeleton, each molecule having the benzyl ether skeleton shown in formula (b3) above has the following linking group (L 3 and L 4 The quantity of the total number is preferably composed of the following (1) to (4). (1) The number of the linking group "-CH2-" is preferably 0.65 or more and 1.4 or less. (2) The number of the linking group "-CH2O-CH2-" is preferably 0.07 or more and 0.2 or less, more preferably 0.08 or more and 0.14 or less. (3) The number of the linking group "-(CH2O)2-CH2-" is preferably 0.10 or more and 0.8 or less, more preferably 0.2 or more and 0.8 or less. In other cases, it is preferably more than 0.41 and less than 0.8. (4) The number of the linking group "-(CH2O)3-CH2-" is preferably 0.05 or more and 0.65 or less, preferably 0.09 or more and 0.6 or less, and more preferably 0.10 or more and 0.55 or less.

[0110] In the mixture (b) having a benzyl ether skeleton in this embodiment, it is preferable to have one or more groups selected from -CH2-OH, -CH2O-CH3, -(CH2O)2-CH3, -(CH2O)3-CH3 and -(CH2O)-COH as terminal groups that combine with the end of the molecule constituting the component having the partial structure shown in the above formula (b3).

[0111] Furthermore, in the mixture (b) having a benzyl ether skeleton as a whole, it is preferable to have a benzyl ether skeleton as shown in the above formula (b3), and the number of terminal groups in each molecule is 0.5 or more and 1.5 or less. In the mixture (b) having a benzyl ether skeleton as a whole, the number of the following terminal groups in each molecule having a benzyl ether skeleton is preferably composed of the following (5) to (9). (5) The number of terminal groups "-CH2-OH" is preferably 0.17 or more and 0.4 or less, more preferably 0.18 or more and 0.25 or less. (6) The number of terminal groups “-CH2O-CH3” is preferably 0.17 or more and 0.7 or less, more preferably 0.18 or more and 0.44 or less. (7) The number of terminal groups “-(CH2O)2-CH3” is preferably 0.08 or more and 0.6 or less, and more preferably 0.09 or more and 0.3 or less. (8) The number of terminal groups "-(CH2O)3-CH3" is preferably substantially non-existent, more preferably 0.3 or less, and even more preferably 0.2 or less. (9) The number of terminal groups "-(CH2O)-COH" is preferably 0 or more and 0.1 or less, more preferably 0.01 or more and 0.1 or less.

[0112] In the mixture (b) having a benzyl ether skeleton in this embodiment, the chemical structure and number of the linking groups, and the chemical structure and number of the terminal groups, as shown in the column of the examples described later, can be calculated based on NMR or referred to the manufacturer's product catalog.

[0113] In this embodiment, the compound (b) having a benzyl ether skeleton can be either a synthetic product or a commercially available product. As a commercially available compound (b) having a benzyl ether skeleton, xylene resin (trade name: NIKANOL (Y-50, Y-100, Y-300, Y-1000, LLL, LL, L or H) manufactured by Fudow Corporation is preferred.

[0114] In this embodiment, relative to the total amount (100% by mass) of component (1A), the structural unit of compound (b) having a benzyl ether skeleton preferably contains 1 to 99% by mass, more preferably 5 to 95% by mass. The structural unit of compound (b) having a benzyl ether skeleton refers to the group shown in formula (1) above.

[0115] <<Malic anhydride>> In this embodiment, maleic anhydride is included in the reaction raw material (1) of component (1A), as described later, for the reaction of maleimidizing the amino group from the aromatic amine compound (a).

[0116] As a specific method of manufacturing component (1A), an example of a manufacturing method includes the following steps (1) and (2). Step (1): As a reaction raw material (2), the aromatic amine compound (a) shown in the above formula (a1) is reacted with a compound (b) having a benzyl ether skeleton to obtain the intermediate amine compound (c) in this embodiment. Step (2): The process of reacting the intermediate amine compound (c) obtained in step (1) with maleic anhydride as a reaction raw material (3) to obtain component (1A).

[0117] Specifically, the preferred method for manufacturing component (1A) includes: a step (1) (also called a "crosslinking step") in which an aromatic amine compound (a) of formula (a1) shown above is reacted with a compound (b) having a benzyl ether skeleton under a solid acid catalyst; and a step (2) (also called a "condensation step") in which an intermediate amine compound (c) generated by step (1) is condensed with maleic anhydride. The steps of the method for manufacturing component (1A) will be described in turn below.

[0118] <Process (1): Manufacturing process of intermediate amine compound (c)>> The manufacturing process of the intermediate amine compound (c) in this embodiment will be described below. Step (1) is a process of reacting the above-mentioned aromatic amine compound (a), the above-mentioned compound (b) having a benzyl ether skeleton (e.g., NIKANOL), and other compounds added as needed in the presence of an acid catalyst. As a result, the intermediate amine compound (c) can be generated.

[0119] As for the mixing ratio of the aromatic amine compound (a) and the compound (b) having the benzyl ether skeleton, considering the balance of formability and curability during the manufacture of the resulting cured product, the molar ratio of the compound (b) having the benzyl ether skeleton to 1 mole of the aromatic amine compound (a) is preferably 0.001 to 1 mole, more preferably 0.1 to 0.5 moles.

[0120] Furthermore, when using a mixture of the aforementioned mixture (b) having a benzyl ether skeleton as the compound (b) having a benzyl ether skeleton, the reaction site (reactive site) with the aromatic amine compound (a) can be the methylene oxide portion (e.g., benzyl ether portion (Ph-CH2O-CH2-), benzyl alcohol portion (Ph-CH2O-H), or methylene oxide portion (-CH2-O-)) of the compound (b) having a benzyl ether skeleton contained in the mixture. Additionally, when the total number of these reaction sites is set to 1, the amount of aromatic amine compound (a) is preferably equal to or greater than 10 times, for example, the amount of aromatic amine compound (a) is preferably 1 to 10 moles relative to the total number of the aforementioned reaction sites of 1 mole.

[0121] Furthermore, as a specific method for carrying out the above reaction, all raw materials are usually added together and the reaction is carried out directly at a specified temperature. Alternatively, one of the aromatic amine compound (a) or the compound having a benzyl ether skeleton (b) and an acid catalyst are added, and the other of the aromatic amine compound (a) or the compound having a benzyl ether skeleton (b) is added dropwise while maintaining the specified temperature, and the reaction is carried out simultaneously. In this case, the dropwise addition time is usually 0.1 to 12 hours, preferably 6 hours or less. After the reaction, if a solvent is used, the solvent and unreacted substances are removed by distillation as needed to obtain the above-mentioned intermediate amine compound (c). If no solvent is used, the above-mentioned intermediate amine compound (c), which is the target substance, can be obtained by removing the unreacted substances by distillation.

[0122] As the acid catalyst used in step (1) of this embodiment, any one of organic acid, inorganic acid, or solid acid can be used. Examples of organic acids include: aliphatic sulfonic acids such as methanesulfonic acid or fluoromethanesulfonic acid; aromatic sulfonic acids such as 3-morpholine propanesulfonic acid, piperazine-1,4-bis(2-ethanesulfonic acid), 10-camphorsulfonic acid, 4-chlorobenzenesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, or trifluoromethanesulfonic acid; alkyl phosphoric acids such as dimethyl phosphate or diethyl phosphate; alkyl sulfuric acids such as dimethyl sulfate, diethyl sulfate, and lauryl sulfate; aromatic sulfuric acids such as phenyl sulfate and phenyl fluorosulfate; and various acids such as oxalic acid. Examples of inorganic acids include phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid, or boric acid. Examples of solid acids include activated clay, acidic clay, alumina, silica alumina, zeolite, layered silicates, heteropoly acids, or strong acidic ion exchange resins. Examples of layered silicates include: dickite, nacrite, kaolinite, silica-rich kaolinite, metahalloysite, halloysite, and other kaolinite groups; chrysotile, lizardite, antigorite, and other serpentine groups; montmorillonite, sauconite, beidellite, and nontronite. Saponite, taeniolite, hectorite, stevensite, and other smectite group minerals; vermiculite and other vermiculite group minerals; mica, illite, sericite, glauconite, and other mica group minerals; and attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, and chlorite group minerals. These layered silicates can also form mixed layers. In addition, the above-mentioned acid catalysts can be used alone or in combination of two or more. After the reaction in the above-mentioned step (1), from the viewpoint of processability, it is also preferable to have a solid acid that can be easily removed by filtration. When using other acids, it is preferable to perform neutralization with alkali and washing with water after the reaction.

[0123] It should be noted that there are no particular limitations on the aforementioned bases; they can be organic or inorganic bases. Examples of such organic bases include: alkali metal alkoxides such as sodium methoxide, lithium methoxide, sodium ethoxide, lithium ethoxide, sodium tert-butoxide, and potassium tert-butoxide; trialkylamines such as triethylamine and ethyl diisopropylamine; aniline derivatives such as N,N-dimethylaniline and N,N-diethylaniline having alkyl groups with 1 to 4 carbon atoms; pyridine derivatives such as pyridine and 2,6-dimethylpyridine having optional alkyl substituents with 1 to 4 carbon atoms; and nitrogen-containing heterocyclic compounds such as 1,8-diazabicyclo[5.4.0]-7-undecene. On the other hand, examples of the aforementioned inorganic bases include: alkali metal hydrides such as sodium hydride and lithium hydride; alkaline earth metal hydrides such as calcium hydride; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; carbonates or bicarbonates of alkali metals or alkaline earth metals such as sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate; and halides of alkali metals or alkaline earth metals such as potassium fluoride, cesium fluoride, and potassium iodide. These bases can be used individually or in combination of two or more.

[0124] In this embodiment, the amount of acid catalyst is in the range of 0.1 to 50 parts by mass relative to 100 parts by mass of the total amount of raw materials (compound (b) having a benzyl ether skeleton and aromatic amine compound (a)). However, from the viewpoint of processability and economy, a range of 1 to 20 parts by mass is preferred. The reaction temperature is usually in the range of 100 to 300°C, but in order to suppress the formation of isomer structures and avoid side reactions such as thermal decomposition, a range of 120 to 250°C is preferred.

[0125] In step (1) of this embodiment, the reaction time of the mixture of compound (b) having a benzyl ether skeleton and aromatic amine compound (a), that is, the crosslinking reaction time, is such that if the reaction is short, the reaction will not proceed completely, and if it is long, side reactions such as thermal decomposition of the product will occur. Therefore, under the above reaction temperature conditions, it is usually in the range of 1 to 60 hours, preferably in the range of 1 to 20 hours.

[0126] In the method for producing the intermediate amine compound (c) in this embodiment, since the aromatic amine compound (a) or its derivative also serves as a solvent, it is not necessary to use other solvents, but a solvent can still be used. For example, as a compound (b) having a benzyl ether skeleton, when NIKANOL L is used as a starting material for the reaction, a solvent that can azeotropically dehydrate, such as toluene, xylene, or chlorobenzene, can be used. The water contained in the catalyst, etc., is azeotropically dehydrated as needed, the solvent is removed by distillation, and then the reaction is carried out within the aforementioned reaction temperature range.

[0127] The intermediate amine compound (c) obtained by the above process (1) preferably has: a partial structure shown in formula (1) below, a partial structure shown in formula (t-1) that is chemically bonded to the partial structure shown in formula (1) above, and a partial structure shown in formula (t-2) that is chemically bonded to the partial structure shown in formula (1) above. [Chemical Formula 17] (In equation (1), R) a1 R a2 R a3 and R a4 Each can independently represent a hydrogen atom or a hydrocarbon group with 1 to 18 carbon atoms. R 13 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. 2 Each represents an integer from 0 to 4 independently, n 1 Indicates the number of repeating units. The two "*" symbols represent connecting keys, indicating that a connecting key is in the following equation (t-1) L. 13 or L 14 One bond is chemically bonded at one position, and the other bond is at L in the following formula (t-2). 11 or L 12 Chemical bonding occurs at specific positions. [Chemical Formula 18] (In the above equations (t-1) and (t-2), R) 11 and R 15 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. R 12 and R 14 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. L 11 L 12 L 13 and L 14 Each represents a connection key independently. Specifically, in L... 11 or L 12 The position is chemically bonded to the partial structure shown in equation (1), and in L 13 or L 14 The position is chemically bonded to the partial structure shown in formula (1). m 1 and m 3 Each can independently represent an integer from 0 to 2.

[0128] The intermediate amine compound (c) involves R in formula (1) a1 R a2 R a3 and R a4 R 13 m 2 and n1 R in equation (1) related to component (1A) a1 R a2 R a3 and R a4 R 13 m 2 and n 1 same.

[0129] R in equations (t-1) and (t-2) 11 and R 15 R 12 and R 14 L 11 L 12 L 13 and L 14 m 1 and m 3 R in equations (T-1) and (T-2) 11 and R 15 R 12 and R 14 L 11 L 12 L 13 and L 14 m 1 and m 3 same.

[0130] In this embodiment, the amine equivalent of the intermediate amine compound (c) is preferably 160 to 1200 g / equivalent, more preferably 180 to 600 g / equivalent. It should be noted that the determination of the amine equivalent of the intermediate amine compound (c) in this specification is based on the neutralization titration method specified in JIS K0070 (1992).

[0131] <Process (2): Maleimide>> Step (2) in this embodiment is a step of reacting the intermediate amine compound (c) obtained in step (1) with maleic anhydride. The amino group of the intermediate amine compound (c) can be replaced by a maleimide reaction to form a chemical structure in which the amino group is replaced by an N-substituted maleimide ring, thus obtaining the maleimide compound of this disclosure.

[0132] In this embodiment, the intermediate amine compound (c) having the partial structures shown in formula (1), formula (t-1), and formula (t-2) obtained by step (1) is added to a reactor, dissolved in a suitable solvent, and reacted with maleic anhydride in the presence of a catalyst. After the reaction, unreacted maleic anhydride or other impurities are removed by washing with water, and the solvent is removed by reducing pressure, thereby obtaining the maleimide compound as the target. Alternatively, a dehydrating agent may be used during the reaction if necessary.

[0133] Examples of organic solvents used in step (2) of this embodiment include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, and acetophenone; and nonprotic solvents such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, and sulfolane. Cyclic ethers such as alkanes and tetrahydrofurans, esters such as ethyl acetate and butyl acetate, and aromatic solvents such as benzene, toluene, and xylene can be used alone or in combination.

[0134] In step (2) of this embodiment, the mixing ratio of the intermediate amine compound (c) and maleic anhydride is preferably a ratio of maleic anhydride to the amino equivalent of the intermediate amine compound (c) in the range of 1 to 5, more preferably 1 to 3. The reaction is preferably carried out in an organic solvent with a mass ratio of 0.1 to 10, more preferably 0.2 to 5, relative to the total mass of the intermediate amine compound (c) and maleic anhydride.

[0135] Examples of catalysts that can be used in step (2) of this embodiment include acetates of nickel, cobalt, sodium, calcium, iron, lithium, manganese, etc.; inorganic salts such as chlorides, bromides, sulfates, nitrates, etc.; inorganic acids such as phosphoric acid, hydrochloric acid, sulfuric acid, etc.; organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, fluoromethanesulfonic acid, etc.; solid acids such as activated clay, acid clay, silica alumina, zeolite, strong acid ion exchange resin, etc.; heteropoly acids, etc. Toluenesulfonic acid is preferred, and p-toluenesulfonic acid is more preferred.

[0136] Examples of dehydrating agents used in step (2) of this embodiment include lower aliphatic carboxylic anhydrides such as acetic anhydride, propionic anhydride, and butyric anhydride; oxides such as phosphorus pentoxide, calcium oxide, and barium oxide; inorganic acids such as sulfuric acid; and porous ceramics such as molecular sieves. However, acetic anhydride is preferred. There are no particular restrictions on the amount of catalyst and dehydrating agent used in step (2) of this embodiment. Generally, relative to the amino (-NH2)1 equivalent of the intermediate amine compound (c), the catalyst can be used in amounts of 0.0001 to 1 mole, preferably 0.01 to 0.3 moles, and the dehydrating agent can be used in amounts of 1 to 3 moles, preferably 1 to 1.5 moles.

[0137] In step (2) of this embodiment, as the reaction conditions for maleimide formation, the above-mentioned intermediate amine compound (c) and maleic anhydride can be added and reacted at a temperature range of 10 to 100°C, preferably 30 to 60°C, for 0.5 to 12 hours, preferably 1 to 4 hours. Then, the above-mentioned catalyst is added and reacted at a temperature range of 90 to 130°C, preferably 105 to 120°C, for 1 to 24 hours, preferably 1 to 10 hours.

[0138] <(1A) Second manufacturing method relating to maleimide compounds having a first specific structure> In another embodiment (second manufacturing method), component (1A) may be, for example, a component that makes... (x1-1) alkyl-substituted aniline compounds, and (x1-2) optionally substituent-containing divinylbenzene compounds. The maleimide of the intermediate amine compound (x1) obtained by the reaction. According to the second manufacturing method, n in formula (1) can be manufactured. 1 The (1A) component is 1.

[0139] When obtaining the intermediate amine compound (x1), in addition to the components (x1-1) and (x1-2) mentioned above, (x1-3) can be further reacted with a monovinylbenzene compound having substituents.

[0140] Therefore, in another embodiment, component (1A) is an aniline compound in which (x1-1) is alkyl-substituted. (x1-2) optional divinylbenzene compounds having substituents, and (x1-3) optional monovinylbenzene compounds having substituents. The maleimide of the intermediate amine compound (x1) obtained by the reaction.

[0141] <<(x1-1) Alkyl-substituted aniline compounds>> The component (x1-1) is an alkyl-substituted aniline compound, represented by the formula (x1-1).

[0142] [Chemical Formula 19] (In formula (x1-1), R) 11 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. R 12 This indicates a hydrocarbon group with 1 to 18 carbon atoms. 1 Each can independently represent an integer from 0 to 2.

[0143] R in equation (x1-1) 11 R 12 and m 1 R in equation (T-2) 11 R 12 and m 1 The same applies. As for component (x1-1), the structure can be appropriately determined to achieve the target structure of component (1A). It should be noted that, from the viewpoint that component (1A) can be successfully synthesized in combination with components (x1-2) or (x1-3), it is preferable that at least one carbon atom at positions 2, 4, and 6 of the benzene ring of component (x1-1) is unsubstituted. Specific examples of component (x1-1) include, for instance, 2-ethylaniline.

[0144] <<(x1-2)Optional divinylbenzene compounds with substituents>> (x1-2) is a divinylbenzene compound with optional substituents, represented by the following formula (x1-2).

[0145] [Chemical Formula 20] (In formula (x1-2), R) 13 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. 2 (Represents integers from 0 to 4.)

[0146] R in equation (x1-2) 13 and m 2 R in equation (1) 13 and m 2 Same. As a component of (x1-2), the structure of the (1A) component, in order to achieve the target, can be appropriately determined. m in the (1A) component as the target 2 When the value is 0, divinylbenzene can be used.

[0147] <(x1-3)Optional monovinylbenzene compounds with substituents> (x1-3) are optional monovinylbenzene compounds with substituents, represented by the following formula (x1-3).

[0148] [Chemical Formula 21] (In formula (x1-3), R) 16 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. 4 Represents integers from 0 to 5.

[0149] R in equation (x1-3) 16 and m 4 R in equation (4) 16 and m 4 Same. As a component of (x1-3), the structure of the (1A) component, in order to achieve the target, can be appropriately determined. m in the (1A) component as the target 4 When the value is 0, monovinylbenzene can be used. Specific examples of (x1-3) components include, for example, ethyl styrene.

[0150] The aforementioned components (x1-1) and (x1-2), and further (x1-3) if necessary, are reacted in the presence of an acid catalyst to yield the intermediate amine compound (x1). In this reaction, the vinyl group of component (x1-2) or (x1-3) generates a carbocation in the presence of an acid catalyst, which reacts with and combines with the unsubstituted carbon of the benzene ring of component (x1-1).

[0151] Regarding the mixing ratio of components (x1-1) and (x1-2), from the viewpoint of component (1A) which, in combination with components (B) and (C), can produce a cured product that simultaneously exhibits superior stain removal and higher adhesion strength, it is preferable to use 0.1 to 10 moles of component (x1-1), more preferably 0.2 to 3 moles of component (x1-2), relative to 1 mole of component (x1-1). Furthermore, when component (x1-3) is used in combination, it is preferable to use 0.1 to 10 moles of component (x1-1), more preferably 0.2 to 3 moles of component (x1-3), relative to 1 mole of component (x1-1).

[0152] The reaction can be carried out in a solvent-free system or in an organic solvent system. Examples of organic solvents used in the reaction include aromatic hydrocarbon solvents such as toluene and xylene; halogenated aromatic hydrocarbon solvents such as chlorobenzene; and ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. One organic solvent can be used alone, or two or more can be used in combination.

[0153] Examples of acid catalysts used in reactions include inorganic acids such as phosphoric acid, hydrochloric acid, and sulfuric acid; organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and fluoromethanesulfonic acid; and solid acids and heteropoly acids such as activated clay, acid clay, silica alumina, zeolite, and strongly acidic ion exchange resins.

[0154] As long as the reaction proceeds, the reaction temperature is not particularly limited, for example, it can be in the range of 100 to 250°C. In addition, the reaction time is not particularly limited as long as the structure of the target intermediate amine compound (x1) is achieved, for example, it can be in the range of 30 minutes to 48 hours.

[0155] The intermediate amine compound (x1) can also be purified after the reaction. For example, after the reaction, purification steps such as filtration and distillation can be performed to remove the catalyst or excess starting material from the system.

[0156] Thus, intermediate amine compounds with the structure shown in the following formula (x1) can be obtained.

[0157] [Chemical Formula 22] [Chemical Formula 23] In equations (x1), (4), and (x1-5), R a1 R a2 R a3 R a4 R a5 and R a6 Each can independently represent a hydrogen atom or a hydrocarbon group with 1 to 18 carbon atoms. R 11 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. R 12 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. R 13 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. R 16 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. 1 Each represents an integer from 0 to 2 independently, m 6 Each represents an integer from 0 to 2 independently, m 5 Each element independently represents an integer from 0 to 3, satisfying m 1 +m 6 ≤2 and m 1 +m 5 ≤3. m 2 Each represents an integer from 0 to 4 independently, m 4 Each represents an integer from 0 to 5 independently, n 1 Each element independently represents the number of repeating units, and each of n independently represents an integer greater than 1. X M1 X represents a hydrogen atom or a monovalent group as shown in formula (4). M2 This represents a hydrogen atom or a monovalent group as shown in formula (5). * indicates a connection key.

[0158] Next, the obtained intermediate amine compound (x1) is reacted with maleic anhydride to undergo maleimide reaction, yielding component (1A).

[0159] The reaction of component (x1) with maleic anhydride can be carried out by maleimide reaction of the amino group of maleic anhydride, which is known in the past. The reaction can be carried out in a solvent-free system without the use of a solvent, or in an organic solvent system using an organic solvent. The type of organic solvent that can be used is related to the reactions of components (x1-1), (x1-2), and (x1-3), as described above.

[0160] As long as the reaction proceeds, the reaction temperature is not particularly limited, and can be in the range of 0 to 100°C. Furthermore, the reaction time is not particularly limited as long as the structure of the target component (1A) is achieved, and can be in the range of 1 to 24 hours. After the reaction, purification processes such as water washing or fine filtration can be performed.

[0161] The reaction can be carried out in the presence of a catalyst, such as acetates of nickel, cobalt, sodium, calcium, iron, lithium, manganese, etc.; inorganic salts such as chlorides, bromides, sulfates, nitrates, etc.; inorganic acids such as phosphoric acid, hydrochloric acid, sulfuric acid, etc.; organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, fluoromethanesulfonic acid, etc.; solid acids such as activated clay, acid clay, silica alumina, zeolite, strong acid ion exchange resin, etc.; heteropoly acids, etc. Toluenesulfonic acid is preferred, and p-toluenesulfonic acid is more preferred.

[0162] Regarding the ratio of intermediate amine compound (x1) to maleic anhydride, from the viewpoint that the combination with components (B) and (C) can result in a cured product that simultaneously exhibits superior stain removal and higher adhesion strength, component (1A) is preferably formulated with an equivalent ratio of maleic anhydride to the amino equivalent of intermediate amine compound (x1) in the range of 1 to 5.

[0163] <(B) Epoxy Resin> The resin composition layer of the resin sheet according to the first embodiment of the present invention contains (B) epoxy resin. (B) epoxy resin can be used alone or in combination of two or more types. In one embodiment, (B) epoxy resin is preferably used in combination of two or more types, more preferably in combination of three or more types.

[0164] (B) The type of epoxy resin is not particularly limited as long as it has one or more (preferably two or more) epoxy groups in one molecule. Examples of epoxy resins (B) include, for example, xylenol-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol C-type epoxy resin, bisphenol S-type epoxy resin, bisphenol AF-type epoxy resin, dicyclopentadiene-type epoxy resin, triphenol-type epoxy resin, naphthol phenolic varnish-type epoxy resin, phenol phenolic varnish-type epoxy resin, tert-butyl-catechol-type epoxy resin, naphthol-type epoxy resin, anthracene-type epoxy resin, glycidylamine-type epoxy resin, glycidyl ester-type epoxy resin, cresol phenolic varnish-type epoxy resin, phenol aralkyl-type epoxy resin, biphenyl-type epoxy resin, and biphenyl aralkyl-type epoxy resin. The epoxy resins include esters, linear aliphatic epoxy resins, epoxy resins with a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, epoxy resins containing spirocyclic rings, cyclohexane-type epoxy resins, cyclohexane-diethanol-type epoxy resins, naphthyl ether-type epoxy resins, trimethylolpropionic acid epoxy resins, tetraphenylethane-type epoxy resins, isocyanurate-type epoxy resins, phenolphthalimidine-type epoxy resins, Glycirol-type epoxy resins, epoxy resins containing an alkylene oxide backbone, epoxy resins containing a fluorene structure, halogenated epoxy resins, and resorcinol-type epoxy resins. Bisphenol A-type epoxy resins, bisphenol C-type epoxy resins, naphthyl-type epoxy resins, or biphenyl-type epoxy resins are preferred; more preferably, bisphenol C-type epoxy resins, naphthyl-type epoxy resins, or biphenyl-type epoxy resins are preferred; and even more preferably, naphthyl-type epoxy resins or biphenyl-type epoxy resins are preferred. In one embodiment, component (B) preferably comprises an epoxy resin having an aromatic backbone.

[0165] In the resin composition layer of the resin sheet according to the first embodiment of the present invention, component (B) preferably includes an epoxy resin having two or more epoxy groups per molecule. From the viewpoint of significantly obtaining the desired effect of the present invention, the proportion of epoxy resin having two or more epoxy groups per molecule relative to 100% by mass of epoxy resin (B) is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

[0166] (B) The epoxy resins include epoxy resins that are liquid at 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at 20°C (hereinafter sometimes referred to as "solid epoxy resins"). In the resin composition of the present invention, component (B) may contain only liquid epoxy resin, only solid epoxy resin, or a combination of both. In one embodiment, the resin composition of the present invention preferably contains a combination of liquid epoxy resin and solid epoxy resin.

[0167] As a liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferred.

[0168] Examples of liquid epoxy resins include, for instance, Glycirol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidylamine type epoxy resins, phenolic varnish type epoxy resins, alicyclic epoxy resins with an ester backbone, cyclohexanediol type epoxy resins, cyclic aliphatic glycidyl ethers, epoxy resins with a butadiene structure, dicyclopentadiene type epoxy resins, epoxy resins containing an alkylene oxide backbone, epoxy resins containing a fluorene structure, and resorcinol type epoxy resins. Bisphenol A type resins or naphthalene type epoxy resins are preferred, and naphthalene type epoxy resins are more preferred.

[0169] Specific examples of liquid epoxy resins include: Nagase ChemteX's "EX-992L", Mitsubishi Chemical's "YX7400", DIC's "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resin); Mitsubishi Chemical's "828US", "jER828EL", "828EL", "825", "EPIKOTE 828EL", and DIC's "850S" (bisphenol A type epoxy resin); Mitsubishi Chemical's "jER807" and "1750" (bisphenol F type epoxy resin); Mitsubishi Chemical's "YL9133" (bisphenol C type epoxy resin); Mitsubishi Chemical's "jER152" (phenolic varnish type epoxy resin); and Mitsubishi Chemical's "630", "630LSD", and "604" (glycidylamine type epoxy resin). (Glycirol) epoxy resins; ADEKA's "ED-523T" (Glycirol type epoxy resin); ADEKA's "EP-3950L" and "EP-3980S" (glycidylamine type epoxy resin); ADEKA's "EP-4088S" (dicyclopentadiene type epoxy resin); Nippon Steel Chemical Materials Co., Ltd.'s "ZX-1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); Nagase The following epoxy resins are available: ChemteX's "EX-721" (glycidyl ester type epoxy resin); Nagase ChemteX's "EX-991L" (epoxy resin containing an alkylene oxide backbone); Daicel's "CELLOXIDE 2021P" (alicyclohexane epoxy resin with an ester backbone); Daicel's "PB-3600"; Nippon Soda's "JP-100" and "JP-200" (epoxy resins with butadiene structures); Nippon Steel Chemical Materials' "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin); Osaka Gas Chemical's "EG-280" (epoxy resin containing a fluorene structure); and Nagase ChemteX's "EX-201" (resorcinol type epoxy resin). These can be used individually or in combination of two or more.

[0170] As a solid epoxy resin, a solid epoxy resin having two or more epoxy groups in one molecule is preferred, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferred.

[0171] As a solid epoxy resin, the preferred types are xylenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, naphthol phenolic varnish-type epoxy resin, cresol phenolic varnish-type epoxy resin, dicyclopentadiene-type epoxy resin, triphenol-type epoxy resin, naphthol-type epoxy resin, biphenyl-type epoxy resin, biphenyl aralkyl-type epoxy resin, naphthalene ether-type epoxy resin, anthracene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol AF-type epoxy resin, phenol aralkyl-type epoxy resin, tetraphenylethane-type epoxy resin, phenol benzopyrrolidone-type epoxy resin, and epoxy resin containing a fluorene structure, etc., preferably biphenyl aralkyl-type epoxy resin or biphenyl-type epoxy resin, and more preferably biphenyl-type epoxy resin.

[0172] Specific examples of solid epoxy resins include: DIC's "HP4032H" (naphthalene-type epoxy resin); DIC's "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resins); DIC's "N-690" and "N-695" (cresol phenolic varnish type epoxy resins); DIC's "HP-7200," "HP-7200HH," "HP-7200H," and "HP-7200L" (dicyclopentadiene type epoxy resins); and DIC's "EXA-7311" and "EXA-7311- G3, EXA-7311-G4, EXA-7311-G4S, HP-6000, HP-6000L (naphthalene ether type epoxy resin); EPPN-502H (triphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; NC-7000L (naphthalene phenolic varnish type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; NC-3000, NC-3000L, NC-3000FH, NC-3100 (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; NC-3000H (biphenyl aryl type) manufactured by Nippon Kayaku Co., Ltd. Epoxy resins; Nippon Steel Chemical Materials Co., Ltd.'s "ESN475V" and "ESN4100V" (naphthalene-type epoxy resins); Nippon Steel Chemical Materials Co., Ltd.'s "ESN485" (naphthol-type epoxy resins); Nippon Steel Chemical Materials Co., Ltd.'s "ESN375" (dihydroxynaphthalene-type epoxy resins); Mitsubishi Chemical Corporation's "YX4000H", "YX4000", "YX4000HK", and "YL7890" (bi-xylenol-type epoxy resins); Mitsubishi Chemical Corporation's "YL6121" (biphenyl-type epoxy resins); Mitsubishi Chemical Corporation's "YX8800" (anthracite-type epoxy resins). These include: epoxy resins such as Mitsubishi Chemical's "YX7700" (phenolic aralkyl type epoxy resin); Osaka Gas Chemical's "PG-100" and "CG-500"; Mitsubishi Chemical's "YL7760" (bisphenol AF type epoxy resin); Mitsubishi Chemical's "YL7800" (fluorene-containing epoxy resin); Mitsubishi Chemical's "jER1010" (bisphenol A type epoxy resin); Mitsubishi Chemical's "jER1031S" (tetraphenylethane type epoxy resin); and Nippon Kayaku Co., Ltd.'s "WHR991S" (phenolic benzopyrrolidone type epoxy resin). These can be used individually or in combination of two or more.

[0173] (B) The epoxy equivalent of the epoxy resin is preferably 50 to 5000 g / eq. The lower limit of the epoxy equivalent is more preferably 60 g / eq. or more, further preferably 80 g / eq. or more, and particularly preferably 110 g / eq. or more. The upper limit of the epoxy equivalent is preferably 3000 g / eq. or less, more preferably 2000 g / eq. or less, further preferably 1000 g / eq. or less, and particularly preferably 500 g / eq. or less, 400 g / eq. or less, or 300 g / eq. or less. The epoxy equivalent is the mass of epoxy resin containing 1 equivalent of epoxy groups, and can be determined according to JIS K 7236.

[0174] (B) The weight-average molecular weight (Mw) of the epoxy resin is preferably 100–5000, more preferably 250–3000, and even more preferably 400–1500. The weight-average molecular weight (Mw) of the epoxy resin can be determined by using the GPC method as a value converted from polystyrene.

[0175] From the viewpoint of significantly obtaining the effects of the present invention, when the resin component in the resin composition layer is set to 100% by mass, the content of component (B) in the resin composition layer is preferably 1% by mass or more, more preferably 5% by mass or more or 10% by mass or more, further preferably 15% by mass or more or 20% by mass or more, and particularly preferably 25% by mass or more or 30% by mass or more. The upper limit is preferably 70% by mass or less or 65% by mass or less, more preferably 60% by mass or less or 55% by mass or less, further preferably 50% by mass or less or 45% by mass or less, and particularly preferably 40% by mass or less or 35% by mass or less.

[0176] From the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile component in the resin composition layer is set to 100% by mass, the content of component (B) in the resin composition layer is preferably 0.1% by mass or more or 0.5% by mass or more, more preferably 1% by mass or more or 2% by mass or more, further preferably 3% by mass or more, 4% by mass or more or 5% by mass or more, particularly preferably 6% by mass or more, 7% by mass or more or 8% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 35% by mass or less or 30% by mass or less, further preferably 25% by mass or less or 20% by mass or less, particularly preferably 15% by mass or less or 10% by mass or less.

[0177] <(C) Polycarbodiimide compounds> The resin composition layer of the resin sheet according to the first embodiment of the present invention contains (C) polycarbodiimide compound. (C) polycarbodiimide compound can be used alone or in combination of two or more.

[0178] (C) Polycarbodiimide compounds are compounds having two or more carbodiimide groups (-N=C=N-) in one molecule. Examples of (C) polycarbodiimide compounds include: aliphatic dicarbodiimides such as tetramethylene-bis(tert-butylcarbodiimide) and cyclohexane-bis(methylene-tert-butylcarbodiimide); aromatic dicarbodiimides such as phenylene-bis(xylylcarbodiimide); aliphatic polycarbodiimides such as polyhexamethylene carbodiimide, polytrimethylhexamethylene carbodiimide, polycyclohexylcarbodiimide, poly(methylene biscyclohexylcarbodiimide), and poly(isophorone carbodiimide); poly(phenylene carbodiimide), poly... Aromatic polycarbodiimides such as (naphthylcarbodiimide), poly(tolylcarbodiimide), poly(methyldiisopropylphenylcarbodiimide), poly(triethylphenylcarbodiimide), poly(diethylphenylcarbodiimide), poly(triisopropylphenylcarbodiimide), poly(diisopropylphenylcarbodiimide), poly(xylylcarbodiimide), poly(tetramethylxylylcarbodiimide), poly(methylenediphenylcarbodiimide), poly[methylenebis(methylphenyl)carbodiimide], etc., are also considered polycarbodiimides. They can be used alone or in combination of two or more.

[0179] From the viewpoint of achieving significant effects of the present invention, the weight-average molecular weight of (C) polycarbodiimide compound is preferably 500 or more, more preferably 600 or more, further preferably 700 or more, even more preferably 800 or more, and particularly preferably 900 or more or 1000 or more. Furthermore, from the viewpoint of obtaining good compatibility, the upper limit of the weight-average molecular weight of (C) polycarbodiimide compound is preferably 10000 or less, 8000 or less, 7000 or less, 6000 or less, or 5000 or less, more preferably 4500 or less, even more preferably 4000 or less, even more preferably 3500 or less, and particularly preferably 3000 or less. The weight-average molecular weight of (C) polycarbodiimide compound can be determined, for example, by gel permeation chromatography (GPC) (polystyrene conversion).

[0180] From the viewpoint of achieving significant effects of the present invention, the carbodiimide equivalent of the polycarbodiimide compound (C) is preferably 150 g / eq. or more, more preferably 200 g / eq. or more, even more preferably 250 g / eq. or more, preferably 1000 g / eq. or less, more preferably 800 g / eq. or less, and even more preferably 600 g / eq. or less. The carbodiimide equivalent represents the mass of resin per 1 equivalent of carbodiimide groups.

[0181] Commercially available examples of (C) polycarbodiimide compounds include, for example, CARBODILITE V-03 (carbodiimide equivalent: 216 g / eq., the carbodiimide compound represented by formula (C1) described below), CARBODILITE V-05 (carbodiimide equivalent: 262 g / eq.), CARBODILITE V-07 (carbodiimide equivalent: 200 g / eq.), and CARBODILITE V-09 (carbodiimide equivalent: 200 g / eq.) manufactured by Nisshinbo Chemical Co., Ltd.; and Stabaxol P (carbodiimide equivalent: 302 g / eq.) manufactured by LANXESS Co., Ltd.

[0182] In one embodiment, (C) the polycarbodiimide compound preferably contains the structural unit shown in the following formula (C1).

[0183] [Chemical Formula 24] (In formula (C1), X represents an alkylene, cycloalkylene, or aryl group, which may optionally have substituents. p represents an integer from 1 to 5. When multiple Xs are present, they may be the same or different. * indicates a linking bond.)

[0184] The alkylene group represented by X preferably has 1 to 20 carbon atoms, more preferably 1 to 10, and even more preferably 1 to 6, 1 to 4, or 1 to 3. This number of carbon atoms does not include the number of carbon atoms of substituents. Preferred examples of this alkylene group include methylene, ethylene, propylene, and butylene.

[0185] The number of carbon atoms in the cycloalkyl group represented by X is preferably 3 to 20, more preferably 3 to 12, and even more preferably 3 to 6. This number of carbon atoms does not include the number of carbon atoms of the substituents. Preferred examples of this cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0186] The arylene group represented by X is a group obtained by removing two hydrogen atoms from the aromatic ring of an aromatic hydrocarbon. The arylene group preferably has 6 to 24 carbon atoms, more preferably 6 to 18, even more preferably 6 to 14, and even more preferably 6 to 10. This number of carbon atoms does not include the number of carbon atoms from substituents. Preferred examples of arylene groups include phenylene, naphthylene, and anthracene.

[0187] From the viewpoint of achieving significant effects of the present invention, X is preferably an alkylene or cycloalkylene group, which may optionally have substituents.

[0188] The alkylene, cycloalkylene, or arylene group represented by X may optionally have substituents. There are no particular limitations on the substituent, and examples include halogen atoms, alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkyloxy groups, aryl groups, aryloxy groups, acyl groups, and acyloxy groups. Examples of halogen atoms used as substituents include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. The alkyl or alkoxy group used as a substituent may be either straight-chain or branched, and its carbon number is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6, 1 to 4, or 1 to 3. The cycloalkyl or cycloalkyloxy group used as a substituent preferably has 3 to 20 carbon atoms, more preferably 3 to 12, and even more preferably 3 to 6. The aryl group used as a substituent is a group obtained by removing one hydrogen atom from the aromatic ring of an aromatic hydrocarbon, and its carbon number is preferably 6 to 24, more preferably 6 to 18, even more preferably 6 to 14, and even more preferably 6 to 10. The aryloxy group used as a substituent preferably has 6 to 24 carbon atoms, more preferably 6 to 18, even more preferably 6 to 14, and even more preferably 6 to 10. The acyl group used as a substituent refers to the group with the formula: -C(=O)-R 1 The group represented (where R is a radical) 1 (Indicates alkyl or aryl). R 1 The alkyl group can be either straight-chain or branched, and its carbon number is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6, 1 to 4, or 1 to 3. 1 The aryl group preferably has 6 to 24 carbon atoms, more preferably 6 to 18, even more preferably 6 to 14, and even more preferably 6 to 10. The acyloxy group used as a substituent refers to the group with the formula: -OC(=O)-R 1 The group represented (where R is a radical) 1 (This has the same meaning as above). The substituents are preferably alkyl, alkoxy, and acyloxy groups, with alkyl being more preferred.

[0189] In formula (C1), p represents an integer from 1 to 5. From the viewpoint of significantly obtaining the effects of the present invention, p is preferably 1 to 4, more preferably 2 to 4, and even more preferably 2 or 3.

[0190] When multiple X's are present in formula (C1), they can be the same or different. In a preferred embodiment, at least one X' is an alkylene or cycloalkylene group, which may optionally have substituents.

[0191] In a preferred embodiment, when the total mass of the polycarbodiimide compound is set to 100% by mass, (C) the polycarbodiimide compound contains, preferably, 50% or more by mass, more preferably 60% or more by mass, further preferably 70% or more by mass, further preferably 80% or more by mass, or 90% or more by mass of the structural unit shown in formula (C1). Besides the terminal structure, the polycarbodiimide compound may also be substantially formed from the structural unit shown in formula (C1). The terminal structure of the polycarbodiimide compound is not particularly limited, and examples include alkyl, cycloalkyl, and aryl groups, which optionally have substituents. The alkyl, cycloalkyl, and aryl groups used as terminal structures can have the same meaning as the alkyl, cycloalkyl, and aryl groups described with respect to the substituents optionally present in the group shown in X. Furthermore, the substituents optionally present in the group used as terminal structures can have the same meaning as the substituents optionally present in the group shown in X.

[0192] In one embodiment, (C) the polycarbodiimide compound preferably contains the structural unit shown in the following formula (C2). [Chemical Formula 25] (In formula (C2), Y represents an optional divalent hydrocarbon group with substituents. * indicates a linking bond.)

[0193] In formula (C2), Y represents a divalent hydrocarbon group optionally having substituents. The number of carbon atoms in the divalent hydrocarbon group of Y is usually 1 or more, preferably 2 or more, and usually 30 or less. The divalent hydrocarbon group can be a divalent saturated hydrocarbon group or a divalent unsaturated hydrocarbon group. Unless otherwise specified, a divalent unsaturated hydrocarbon group represents a hydrocarbon group having at least one carbon-carbon double bond, carbon-carbon triple bond, or aromatic hydrocarbon ring, including any of the straight-chain, branched, and cyclic forms.

[0194] Examples of preferred divalent hydrocarbon groups in Y include alkylene, cycloalkylene, arylene, and groups formed by combining them.

[0195] The alkylene group in Y preferably has 1 to 20 carbon atoms, more preferably 1 to 10, and even more preferably 1 to 6, 1 to 4, or 1 to 3. This number of carbon atoms does not include the number of carbon atoms of substituents. Preferred examples of alkylene groups include methylene, ethylene, propylene, and butylene.

[0196] The number of carbon atoms in the cycloalkyl group Y is preferably 3 to 20, more preferably 3 to 12, and even more preferably 3 to 6. This number of carbon atoms does not include the number of carbon atoms of the substituents. Preferred examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0197] In Y, the arylene group represents the group formed by removing two hydrogen atoms from the aromatic ring of an aromatic hydrocarbon. The arylene group preferably has 6 to 24 carbon atoms, more preferably 6 to 18, even more preferably 6 to 14, or 6 to 10. This number of carbon atoms does not include the number of carbon atoms from substituents. Preferred examples of arylene groups include phenylene, naphthylene, and anthracene.

[0198] Substituents in Y are not particularly limited, and examples include halogen atoms, alkyl-oxy groups, alkenyl-oxy groups, aryl-oxy groups, alkyl-oxy-carbonyl groups, alkenyl-oxy-carbonyl groups, aryl-oxy-carbonyl groups, alkyl-carbonyl-oxy groups, alkenyl-carbonyl-oxy groups, aryl-carbonyl-oxy groups, etc. Preferably, the divalent hydrocarbon group in Y does not have substituents.

[0199] More preferably, Y represents a divalent saturated hydrocarbon group having 2 to 30 carbon atoms, optionally having a substituent, or a divalent unsaturated hydrocarbon group having 2 to 30 carbon atoms, optionally having a substituent. More preferably, Y represents a divalent saturated hydrocarbon group having 2 to 30 carbon atoms, optionally having a substituent and having a cyclic structure (e.g., a cyclic structure selected from cycloalkane rings, benzene rings, and naphthalene rings), or a divalent unsaturated hydrocarbon group having 2 to 30 carbon atoms, optionally having a substituent and having a cyclic structure (e.g., a cyclic structure selected from cycloalkane rings, benzene rings, and naphthalene rings).

[0200] In formula (C2), Y preferably represents the divalent group shown in formula (C3) below. [Chemical Formula 26] (In formula (C3), Y) a Y b and Y c Each independently represents a single bond or C(R) bond. y )2;R y Each independently represents a hydrogen atom or a methyl group; the ring Y 1 and Y 2 Each can independently represent a cycloalkane ring with 4 to 10 carbon atoms that may optionally have substituents, a benzene ring that may optionally have substituents, or a naphthalene ring that may optionally have substituents; n y Represents 0 or 1; * represents a hyphen.

[0201] In equation (C3), Y a Y b and Y c Each independently represents a single bond or C(R) bond. y 2. Preferably, Y a and Y c It is a single bond and Y b Represents C(R) y )2. R yEach can be independently represented by a hydrogen atom or a methyl group, preferably a hydrogen atom.

[0202] In equation (C3), ring Y 1 and ring Y 2 Each of these can independently represent a cycloalkane ring with 4 to 10 carbon atoms, a benzene ring, or a naphthalene ring, optionally with substituents. Preferably, ring Y... 1 and ring Y 2 Each can be independently represented as a cycloalkane ring with 4 to 10 carbon atoms, optionally containing substituents. Examples of cycloalkane rings with 4 to 10 carbon atoms include monocyclic saturated hydrocarbon rings such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, and cyclodecane; bicyclic saturated carbon rings such as [2.2.1]heptane (norbornene), [4.4.0]decane (decahydronaphthalene), [5.3.0]decane, [4.3.0]nonane (hexahydroindene), [3.3.0]octane, and [3.3.1]nonane; and tricyclic [5.2.1.0]nonane. 2,6 Decane ring (tetrahydrobicyclopentadiene ring), tricyclic [3.3.1.1] 3 ,7 Saturated carbocyclic tricyclic systems such as decane ring (adamantane ring). More preferably, cyclic Y... 1 and ring Y 2 Each group independently represents a cyclohexane ring optionally having substituents. Substituents in cycloalkane rings, benzene rings, and naphthalene rings are not particularly limited, and examples include halogen atoms, alkyl, alkenyl, aryl, aryl-alkyl (alkyl groups substituted with aryl), alkyl-aryl (aryl groups substituted with alkyl), alkyl-oxy, alkenyl-oxy, aryl-oxy, alkyl-oxy-carbonyl, alkenyl-oxy-carbonyl, aryl-carbonyl-carbonyl, alkyl-carbonyl-oxy, alkenyl-carbonyl-oxy, aryl-carbonyl-oxy, etc. Among them, cyclohexane ring Y... 1 and ring Y 2 Unsubstituted cyclohexane rings are particularly preferred.

[0203] As specific examples of Y, the divalent groups shown in formulas (Y1) to (Y14) can be cited, with the divalent group shown in formula (Y1) being particularly preferred. In formulas (Y1) to (Y14), * denotes a connecting bond. [Chemical Formula 27]

[0204] In a preferred example, the proportion of the structural unit represented by formula (C2) contained in component (C) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more, and may also be 90% by mass or more, relative to 100% by mass of the total molecular mass of component (C).

[0205] In one embodiment, (C) the polycarbodiimide compound is preferably the compound represented by formula (C4). [Chemical Formula 28] (In formula (C4), R independently represents either a hydrogen atom or a methyl group;) X 1 Each can independently represent carbonyl, methylene, phenylene, or phenylene-methylene; X 2 Each of the following units independently represents a divalent saturated hydrocarbon group with 2 to 4 carbon atoms; each of the following units independently represents a divalent saturated hydrocarbon group with 2 to 300 carbon atoms that may have optional substituents, or a divalent unsaturated hydrocarbon group with 2 to 300 carbon atoms that may have optional substituents; each of the following units independently represents an integer of 0 or more; each of the following units independently represents b ≤ 1; each of the following units independently represents c ≤ 1 or more; each of the following units independently represents 0 or d ≤ 1 or more; each of the following units independently represents the aforementioned groups. For units a, b, c, and d, each unit may be the same or different.

[0206] In formula (C4), R independently represents either a hydrogen atom or a methyl group.

[0207] In equation (C4), X 1 Each can independently represent a carbonyl group, methylene group, phenylene group, or phenylene-methylene group (the bonding direction is not particularly limited, but preferably the phenylene side is bonded to the C in "RC"). Preferably, X 1 Each group can be either methylene or carbonyl. Phenylidene-methylene includes 1,2-phenyl-methylene, 1,3-phenyl-methylene, and 1,4-phenyl-methylene.

[0208] In equation (C4), X 2 Each of these groups independently represents a divalent saturated hydrocarbon group having 2 to 4 carbon atoms. The divalent saturated hydrocarbon group can be straight-chain, branched, or cyclic. Specific examples of divalent saturated hydrocarbon groups having 2 to 4 carbon atoms include: straight-chain alkylene groups having 2 to 4 carbon atoms, such as ethylene, trimethylene, and tetramethylene; and branched alkylene groups having 2 to 4 carbon atoms, such as ethoxylide, propyleneide, isopropyleneide, and ethylmethylmethylene. In one embodiment, X 2Each is preferably a divalent saturated hydrocarbon group with 2 or 3 carbon atoms, and more preferably an ethylene group (-CH2-CH2-).

[0209] In formula (C4), each Z independently represents either a divalent saturated hydrocarbon group having 2 to 300 carbon atoms, optionally having a substituent, or a divalent unsaturated hydrocarbon group having 2 to 300 carbon atoms, optionally having a substituent. Preferably, each Z independently represents either a divalent saturated hydrocarbon group having 2 to 300 carbon atoms, or a divalent unsaturated hydrocarbon group having 2 to 300 carbon atoms. More preferably, each Z independently represents a divalent hydrocarbon group having 300 or fewer carbon atoms, having structural units selected from formulas (Z1) to (Z8) below. Even more preferably, each Z independently represents a divalent hydrocarbon group having 300 or fewer carbon atoms formed from structural units selected from formulas (Z1) to (Z8). [Chemical Formula 29] (In the formula, * represents a connector.)

[0210] Z more preferably represents a divalent hydrocarbon group having 300 or fewer carbon atoms in the structural unit shown in formula (Z1); more preferably, it represents a divalent hydrocarbon group formed from structural units selected from formulas (Z1) to (Z8) and having at least 300 or fewer carbon atoms in the structural unit shown in formula (Z1). In particular, Z preferably represents a divalent hydrocarbon group having 300 or fewer carbon atoms in the form of the following formula (Z-1). [Chemical Formula 30] (In formula (Z-1), n) z Represents an integer greater than or equal to 1; * represents a concatenation key.

[0211] In formula (C4), each a independently represents an integer greater than or equal to 0 or 1, preferably an integer from 0 or 1 to 10, and more preferably 0 or 1.

[0212] In formula (C4), b represents the average degree of polymerization of the carbodiimide group. Each b independently represents b≤1 or more, preferably an integer of 1 or more, more preferably 1 to 100, and even more preferably an integer of 1 to 100, 1 to 10, or an integer of 1 to 10.

[0213] In formula (C4), c represents the average degree of polymerization of the divalent saturated hydrocarbon group with 2 to 300 carbon atoms, which is optionally represented by substituents, as shown in Z. Each c independently represents c ≤ 1 or more, preferably an integer of 1 or more, more preferably 1 to 100, and even more preferably an integer of 1 to 100, 1 to 10, an integer of 1 to 10, or 1.

[0214] In formula (C4), d represents the average degree of polymerization of the group represented by Z with polycarbodiimide. Each d independently represents 0 or d≤1 or more, preferably 0 or 1 to 100, more preferably an integer of 0 or 1 to 100, and even more preferably 0 or 1 to 10, or an integer of 0 or 1 to 10.

[0215] (C) Depending on its preparation method, the molecule of component (C) may sometimes contain isocyanate groups (-N=C=O). The content of isocyanate groups in component (also referred to as "NCO content") is preferably 5% by mass or less, more preferably 4% by mass or less, even more preferably 3% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1% by mass or less or 0.5% by mass or less.

[0216] Specific examples of component (C) as shown in formula (C4) can be given by the compounds shown in (S1) to (S5) below. However, component (C) is not limited to these specific examples. In the formula, b' is the same as b in formula (C4), d' is the same as d in formula (C4), and e' is the same as c in formula (C4). It should be noted that in formula (S5), the e' unit only represents the 1,2-addition structural unit, but also includes the 1,4-addition structural unit (cis, trans). [Chemical Formula 31]

[0217] Component (C) having the structural unit shown in formula (C2) and component (C) having the structural unit shown in formula (C4) can be manufactured, for example, by the following method. Specifically, the following method can be used: a diisocyanate compound such as dicyclohexylmethane-4,4'-diisocyanate and a carbodiimide catalyst such as 3-methyl-1-phenyl-2-phospho-1-oxide are mixed and stirred to carry out a carbodiimide reaction to obtain an isocyanate-terminated polycarbodiimide. Then, the obtained isocyanate-terminated polycarbodiimide, a compound having free radical polymerizable groups such as (meth)acryloyl groups, and other polymerizable compounds such as polybutadiene with two terminal hydroxyl groups as needed are reacted.

[0218] From the viewpoint of significantly obtaining the effects of the present invention, when the resin component in the resin composition layer is set to 100% by mass, the content of component (C) in the resin composition layer is preferably 0.01% by mass or more or 0.05% by mass or more, more preferably 0.1% by mass or more or 0.5% by mass or more, further preferably 1% by mass or more or 1.5% by mass or more, particularly preferably 2% by mass or more, 2.5% by mass or more, or 3% by mass or more. The upper limit is preferably 30% by mass or less or 25% by mass or less, more preferably 20% by mass or less or 15% by mass or less, further preferably 10% by mass or less or 9% by mass or less, particularly preferably 8% by mass or less or 7% by mass or less. Additionally, in one embodiment, it can be 6% by mass or less, 5% by mass or less, 4% by mass or less, etc.

[0219] From the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile component in the resin composition layer is set to 100% by mass, the content of component (C) in the resin composition layer is preferably 0.001% by mass or more, 0.005% by mass or more, or 0.01% by mass or more, more preferably 0.05% by mass or more, 0.1% by mass or more, or 0.2% by mass or more, further preferably 0.3% by mass or more, 0.4% by mass or more, or 0.5% by mass or more, particularly preferably 0.6% by mass or more, 0.7% by mass or more, or 0.8% by mass or more. The upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, further preferably 5% by mass or less, or 4% by mass or less, particularly preferably 3% by mass or less, or 2% by mass or less. In addition, in one embodiment, it can be 1.8% by mass or less, 1.5% by mass or less, 1.2% by mass or less, 1% by mass or less, etc.

[0220] When the resin component in the resin composition layer is set to 100% by mass, from the viewpoint of significantly obtaining the effects of the present invention, the total content of component (1A), component (B), and component (C) in the resin composition layer is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 35% by mass or more or 40% by mass or more. There is no particular upper limit; it can be 100% by mass, or it can be 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, etc.

[0221] From the viewpoint of significantly obtaining the effects of the present invention, the mass ratio of component (1A) to component (C) in the resin composition layer [(1A) component / (C) component] is preferably 0.1 or more or 0.2 or more, more preferably 0.5 or more or 0.8 or more, further preferably 1 or more or 1.2 or more, and particularly preferably 1.5 or more or 1.8 or more. In one embodiment, it can be 2 or more, 2.5 or more, 3 or more, etc. The upper limit is preferably 50 or less or 40 or less, more preferably 30 or less or 25 or less, further preferably 20 or less, 15 or less or 10 or less, and particularly preferably 8 or less, 6 or less or 5 or less. In another embodiment, it can be 4 or less, 3.5 or less, etc. In one embodiment, the mass ratio [(1A) component / (C) component] is preferably 0.1 to 50.

[0222] <(D) Curing Agent> In the resin composition layer of the resin sheet according to the first embodiment of the present invention, (D) curing agent may be included as an optional component, and (D) curing agent is preferred. However, substances belonging to component (C) are excluded from component (D). One type of (D) curing agent may be used alone, or two or more types may be used in combination. In one embodiment, two or more types of (D) curing agents are preferably used in combination. In one embodiment, (D) curing agent preferably includes an epoxy resin curing agent, and (D) curing agent is more preferably an epoxy resin curing agent.

[0223] The reactive base equivalent of (D) curing agent is preferably 50 g / eq. to 3000 g / eq., more preferably 100 g / eq. to 1000 g / eq., even more preferably 100 g / eq. to 500 g / eq., and particularly preferably 100 g / eq. to 300 g / eq. The reactive base equivalent is the mass of (D) curing agent per 1 equivalent of reactive base.

[0224] In a preferred embodiment, in the resin composition layer of the resin sheet of the present invention, the (D) curing agent comprises an active ester resin. By including an active ester resin in the (D) curing agent, a cured product with high reflow soldering resistance can also be obtained.

[0225] As an active ester resin, a compound having one or more active ester groups per molecule can be used. Among these, compounds having two or more highly reactive ester groups per molecule, such as phenolic esters, thiophenolic esters, N-hydroxylamine esters, and heterocyclic hydroxyl compounds, are preferred. This active ester resin is preferably a resin obtained through a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxyl compound and / or a thiol compound. Particularly from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound and a hydroxyl compound is preferred, and an active ester resin obtained from a carboxylic acid compound and a phenolic compound and / or a naphthol compound is more preferred.

[0226] Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

[0227] Examples of phenolic or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthol, 1,6-dihydroxynaphthol, 2,6-dihydroxynaphthol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyroglucinol, dicyclopentadiene-type diphenol compounds, and linear phenolic resins. Here, "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

[0228] Preferred examples of reactive ester resins include reactive ester resins containing a dicyclopentadiene-type diphenol structure (hereinafter also referred to as "dicyclopentadiene-type reactive ester resins"), reactive ester resins containing a naphthalene structure, reactive ester resins containing phosphorus, reactive ester resins containing acetylated linear phenolic resins, reactive ester resins containing benzoylated linear phenolic resins, and reactive ester resins containing a butadiene structure. Among these, reactive ester resins containing a naphthalene structure, reactive ester resins containing a dicyclopentadiene-type diphenol structure, or reactive ester resins containing a butadiene structure are preferred, and reactive ester resins containing a naphthalene structure are more preferred. "Dicyclopentadiene-type diphenol structure" refers to a divalent structural unit formed from a phenylene-dicyclopentylene-phenylene group.

[0229] Regarding commercially available reactive ester resins, examples of reactive ester resins containing a dicyclopentadiene-type diphenol structure include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "EXB-8000H", "HPC-8000L-65TM", and "EXB-8000L-65TM" (manufactured by DIC Corporation); examples of naphthalene-type reactive ester resins containing a naphthalene structure include "EXB-9416-70BK", "EXB-8100L-65T", "EXB-8150L-65T", "HPC-8150-62T", "EXB-8100L-65T", "EXB-8" (manufactured by DIC Corporation), "PC1300-02-65T", and "PC1300-02-65MA" (Air Water Corporation (manufactured); as a phosphorus-containing reactive ester resin, "EXB-9401" (manufactured by DIC Corporation) can be cited; as a reactive ester curing agent containing acetylated linear phenolic resin, "DC808" (manufactured by Mitsubishi Chemical Corporation) can be cited; as a reactive ester curing agent containing benzoylated linear phenolic resin, "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation), "EXB-8500-65T" (manufactured by DIC Corporation) can be cited, etc.

[0230] The resin composition layer of the resin sheet according to the first embodiment of the present invention may further include a curing agent other than an active ester resin. Examples of curing agents other than active ester resins include phenolic curing agents, acid anhydride curing agents, amine curing agents, benzoxazine curing agents, cyanate ester curing agents, and thiol curing agents. In one embodiment, in the resin composition layer of the resin sheet according to the first embodiment of the present invention, (D) the curing agent preferably includes an active ester resin and a phenolic curing agent.

[0231] As a phenolic curing agent, a curing agent having one or more, preferably two or more, hydroxyl groups (phenolic hydroxyl groups) bonded to aromatic rings such as benzene rings or naphthalene rings in one molecule can be used. From the viewpoint of heat resistance and water resistance, phenolic curing agents with a phenolic structure are preferred. Furthermore, from the viewpoint of adhesion to the adhered materials, nitrogen-containing phenolic curing agents are preferred, and phenolic curing agents containing a triazine skeleton are more preferred. Among these, linear phenolic resins containing a triazine skeleton are preferred from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion.

[0232] Specific examples of phenolic curing agents include UBE's "MEH-7700", "MEH-7810", "MEH-7851", "MEH-7600", "MEH-7851", and "MEH-8000H"; Nippon Kayaku Co., Ltd.'s "NHN", "CBN", "GPH", "GPH-65", and "GPH-103"; and Nippon Steel Chemical Materials Co., Ltd.'s "SN-170", "SN-180", "SN-190", and "SN-180". "SN-475", "SN-485", "SN-495V", "SN-495", "SN-375", "SN-395"; and DIC's "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD-2090", "TD2131", "TD-2090-60M", "KA-1160", "KA-1163", "KA-1165", etc. These can be used individually or in combination of two or more.

[0233] As an anhydride-based curing agent, a curing agent having one or more anhydride groups in one molecule can be used, preferably a curing agent having two or more anhydride groups in one molecule. Specific examples of anhydride-based curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, and diphenyltricarboxylic anhydride. Benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxophthalic dianhydride, 3,3'-4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(trimethacrylate), and styrene-maleic acid resin obtained by copolymerizing styrene and maleic acid are all polymeric anhydrides. They can be used alone or in combination of two or more.

[0234] Commercially available anhydride-based curing agents include: "HNA-100", "MH-700", "MTA-15", "DDSA", and "OSA" manufactured by New Japan Rika Co., Ltd.; "YH-306" and "YH-307" manufactured by Mitsubishi Chemical Co., Ltd.; "HN-2200" and "HN-5500" manufactured by Lisennoco Co., Ltd.; and "EF-30", "EF-40", "EF-60", and "EF-80" manufactured by Cray Valley Co., Ltd. These can be used individually or in combination of two or more.

[0235] As an amine-based curing agent, a curing agent having one or more, preferably two or more, amino groups per molecule can be used. The amino groups in the amine-based curing agent are preferably primary or secondary amino groups, more preferably primary amino groups. Examples of amine-based curing agents include aliphatic amines, polyether amines, alicyclic amines, and aromatic amines, among which aromatic amines are preferred from the viewpoint of achieving the desired effect of the present invention. The amine-based curing agent is preferably a primary or secondary amine, more preferably a primary amine.

[0236] Specific examples of amine-based curing agents include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, m-phenylenediamine, m-phenylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, and 2,2-bis(3-amino-4-hydroxy) 2,2-bis(4-aminophenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, etc. Amine-based curing agents can be commercially available, such as SEIKA's "SEIKACURE-S"; Nippon Kayaku Co.'s "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", and "KAYAHARD AS"; Mitsubishi Chemical's "Epicure W"; and Sumitomo Seikan's "DTDA". They can be used individually or in combination of two or more.

[0237] Specific examples of benzoxazine-based curing agents include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemicals; "HFB2006M" manufactured by Showa Polymers; and "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd. They can be used individually or in combination of two or more.

[0238] Examples of difunctional cyanate ester resins that can be used as cyanate ester curing agents include bisphenol A dicyanate, polyphenol cyanate (oligomeric (3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethoxydiphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanoxyphenylmethane), bis(4-cyanoxy-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanoxyphenyl-1-(methylethoxy))benzene, bis(4-cyanoxyphenyl) sulfide, and bis(4-cyanoxyphenyl) ether; multifunctional cyanate ester resins derived from phenolic varnish resins and cresol varnish resins; and prepolymers obtained by partially triazinizing these cyanate ester resins. Specific examples of cyanate ester-based curing agents include Arxada's "PT30" and "PT60" (both linear phenolic resin-type multifunctional cyanate ester resins), "BA230," and "BA230S75" (prepolymers obtained by triazinization of part or all of bisphenol A dicyanate to form trimers). They can be used individually or in combination of two or more.

[0239] Examples of thiol-based curing agents include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptobutyrate), and tris(3-mercaptopropyl)isocyanurate. They can be used individually or in combination of two or more.

[0240] When the resin composition layer of the resin sheet according to the first embodiment of the present invention contains a curing agent (D), from the viewpoint of significantly obtaining the effects of the present invention, when the resin component in the resin composition layer is set to 100% by mass, the content of the (D) component in the resin composition layer is preferably 1% by mass or more or 5% by mass or more, more preferably 10% by mass or more or 15% by mass or more, further preferably 20% by mass or more or 25% by mass or more, particularly preferably 30% by mass or more, 35% by mass or more or 40% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less or 70% by mass or less, further preferably 65% ​​by mass or less or 60% by mass or less, particularly preferably 55% by mass or less or 50% by mass or less.

[0241] In the case where the resin composition layer of the resin sheet according to the first embodiment of the present invention contains a curing agent (D), from the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile component in the resin composition layer is set to 100% by mass, the content of component (D) in the resin composition layer is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 3% by mass or more or 5% by mass or more, particularly preferably 8% by mass or more or 10% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less or 18% by mass or less, particularly preferably 15% by mass or less or 13% by mass or less.

[0242] When the resin composition layer of the resin sheet according to the first embodiment of the present invention contains curing agent (D), when the resin component in the resin composition layer is set to 100% by mass, the total content of component (1A), component (B), component (C), and component (D) in the resin composition layer is preferably 50% by mass or more, more preferably 60% by mass or more or 70% by mass or more, further preferably 75% by mass or more or 80% by mass or more, and particularly preferably 85% by mass or more or 90% by mass or more. There is no particular limitation on the upper limit; it can also be 100% by mass, and can be 99% by mass or less, 98% by mass or less, 97% by mass or less, 96% by mass or less, 95% by mass or less, etc.

[0243] From the viewpoint of significantly obtaining the effects of the present invention, the ratio of the molar number of active groups of the curing agent (D) to the molar number of epoxy groups of the epoxy resin (B) in the resin composition layer (molar number of active groups of the curing agent / molar number of epoxy groups of the epoxy resin) is preferably 0.01 or more or 0.05 or more, more preferably 0.1 or more or 0.2 or more, further preferably 0.5 or more or 0.8 or more, and particularly preferably 1 or more or 1.05 or more. The upper limit is preferably 100 or less or 50 or less, more preferably 10 or less or 8 or less, further preferably 5 or less, 3 or less or 2 or less, and particularly preferably 1.8 or less, 1.5 or less or 1.2 or less. The "molar number of active groups of the curing agent" can be calculated by "the amount of curing agent ÷ the equivalent of reactive groups of the curing agent". The "molar number of epoxy groups of the epoxy resin" can be calculated by "the amount of epoxy resin ÷ the epoxy equivalent of the epoxy resin".

[0244] <(E) Inorganic Filler Materials> In the resin composition layer of the resin sheet according to the first embodiment of the present invention, (E) inorganic filler material may be included as an optional component, and (E) inorganic filler material is preferred. By including (E) inorganic filler material in the resin composition layer, the dielectric loss tangent of the cured product can be further reduced.

[0245] Inorganic compounds can be used as the inorganic filler material in (E). Examples of inorganic fillers in (E) include silicon dioxide, alumina, aluminum silicate, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silicon dioxide is preferred. Examples of silicon dioxide include amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, and hollow silicon dioxide. Furthermore, spherical silicon dioxide is preferred in terms of its shape. (E) Inorganic filler materials can be used alone or in combination of two or more in any ratio.

[0246] Commercially available products as (E) inorganic filler materials include, for example, “SP60-05” and “SP507-05” manufactured by Nippon Steel Chemical Materials Co., Ltd.; “YC100C”, “YA050C”, “YA050C-MJE”, “YA010C”, “SC2500SQ”, “SO-C4”, “SO-C2”, “SO-C1”, “SC2300-SVJ”, “SC2050-SXF”, and “180nmSX-C1” manufactured by Yatuma Co., Ltd.; “UFP-30”, “DAW-03”, and “FB-105FD” manufactured by Denka Co., Ltd.; “Silfil NSS-3N”, “Silfil NSS-4N”, and “Silfil NSS-5N” manufactured by Tokuyama Co., Ltd.; and “CellSpheres” and “MGH-005” manufactured by Pacific Cement Co., Ltd.

[0247] From the viewpoint that the surface of the cured material (insulating layer) has low roughness and is easy to form fine wiring, the average particle size of the inorganic filler material (E) is preferably 10 μm or less, more preferably 5 μm or less, further preferably 2 μm or less, even more preferably 1 μm or less, and particularly preferably 0.7 μm or less or 0.6 μm or less. The lower limit of the average particle size of the inorganic filler material (E) is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, further preferably 0.1 μm or more, and particularly preferably 0.15 μm or more, 0.2 μm or more, 0.3 μm or more, or 0.4 μm or more. The average particle size of the inorganic filler (E) can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler material can be prepared using a laser diffraction scattering particle size distribution measuring device with a volume reference, and the median diameter can be used as the average particle size for measurement. The sample to be measured can be prepared by weighing 100 mg of inorganic filler material and 10 g of methyl ethyl ketone into a vial and dispersing it ultrasonically for 10 minutes. The light source wavelength used in the laser diffraction particle size distribution measuring device can be set to blue or red, and the measurement is performed in a flow cell. Examples of laser diffraction particle size distribution measuring devices include the "LA-960" manufactured by Horiba Manufacturing Co., Ltd.

[0248] (E) The specific surface area of ​​the inorganic filler material is not particularly limited, but is preferably 0.1 m². 2 / g or more, preferably 0.5m 2 / g or more, further preferably 1m 2 / g or more or 3m 2 / g or more. (E) There is no particular limit to the upper limit of the specific surface area of ​​the inorganic filler material, but it is preferably 100m². 2 / g or less, preferably 70m 2 / g or less, more preferably 50m 2 / g or less, especially preferably 40m 2 / g or less, 30m 2 / g or less, 20m 2 / g or less or 10m 2 / g or less. The specific surface area of ​​inorganic fillers can be calculated using the BET method, by using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) to adsorb nitrogen gas onto the sample surface and then using the BET multi-point method.

[0249] (E) The inorganic filler material is preferably surface-treated with a surface treatment agent. Surface treatment improves the moisture resistance and dispersibility of the (E) inorganic filler material. Examples of surface treatment agents include: vinyl silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; epoxy silane coupling agents such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, and 3-epoxypropoxypropyltriethoxysilane; styrene-based silane coupling agents such as p-styrenetrimethoxysilane; and 3-methylpropene. Methacrylic acid-based silane coupling agents for acyloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, etc.; acrylic acid-based silane coupling agents for 3-acryloxypropyltrimethoxysilane, etc.; N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminoethyl... Amino silane coupling agents such as tri(trimethoxysilylpropyl)isocyanurate, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-8-aminooctyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; isocyanurate silane coupling agents such as tri(trimethoxysilylpropyl)isocyanurate; ureoyl silane coupling agents such as 3-ureopropyltrialkoxysilane; 3-mercaptopropyl... The surface treatment agent includes mercapto-based silane coupling agents such as methyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; isocyanate-based silane coupling agents such as 3-isocyanatopropyltriethoxysilane; anhydride-based silane coupling agents such as 3-trimethoxysilylpropylsuccinic anhydride; sulfide-based silane coupling agents such as bis(triethoxysilylpropyl)tetrasulfide; and other silane coupling agents, as well as non-silane coupling-alkoxysilane compounds such as methyltrimethoxysilane and phenyltrimethoxysilane, organosilazane compounds, titanate-based coupling agents, etc. Furthermore, a single surface treatment agent can be used alone, or two or more can be used in any ratio. In one embodiment, (E) the inorganic filler material is preferably surface-treated with an amino-based silane coupling agent, and more preferably with N-phenyl-3-aminopropyltrimethoxysilane.

[0250] From the viewpoint of improving the dispersibility of inorganic filler materials, the degree of surface treatment by surface treatment agent is preferably within a specified range. Specifically, 100 parts by mass of inorganic filler material is preferably surface treated with 0.2 parts by mass to 5 parts by mass of surface treatment agent, preferably with 0.2 parts by mass to 3 parts by mass of surface treatment agent, and preferably with 0.3 parts by mass to 2 parts by mass of surface treatment agent.

[0251] The degree of surface treatment by the surface treatment agent can be evaluated by the carbon content per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the preferred carbon content per unit surface area of ​​the inorganic filler is 0.02 mg / m². 2 The above, more preferably 0.1 mg / m 2 The above is further preferred to be 0.2 mg / m². 2 The above. The preferred upper limit is 1.0 mg / m². 2 The following is more preferably 0.8 mg / m 2 The following is a further preferred dosage: 0.5 mg / m² 2 the following.

[0252] (E) The carbon content per unit surface area of ​​the inorganic filler material can be determined after cleaning the surface-treated inorganic filler material with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, sufficient MEK as a solvent is added to the surface-treated inorganic filler material, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid components, the carbon content per unit surface area of ​​the inorganic filler material can be determined using a carbon analyzer. A carbon analyzer such as the "EMIA-320V" manufactured by Horiba Corporation can be used.

[0253] In the case where the resin composition layer of the resin sheet according to the first embodiment of the present invention contains (E) inorganic filler material, from the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile component in the resin composition layer is set to 100% by mass, the content of the (E) component in the resin composition layer is preferably 10% by mass or more or 20% by mass or more, more preferably 30% by mass or more or 40% by mass or more, further preferably 45% by mass or more, 50% by mass or more or 55% by mass or more, particularly preferably 60% by mass or more, 65% by mass or more or 70% by mass or more. The upper limit is preferably 90% by mass or less, more preferably 85% by mass or less, further preferably 80% by mass or less, and particularly preferably 75% by mass or less.

[0254] In the case where the resin composition layer of the resin sheet according to the first embodiment of the present invention contains inorganic filler material (E), when the non-volatile component in the resin composition layer is set to 100% by mass, the total content of component (1A), component (B), component (C), and component (E) in the resin composition layer is preferably 50% by mass or more, more preferably 60% by mass or more or 65% by mass or more, further preferably 70% by mass or more or 75% by mass or more, and particularly preferably 80% by mass or more or 84% by mass or more. There is no particular limitation on the upper limit; it can also be 100% by mass, or it can be 99% by mass or less, 98% by mass or less, 95% by mass or less, 92% by mass or less, 90% by mass or less, 88% by mass or less, etc.

[0255] <(1F) Other maleimide compounds> In the resin composition layer of the resin sheet according to the first embodiment of the present invention, maleimide compounds other than component (1A) may be included as an optional component (hereinafter referred to as "(1F) other maleimide compounds"). One of the (1F) other maleimide compounds may be used alone, or two or more may be used in combination.

[0256] As for other maleimide compounds in (1F), there is no particular limitation on their type as long as they have one or more (preferably two or more) maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrole-1-yl) in one molecule and are not part of (1A). Examples of maleimide compounds include “BMI-3000J”, “BMI-5000”, “BMI-1400”, “BMI-1500”, “BMI-1700”, and “BMI-689” (all designed by Designer Molecules). Maleimide compounds derived from dimeric diamines, including those containing an aliphatic skeleton with 36 carbon atoms (such as those manufactured by Shin-Etsu Chemical Co., Ltd.), "SLK-1500" (manufactured by Shin-Etsu Chemical Co., Ltd.), "SLK-6895" (manufactured by Shin-Etsu Chemical Co., Ltd.), and "BMI-TMH" (manufactured by Yamato Chemical Co., Ltd.); maleimide compounds containing an indane skeleton as described in Japan Invention Association Publication No. 2020-500211; and maleimide compounds containing an aromatic ring skeleton directly bonded to the nitrogen atom of the maleimide group, such as "MIR-3000-70MT", "MIR-5000-60T" (manufactured by Nippon Kayaku Co., Ltd.), "BMI-4000", "BMI-2300" (manufactured by Yamato Chemical Co., Ltd.), "BMI-80", and "BMI-70" (manufactured by KI Chemical Co., Ltd.).

[0257] In the case where the resin composition layer of the resin sheet according to the first embodiment of the present invention contains other maleimide compounds (1F), from the viewpoint of significantly obtaining the effects of the present invention, when the resin component in the resin composition layer is set to 100% by mass, the content of the (1F) component in the resin composition layer is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more or 0.2% by mass or more, particularly preferably 0.5% by mass or more or 0.8% by mass or more. In another embodiment, it can be 1% by mass or more, 1.5% by mass or more, 2% by mass or more, 2.5% by mass or more, 3% by mass or more, etc. The upper limit is preferably 20% by mass or less, more preferably 18% by mass or less or 15% by mass or less, further preferably 12% by mass or less or 10% by mass or less, particularly preferably 8% by mass or less or 7% by mass or less. In another embodiment, it can be 6% by mass or less, 5.5% by mass or less, 5% by mass or less, 4.5% by mass or less, 4% by mass or less, etc.

[0258] In the case where the resin composition layer of the resin sheet according to the first embodiment of the present invention contains other maleimide compounds (1F), from the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile component in the resin composition layer is set to 100% by mass, the content of the (1F) component in the resin composition layer is preferably 0.001% by mass or more, more preferably 0.005% by mass or more or 0.01% by mass or more, further preferably 0.05% by mass or more or 0.1% by mass or more, and particularly preferably 0.2% by mass or more or 0.25% by mass or more. In another embodiment, it can be 0.3% by mass or more, 0.5% by mass or more, 0.8% by mass or more, 1% by mass or more, etc. The upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, further preferably 5% by mass or less or 3% by mass or less, and particularly preferably 2% by mass or less or 1.8% by mass or less. In another embodiment, it can be 1.5% by mass or less, 1.2% by mass or less, etc.

[0259] <(G) Free Radical Polymerizing Resin> The resin composition layer of the resin sheet according to the first embodiment of the present invention may also contain (G) free radical polymerizable resin as an optional component. Substances belonging to (1A) or (1F) components are excluded from the (G) component. One type of (G) free radical polymerizable resin may be used alone, or two or more types may be used in combination.

[0260] (G) Free radical polymerizable resins may contain olefinically unsaturated bonds. Therefore, (G) free radical polymerizable resins may have free radical polymerizable groups containing olefinically unsaturated bonds. Examples of free radical polymerizable groups include unsaturated hydrocarbon groups such as vinyl, allyl, 1-propenyl, 3-cyclohexenyl, 3-cyclopentenyl, 2-vinylphenyl, 3-vinylphenyl, and 4-vinylphenyl; and α,β-unsaturated carbonyl groups such as acryloyl and methacryloyl. (G) Free radical polymerizable resins preferably have two or more free radical polymerizable groups.

[0261] Examples of (G) free radical polymerizable resins include (meth)acrylic acid-based free radical polymerizable resins, styrene-based free radical polymerizable resins, and allyl-based free radical polymerizable resins. As component (G), it is preferable to include any one of styrene-based free radical polymerizable resins, allyl-based free radical polymerizable resins, and styrene-based free radical polymerizable resins; more preferably, it includes a styrene-based free radical polymerizable resin.

[0262] (Meth)acrylic acid-based free radical polymerizable resins are, for example, compounds having one or more, preferably two or more, acryloyl groups and / or methacryloyl groups. Examples of low molecular weight (molecular weight less than 1000) aliphatic (meth)acrylate compounds, such as cyclohexane-1,4-diethanol di(meth)acrylate, cyclohexane-1,3-diethanol di(meth)acrylate, tricyclodecanediethanol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, etc.; dioxanediol di(meth)acrylate, 3,6-dioxane-1,8-octanediol di(meth)acrylate, etc. Low molecular weight (molecular weight less than 1000) ether-containing (meth)acrylate compounds such as glycol di(meth)acrylate, 3,6,9-trioxaundecane-1,11-diol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, etc.; low molecular weight (molecular weight less than 1000) isocyanurate-containing (meth)acrylate compounds such as tri(3-hydroxypropyl)isocyanurate tri(meth)acrylate, tri(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, etc.; high molecular weight (molecular weight greater than 1000) acrylate compounds such as (meth)acrylate-modified polyphenylene ether resin, etc. Commercially available (meth)acrylic acid-based free radical polymerizable resins include, for example: "A-DOG" (dioxanediol diacrylate) manufactured by Shin-Nakamura Chemical Industry Co., Ltd.; "DCP-A" (tricyclodecanediethanol diacrylate) and "DCP" (tricyclodecanediethanol dimethacrylate) manufactured by Kyoeisha Chemical Co., Ltd.; "KAYARAD R-684" (tricyclodecanediethanol diacrylate) and "KAYARAD R-604" (dioxanediol diacrylate) manufactured by Nippon Kayaku Co., Ltd.; and "SA9000" and "SA9000-111" (methacrylic acid modified polyphenylene ether) manufactured by SABIC Co., Ltd.

[0263] Styrene-based free radical polymerizable resins are, for example, compounds having one or more, preferably two or more, vinyl groups directly bonded to aromatic carbon atoms. Examples of styrene-based free radical polymerizable resins include low molecular weight (molecular weight less than 1000) styrene-based compounds such as divinylbenzene, 2,4-divinyltoluene, 2,6-divinylnaphthalene, 1,4-divinylnaphthalene, 4,4'-divinylbiphenyl, 1,2-bis(4-vinylphenyl)ethane, 2,2-bis(4-vinylphenyl)propane, and bis(4-vinylphenyl) ether; and high molecular weight (molecular weight 1000 or more) styrene-based compounds such as styrene-modified polyphenylene ether resins and styrene-divinylbenzene copolymers. Commercially available styrene-based free radical polymerizable resins include, for example, "ODV-XET(X03)", "ODV-XET(X04)", and "ODV-XET(X05)" (styrene-divinylbenzene copolymer) manufactured by Nippon Steel Chemical Materials Co., Ltd., and "OPE-2St 1200" and "OPE-2St 2200" (styrene-modified polyphenylene ether resin) manufactured by Mitsubishi Gas Chemical Co., Ltd. Additionally, styrene-based free radical polymerizable resins include, for example, copolymer A described in International Publication No. 2017 / 115813.

[0264] Allyl-based free radical polymerizable resins can be, for example, compounds having one or more, preferably two or more, allyl groups. Examples of allyl-based free radical polymerizable resins include, for instance, aromatic carboxylic acid allyl ester compounds such as diallyl diphenate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2,6-naphthalenedicarboxylate, and diallyl 2,3-naphthalenedicarboxylate; and 1,3,5-triallyl isocyanurate and 1,3-diallyl-5-glycidyl isocyanurate. Allyl isocyanurate compounds such as esters; aromatic allyl compounds containing epoxy groups such as 2,2-bis[3-allyl-4-(glycidoxy)phenyl]propane; aromatic allyl compounds containing benzoxazine such as bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazine-3-yl)phenyl]methane; aromatic allyl compounds containing ethers such as 1,3,5-triallyl ether benzene; and allylsilane compounds such as diallyl diphenylsilane. Commercially available allyl-based free radical polymerizable resins include, for example: TAIC (1,3,5-triallyl isocyanurate) manufactured by Nippon Chemical Co., Ltd.; DAD (dallyl biphenylate) manufactured by Nisshoku Techno Fine Chemical Co., Ltd.; TRIAM-705 (triallyl trimellitate) manufactured by Fujifilm and Koujun Pharmaceutical Co., Ltd.; and Nisshoku Techno Fine Chemical Co., Ltd. Products manufactured under the trade name "DAND" (2,3-naphthoic acid diallyl ester) by Chemical Co., Ltd., "ALP-d" (bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane) by Shikoku Chemical Industry Co., Ltd., "RE-810NM" (2,2-bis[3-allyl-4-(glycidoxy)phenyl]propane) by Nippon Kayaku Co., Ltd., and "DA-MGIC" (1,3-diallyl-5-glycidyl isocyanurate) by Shikoku Chemical Industry Co., Ltd., etc.

[0265] (G) The olefin unsaturated bond equivalent of the free radical polymerizable resin is preferably 20 g / eq. to 3000 g / eq., more preferably 50 g / eq. to 2500 g / eq., even more preferably 70 g / eq. to 2000 g / eq., and particularly preferably 90 g / eq. to 1500 g / eq. The olefin unsaturated bond equivalent represents the mass of the free radical polymerizable resin per 1 olefin unsaturated bond.

[0266] (G) The weight-average molecular weight (Mw) of the free radical polymerizable resin is preferably 100,000 or less, 80,000 or less, 50,000 or less, or 40,000 or less, more preferably 10,000 or less, further preferably 5,000 or less, and particularly preferably 3,000 or less. The lower limit is not particularly limited; for example, it can be 150 or more. The weight-average molecular weight can be determined by gel permeation chromatography (GPC) as a value converted from polystyrene.

[0267] When the resin composition layer of the resin sheet according to the first embodiment of the present invention contains a (G) free radical polymerizable resin, from the viewpoint of significantly obtaining the effects of the present invention, when the resin component in the resin composition layer is set to 100% by mass, the content of the (G) component in the resin composition layer is preferably 0.1% by mass or more or 0.5% by mass or more, more preferably 1% by mass or more or 2% by mass or more, further preferably 3% by mass or more or 4% by mass or more, and particularly preferably 5% by mass or more or 6% by mass or more. The upper limit is preferably 30% by mass or less or 25% by mass or less, more preferably 20% by mass or less or 15% by mass or less, further preferably 10% by mass or less or 15% by mass or less, and particularly preferably 10% by mass or less or 8% by mass or less.

[0268] In the case where the resin composition layer of the resin sheet according to the first embodiment of the present invention contains a (G) free radical polymerizable resin, when the non-volatile component in the resin composition layer is set to 100% by mass, the content of the (G) component in the resin composition layer is preferably 0.01% by mass or more, more preferably 0.05% by mass or more or 0.1% by mass or more, even more preferably 0.5% by mass or more or 1% by mass or more, particularly preferably 1.2% by mass or more or 1.5% by mass or more. The upper limit is preferably 15% by mass or less or 12% by mass or less, more preferably 10% by mass or less or 8% by mass or less, even more preferably 5% by mass or less or 4% by mass or less, particularly preferably 3% by mass or less or 2% by mass or less.

[0269] <(H) Organic filler materials> In the resin composition layer of the resin sheet according to the first embodiment of the present invention, (H) organic filler material may be included as an optional component, and (H) organic filler material is preferred. One type of (H) organic filler material may be used alone, or two or more types may be used in combination.

[0270] (H) The organic filler material exists in the resin composition in particulate form. Examples of (H) organic filler materials include rubber particles, polyamide microparticles, silicone particles, core-shell particles, etc. In this invention, from the viewpoint of significantly obtaining the desired effect of this invention, the (H) organic filler material preferably includes either rubber particles or core-shell particles, more preferably rubber particles, and even more preferably core-shell rubber particles.

[0271] Examples of rubber components contained in rubber particles include olefin-based thermoplastic elastomers such as polybutadiene, polyisoprene, polychloroprene, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-isobutylene copolymer, acrylonitrile-butadiene copolymer, isoprene-isobutylene copolymer, isobutylene-butadiene copolymer, ethylene-propylene-diene terpolymer, and ethylene-propylene-butene terpolymer; and acrylic thermoplastic elastomers such as poly(meth)acrylate, poly(meth)acrylate, poly(cyclohexyl methacrylate), and poly(octyl methacrylate), with acrylic thermoplastic elastomers being preferred. Rubber particles containing acrylic thermoplastic elastomers as rubber components are called "acrylic rubber particles." Core-shell particles containing acrylic thermoplastic elastomers as rubber components are called "acrylic core-shell particles." Core-shell rubber particles containing acrylic thermoplastic elastomers as rubber components are referred to as "acrylic core-shell rubber particles". That is, the (H) organic filler material preferably contains either acrylic rubber particles or acrylic core-shell particles, more preferably acrylic rubber particles, and even more preferably acrylic core-shell rubber particles. The rubber component may also be further mixed with silicone rubbers such as polysiloxane rubber. The glass transition temperature of the rubber component contained in the rubber particles is preferably below 0°C, more preferably below -10°C, even more preferably below -20°C, and particularly preferably below -30°C.

[0272] Commercially available products can be used as rubber particles, such as Dow Chemical Japan's "EXL-2655", AICA Industries' "STAPHYLOID AC3401N" and "STAPHYLOID AC3816N". "STAPHYLOID AC3816N" also belongs to the core-shell type of rubber particles.

[0273] Core-shell particles are particulate organic filler materials consisting of core particles containing rubber components as listed above, and a shell layer or more covering them. More preferably, core-shell particles are core-shell graft copolymer particles formed by graft copolymerizing core particles containing rubber components as listed above, and a shell layer formed by graft copolymerization of monomer components that can copolymerize with the rubber components contained in the core particles. The term "core-shell" here does not necessarily refer only to types where the core particles and shell layer can be clearly distinguished; it also includes types where the boundary between the core particles and shell layer is unclear, and the core particles may not be completely covered by the shell layer.

[0274] The rubber component preferably contains 40% by mass or more in the core-shell graft copolymer particles, more preferably 50% by mass or more, and even more preferably 60% by mass or more. There is no particular upper limit to the content of the rubber component in the core-shell graft copolymer particles, but from the viewpoint of ensuring sufficient coverage of the core particles by the shell, it is preferably, for example, 95% by mass or less, or 90% by mass or less.

[0275] Examples of monomer components that form the shell portion of core-shell graft copolymer particles include: methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, glycidyl methacrylate, and other methacrylates; methacrylic acid; N-substituted maleimides such as N-methylmaleimide and N-phenylmaleimide; maleimides; α,β-unsaturated carboxylic acids such as maleic acid and itaconic acid; aromatic vinyl compounds such as styrene, 4-vinyltoluene, and α-methylstyrene; and methacrylonitrile, with methacrylates being preferred and methyl methacrylate being more preferred.

[0276] Commercially available products containing core-shell graft copolymer particles include, for example, Samsung SDI's "CHT"; Techno UMG's "B602"; Dow Chemical Japan's "PARALOID EXL-2602", "PARALOID EXL-2603", "PARALOID EXL-2655", "PARALOID EXL-2311", "PARALOID EXL-2313", "PARALOID EXL-2315", "PARALOID KM-330", "PARALOID KM-336P", "PARALOID KCZ-201"; Mitsubishi Chemical's "METABLEN C-223A", "METABLEN E-901", "METABLEN S-2001", "METABLEN W-450A", "METABLEN SRK-200"; and Kaneka's "Kane Ace M-511", "Kane Ace M-600", etc. "Ace M-400", "Kane Ace M-580", "Kane Ace MR-01", etc. They can be used individually or in combination of two or more.

[0277] The average particle size (average primary particle size) of the core-shell graft copolymer particles is not particularly limited, but is preferably 20 nm or more, more preferably 50 nm or more, further preferably 80 nm or more, and particularly preferably 100 nm or more. The upper limit is preferably 5000 nm or less, more preferably 2000 nm or less, further preferably 1000 nm or less, and particularly preferably 500 nm or less. The average particle size (average primary particle size) of the core-shell graft copolymer particles can be measured using a zeta potential particle size distribution measuring device or the like.

[0278] In the case where the resin composition layer of the resin sheet according to the first embodiment of the present invention contains an organic filler (H), from the viewpoint of significantly obtaining the effects of the present invention, when the resin component in the resin composition layer is set to 100% by mass, the content of the (H) component in the resin composition layer is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more or 2% by mass or more, and particularly preferably 3% by mass or more or 4% by mass or more. In another embodiment, it can be 5% by mass or more, 5.5% by mass or more, 6% by mass or more, etc. The upper limit is preferably 30% by mass or less, more preferably 25% by mass or less or 20% by mass or less, further preferably 15% by mass or less or 10% by mass or less, and particularly preferably 9% by mass or less or 8% by mass or less. In another embodiment, it can be 7% by mass or less, 6.5% by mass or less, etc.

[0279] In the case where the resin composition layer of the resin sheet according to the first embodiment of the present invention contains an organic filler material (H), from the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile component in the resin composition layer is set to 100% by mass, the content of the (H) component in the resin composition layer is preferably 0.01% by mass or more or 0.05% by mass or more, more preferably 0.1% by mass or more or 0.2% by mass or more, further preferably 0.5% by mass or more or 0.8% by mass or more, and particularly preferably 1% by mass or more or 1.2% by mass or more. In another embodiment, it can be 1.5% by mass or more, etc. The upper limit is preferably 15% by mass or less or 12% by mass or less, more preferably 10% by mass or less or 8% by mass or less, further preferably 5% by mass or less or 4% by mass or less, and particularly preferably 3% by mass or less or 2% by mass or less.

[0280] <(I) Curing Accelerator> In the resin composition layer of the resin sheet according to the first embodiment of the present invention, (I) a curing accelerator may be included as an optional component, and (I) a curing accelerator is preferred. (I) A curing accelerator may be used alone or in combination of two or more.

[0281] Examples of (I) curing accelerators include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators. One type of (I) curing accelerator may be used alone, or two or more may be used in combination. The (I) curing accelerator preferably includes an amine-based curing accelerator or an imidazole-based curing accelerator, and more preferably includes an imidazole-based curing accelerator.

[0282] Examples of amine-based curing accelerators include trialkylamines such as triethylamine and tributylamine; pyridines such as 4-dimethylaminopyridine; benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene, with pyridines being preferred, and 4-dimethylaminopyridine being more preferred. They can be used alone or in combination of two or more.

[0283] Commercially available products can also be used as amine-based curing accelerators, such as "MY-25" manufactured by Ajinomoto Fine Technology Co., Ltd., and "DMAP" manufactured by Kwangei Chemical Industry Co., Ltd.

[0284] Examples of phosphorus-based curing accelerators include: tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitic phthalate, tetrabutylphosphonium hydrogen hexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butylmethylphosphonium tetraphenylborate, and other aliphatic phosphonium salts; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, and p-phosphonium chloride. Aromatic phosphonium salts including tolyltriphenylphosphonium tetrap-tolylborate, tetraphenylphosphonium tetrap-tolylborate, tetraphenylphosphonium tetrap-tolylborate, triphenylethylphosphonium tetrap-tolylborate, tri(3-methylphenyl)ethylphosphonium tetrap-tolylborate, tri(2-methoxyphenyl)ethylphosphonium tetrap-tolylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-benzoquinone addition reactants such as triphenylphosphine-p-benzoquinone addition reactants; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, and di-tert-butylphosphine. Butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, tricyclohexylphosphine, and other aliphatic phosphines; dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tri(4-ethylphenyl)phosphine, tri(4-propylphenyl)phosphine, tri(4-isopropylphenyl)phosphine, tri(4-butylphenyl)phosphine, tri(4-tert-butylphenyl)phosphine, tri(2,4-dimethylphenyl)phosphine, tri(2,5-dimethylphenyl)phosphine, tri(2,6- Aromatic phosphines include dimethylphenylphosphine, tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether. They can be used alone or in combination of two or more.

[0285] Examples of urea-based curing accelerators include: 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, and 3-(3,4-dimethylphenyl)-1,1-dimethylurea. Aromatic dimethylureas include 1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), and N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea)[toluenebisdimethylurea], etc. They can be used alone or in combination of two or more.

[0286] Examples of guanidine-based curing accelerators include: dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, and 1-(o-tolyl)biguanidine. They can be used alone or in combination of two or more.

[0287] Examples of imidazole-based curing accelerators include: 2-methylimidazolium, 2-undecylimidazolium, 2-heptadecylimidazolium, 1,2-dimethylimidazolium, 2-ethyl-4-methylimidazolium, 2-phenylimidazolium, 2-phenyl-4-methylimidazolium, 1-benzyl-2-methylimidazolium, 1-benzyl-2-phenylimidazolium, 1-cyanoethyl-2-methylimidazolium, 1-cyanoethyl-2-undecylimidazolium, 1-cyanoethyl-2-ethyl-4-methylimidazolium, 1-cyanoethyl-2-phenylimidazolium, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[ [2'-Undecylimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-triazine isocyanuric acid adduct, 2-phenylimidazolyl isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazolium, 2-phenyl-4-methyl-5-hydroxymethylimidazolium, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline and other imidazole compounds, as well as adducts of imidazole compounds and epoxy resins, preferably 1-benzyl-2-phenylimidazolium.

[0288] Commercially available imidazole-based curing accelerators include, for example, those manufactured by Shikoku Chemical Industry Co., Ltd. such as "1B2PZ", "2P4MZ", "2M4MZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK", "2MA-OK-PW", "2PHZ", "2PHZ-PW", "Cl1Z", "Cl1Z-CN", "Cl1Z-CNS", and "C11Z-A"; and "P200-H50" manufactured by Mitsubishi Chemical Co., Ltd. These can be used individually or in combination of two or more.

[0289] Examples of organometallic curing accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include: cobalt(II) acetylacetonate, cobalt(III) acetylacetonate, copper(II) acetylacetonate, zinc(II) acetylacetonate, iron(III) acetylacetonate, nickel(II) acetylacetonate, and manganese(II) acetylacetonate. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. These can be used individually or in combination of two or more.

[0290] When the resin composition layer of the resin sheet according to the first embodiment of the present invention contains (I) a curing accelerator, from the viewpoint of significantly obtaining the effects of the present invention, when the resin component in the resin composition layer is set to 100% by mass, the content of component (I) in the resin composition layer is preferably 0.01% by mass or more or 0.02% by mass or more, more preferably 0.05% by mass or more or 0.08% by mass or more, further preferably 0.1% by mass or more or 0.2% by mass or more, and particularly preferably 0.5% by mass or more or 0.8% by mass or more. The upper limit is preferably 20% by mass or less, 18% by mass or less or 15% by mass or less, more preferably 12% by mass or less, 10% by mass or less or 8% by mass or less, further preferably 5% by mass or less, 4% by mass or less or 3% by mass or less, and particularly preferably 2% by mass or less, 1.5% by mass or less or 1.2% by mass or less.

[0291] When the resin composition layer of the resin sheet according to the first embodiment of the present invention contains (I) a curing accelerator, from the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile component in the resin composition layer is set to 100% by mass, the content of component (I) in the resin composition layer is preferably 0.001% by mass or more or 0.005% by mass or more, more preferably 0.01% by mass or more or 0.02% by mass or more, further preferably 0.05% by mass or more, 0.08% by mass or more or 0.1% by mass or more, particularly preferably 0.15% by mass or more, 0.2% by mass or more or 0.25% by mass or more. The upper limit is preferably 10% by mass or less or 8% by mass or less, more preferably 5% by mass or less or 2% by mass or less, further preferably 1% by mass or less or 0.8% by mass or less, particularly preferably 0.5% by mass or less, 0.4% by mass or less or 0.3% by mass or less.

[0292] <(J) Organic Solvents> In the resin composition layer of the resin sheet according to the first embodiment of the present invention, (J) organic solvent may be included as an optional component. In the case where organic solvent remains in the resin composition layer during drying as described in the <Method for Manufacturing Resin Sheets> section described later, the resin composition layer may contain (J) organic solvent. One type of (J) organic solvent may be used alone, or two or more may be used in combination. In one embodiment, it is preferable to use two or more types of (J) organic solvent in combination.

[0293] As an organic solvent (J), examples include organic solvents composed of atoms selected from carbon, oxygen, nitrogen, phosphorus, sulfur, halogen, and hydrogen atoms. From a safety point of view, the organic solvent (J) is preferably an organic solvent composed of atoms selected from carbon, oxygen, and hydrogen atoms, and more preferably an organic solvent composed of carbon, oxygen, and hydrogen atoms.

[0294] Examples of organic solvents (J) include glycol-based organic solvents, glycol ether-based organic solvents, glycol ether ester-based organic solvents, ketone-based organic solvents, ester-based organic solvents, ether-based organic solvents, alcohol-based organic solvents, aliphatic hydrocarbon-based organic solvents, aromatic organic solvents, nitrogen-based organic solvents, sulfur-based organic solvents, and halogen-based organic solvents. Examples of nitrogen-based organic solvents include amide-based organic solvents, urea-based organic solvents, and nitrile-based organic solvents. From a safety perspective, ester-based organic solvents, ketone-based organic solvents, glycol-based organic solvents, glycol ether-based organic solvents, glycol ether ester-based organic solvents, or aromatic organic solvents are preferred as organic solvents (J), more preferably ester-based organic solvents, glycol ether ester-based organic solvents, ketone-based organic solvents, or aromatic organic solvents, further preferably ketone-based organic solvents or aromatic organic solvents, and particularly preferably ketone-based organic solvents.

[0295] Examples of diol-based organic solvents include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and trimethylene glycol.

[0296] Examples of glycol ether-based organic solvents include ethylene glycol monomethyl ether (also known as methyl cellosolve), ethylene glycol monoethyl ether (also known as cellosolve), ethylene glycol monopropyl ether (also known as propyl cellosolve), ethylene glycol monobutyl ether (also known as butyl cellosolve), ethylene glycol monoisobutyl ether (also known as isobutyl cellosolve), ethylene glycol monotert-butyl ether (also known as tert-butyl cellosolve), and ethylene glycol monohexyl ether; diethylene glycol monomethyl ether (also known as methyl carbitol), diethylene glycol mono... Carbitol derivatives include ethyl ether (also known as carbitol), diethylene glycol monopropyl ether (also known as propyl carbitol), and diethylene glycol monobutyl ether (DB) (also known as butyl carbitol); propylene glycol ethers include propylene glycol monomethyl ether (PGM, also known as 1-methoxy-2-propanol), propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; and dipropylene glycol ethers include dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether. Propylene glycol ethers are preferred, and propylene glycol monomethyl ether (1-methoxy-2-propanol) is more preferred.

[0297] Examples of glycol ether ester-based organic solvents include: ethylene glycol monomethyl ether acetate (also known as methyl cellosolve acetate), ethylene glycol monoethyl ether acetate (also known as cellosolve acetate), ethylene glycol monobutyl ether acetate (also known as butyl cellosolve acetate), and other cellosolve esters; carbitol esters such as diethylene glycol monoethyl ether acetate (EDGAc) (also known as carbitol acetate) and diethylene glycol monobutyl ether acetate (also known as butyl carbitol acetate); propylene glycol ether esters such as propylene glycol monomethyl ether acetate (PGMEAc) and propylene glycol monoethyl ether acetate; and dipropylene glycol ether esters such as dipropylene glycol monomethyl ether acetate, preferably carbitol esters, and more preferably diethylene glycol monoethyl ether acetate.

[0298] Examples of ketone-based organic solvents include aliphatic acyclic ketones such as acetone, methyl ethyl ketone (MEK), diethyl ketone, 2-pentanone, methyl isobutyl ketone, 2-hexanone, 2-heptanone (MAK), and diisobutyl ketone; aliphatic cyclic ketones such as cyclopentanone, cyclohexanone (Anone), and 2-methylcyclohexanone; and aromatic ketones such as acetophenone, with methyl ethyl ketone (MEK) or cyclohexanone being preferred. The lower limit of the number of carbon atoms in the ketone-based organic solvent is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more. The upper limit of the number of carbon atoms in the ketone-based organic solvent is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less.

[0299] Ester-based organic solvents are organic solvents with ester structures that do not belong to the glycol ether ester system. Examples include alkyl esters of fatty acids such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, n-pentyl acetate, isopentyl acetate, ethyl propionate, propyl propionate, and isopropyl propionate; alkyl esters of hydroxy acids such as methyl lactate, ethyl lactate, and butyl lactate; alkyl esters of keto acids such as methyl acetoacetate and ethyl acetoacetate; lactones such as γ-butyrolactone and α-acetyl-γ-butyrolactone; and aromatic esters such as methyl benzoate and ethyl benzoate. Lactones are preferred as ester-based organic solvents. Furthermore, the number of carbon atoms in ester-based organic solvents is preferably 3 to 9.

[0300] Ether-based organic solvents are organic solvents with ether structures that do not belong to the glycol ether system or the glycol ether ester system. Examples include aliphatic noncyclic ethers such as dimethyl ether, diethyl ether, methyl ethyl ether, diisopropyl ether, dibutyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether; aliphatic cyclic ethers such as tetrahydrofuran, 1,4-dioxane, and 1,3-dioxolane; and aromatic ethers such as anisole and phenethyl ether. The preferred number of carbon atoms in ether-based organic solvents is 2 to 9.

[0301] Alcohol-based organic solvents are organic solvents with an alcohol structure that do not belong to the diol-based or diol ether-based organic solvents. Examples include aliphatic noncyclic alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, sec-pentanol, tert-pentanol, neopentanol, n-hexanol, n-heptanol, isoheptanol, n-octanol, and 2-ethylhexanol; aliphatic cyclic alcohols such as cyclohexanol; and aromatic alcohols such as benzyl alcohol and phenethyl alcohol.

[0302] Examples of aliphatic hydrocarbon organic solvents include n-pentane, n-hexane, 2-methylpentane (also known as isohexane), n-heptane, n-octane, cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, and naphthane. The preferred number of carbon atoms in aliphatic hydrocarbon organic solvents is 5 to 10.

[0303] Examples of aromatic organic solvents include benzene, toluene, o-xylene, m-xylene, p-xylene, and ethylbenzene. 6-8 Aromatic hydrocarbons; C9 aromatic hydrocarbons including 1,2,3-trimethylbenzene, 1,3,5-trimethylbenzene (also known as trimethylbenzene), 1,2,4-trimethylbenzene, 4-ethyltoluene, 3-ethyltoluene, 2-ethyltoluene, etc.; C9 aromatic hydrocarbons including 1,2-diethylbenzene, 1,3-diethylbenzene, 1,4-diethylbenzene, 3-ethyl-o-xylene, 4-ethyl-o-xylene, 2-ethyl-p-xylene, 1,2,3,5-tetramethylbenzene, tetrahydronaphthalene, etc. 10Aromatic hydrocarbons; aromatic heterocyclic compounds such as pyridine, furan, and thiophene, preferably toluene. The aromatic organic solvent preferably has 6 to 10 carbon atoms.

[0304] Examples of amide-based organic solvents include aliphatic acyclic amides such as N,N-dimethylacetamide and N,N-dimethylformamide; lactams such as N-methyl-2-pyrrolidone and N-cyclohexyl-2-pyrrolidone; and phosphoramides such as hexamethylphosphoramide. The preferred number of carbon atoms in amide-based organic solvents is 2 to 10.

[0305] Examples of urea-based organic solvents include tetramethylurea and 1,3-dimethyl-2-imidazolinone.

[0306] Examples of nitrile organic solvents include acetonitrile, propionitrile, and benzonitrile. The preferred number of carbon atoms in nitrile organic solvents is 2 to 10.

[0307] Examples of sulfur-based organic solvents include dimethyl sulfoxide.

[0308] Examples of halogenated organic solvents include chloroform, dichloromethane, carbon tetrachloride, and 1,2-dichloroethane. The preferred number of carbon atoms in halogenated organic solvents is 1 to 10.

[0309] The preferred organic solvent for (J) is γ-butyrolactone, methyl ethyl ketone (MEK), cyclopentanone, cyclohexanone, propylene glycol, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, or toluene; more preferably, methyl ethyl ketone (MEK), cyclohexanone, diethylene glycol monoethyl ether acetate, γ-butyrolactone, propylene glycol monomethyl ether, or toluene; even more preferably, methyl ethyl ketone (MEK), cyclohexanone, propylene glycol monomethyl ether, or toluene; and particularly preferably, methyl ethyl ketone (MEK) or cyclohexanone.

[0310] <(K) Other Additives> In the resin composition layer of the resin sheet according to the first embodiment of the present invention, other additives may be further contained as optional components without hindering the purpose of the present invention. Examples of such additives include: free radical polymerization initiators such as peroxide-based and azo-based free radical polymerization initiators; thermoplastic resins such as phenoxy resins, polyvinyl acetal resins, polysulfone resins, polyethersulfone resins, polyetheretherketone resins, and polyester resins; organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium dioxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as organosilicon-based and acrylic polymer-based leveling agents; thickeners such as bentonite and montmorillonite; defoamers such as organosilicon-based, acrylic-based, fluorine-based, and vinyl resin-based defoamers; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; and ureasilanes, etc. Adhesion improvers; adhesion enhancers such as triazole-based, tetraazole-based, and triazine-based adhesion enhancers; antioxidants such as hindered phenolic antioxidants; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorinated and organosilicon surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphonic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide); dispersants such as phosphate ester-based dispersants, polyoxyethylene-based dispersants, acetylene-based dispersants, organosilicon-based dispersants, anionic dispersants, and cationic dispersants; stabilizers such as borate ester stabilizers, titanate ester stabilizers, aluminate ester stabilizers, zirconate ester stabilizers, isocyanate stabilizers, carboxylic acid stabilizers, and carboxylic anhydride stabilizers. The content of the additives can be determined according to the required properties of the resin composition. In addition, the components (1A) to (J) mentioned above may also function as free radical polymerization initiators, thermoplastic resins, organometallic compounds, colorants, polymerization inhibitors, leveling agents, thickeners, defoamers, ultraviolet absorbers, adhesion enhancers, bonding agents, antioxidants, fluorescent whitening agents, surfactants, flame retardants, dispersants, and stabilizers. In this case, the component is not component (K), but is considered as each component of (1A) to (J).

[0311] <Protective Film> The resin sheet according to the first embodiment of the present invention may include a protective film selected based on the support as an additional layer, as needed. The protective film is provided on the side of the resin composition layer that is not in contact with the support (i.e., the side opposite to the support). By laminating the protective film onto the resin sheet, it is possible to suppress the adhesion of debris or other contaminants or the formation of damage on the surface of the resin composition layer.

[0312] Examples of protective films include films containing plastic materials, metal foils, and release paper, with films and metal foils containing plastic materials being preferred.

[0313] When a protective film containing plastic materials is used, examples of such plastic materials include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylics such as polycarbonate (PC), polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, and polyimide. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0314] When using metal foil as a protective film, examples of metal foil include copper foil and aluminum foil, with copper foil being preferred. As copper foil, foil containing a single metal such as copper can be used, or foil containing an alloy of copper with other metals (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can be used.

[0315] The surface where the protective film is bonded to the resin composition layer can be treated with matte finish, corona treatment, and antistatic treatment.

[0316] Alternatively, a protective film with a release layer can also be used as a protective film on the surface bonded to the resin composition layer. Examples of release agents used in the release layer of the protective film with a release layer include, for example, one or more release agents selected from alkyd resins, polyolefin resins, polyurethane resins, and silicone resins. Commercially available release agents include "SK-1," "AL-5," and "AL-7" manufactured by Lintec Corporation. Furthermore, commercially available products can be used for the protective film with a release layer, such as "Purex" manufactured by Toyobo Corporation and "Unipeel" manufactured by Unitech Corporation, which are PET films having a release layer with an alkyd resin-based release agent or a polyolefin resin-based release agent as the main components.

[0317] The thickness of the protective film is not particularly limited, for example, it is 1 μm to 75 μm. When the protective film has a multi-layer structure, such as a protective film with a release layer, it is preferable that the overall thickness of the protective film is within the aforementioned range.

[0318] [Resin sheet for forming the insulating layer of a semiconductor packaging substrate according to the second embodiment] The resin sheet for forming the insulating layer of a semiconductor packaging substrate according to the second embodiment of the present invention has a support and a resin composition layer disposed on the support. The resin composition layer contains (2A) a maleimide compound having a second specific structure, (B) an epoxy resin, and (C) a polycarbodiimide compound. The second specific structure is described below. According to such a resin sheet, excellent contamination removal and excellent heat resistance (glass transition temperature) are exhibited, and high adhesion strength (CZ copper peel strength) is also exhibited even when exposed to high temperature and high humidity environments, resulting in a cured product (insulating layer) that possesses all three characteristics. In the present invention, "adhesion strength" refers to the adhesion strength between the insulating layer and the conductor layer of the cured product containing the resin composition layer of the resin sheet for forming the insulating layer of the semiconductor packaging substrate of the present invention. The inventors have confirmed that the adhesion strength is particularly excellent when the conductor layer is copper. Examples of adhesion strength between the insulating layer and copper include "CZ copper peel strength" and "plating peel strength". "CZ copper peel strength" refers to the adhesion strength between the insulating layer and the conductor layer (copper) when they are bonded together by lamination. "Platinum peel strength" refers to the adhesion strength between the insulating layer and the conductor layer (copper) when a conductor layer (copper) is formed by plating on the insulating layer. According to the present invention, a cured product (insulating layer) exhibits excellent CZ copper peel strength and plating peel strength, especially a cured product (insulating layer) exhibiting excellent CZ copper peel strength. The inventors have also confirmed that the cured product (insulating layer) obtained by the present invention also exhibits excellent dielectric properties (low dielectric constant, low dielectric loss tangent) and excellent reflow solderability, low coefficient of linear thermal expansion (CTE), suppressed warpage, and low arithmetic mean roughness Ra of the surface of the roughened insulating layer.

[0319] The resin sheet for forming the insulating layer of the semiconductor packaging substrate according to the second embodiment of the present invention is useful as an insulating layer for the semiconductor packaging substrate. Examples of semiconductor packaging substrates include FC-CSP, MIS-BGA package, ETS-BGA package, Fan-out type WLP (Wafer Level Package), Fan-in type WLP, Fan-out type PLP (Panel Level Package), and Fan-in type PLP. Hereinafter, "resin sheet for forming the insulating layer of the semiconductor packaging substrate" will sometimes be simply referred to as "resin sheet".

[0320] <Support Body> The resin sheet according to the second embodiment has a support body that is bonded to one side of the resin composition layer. The support body according to the second embodiment is the same as the support body according to the first embodiment.

[0321] <Resin Composition Layer> The resin sheet according to the second embodiment of the present invention has a resin composition layer disposed on a support. An insulating layer can be formed by thermally curing the resin composition layer. Typically, the insulating layer comprises a cured product of the resin composition layer, preferably only comprising a cured product of the resin composition layer. As described above, the resin composition layer contains (2A) a maleimide compound having a second specific structure, (B) an epoxy resin, and (C) a polycarbodiimide compound.

[0322] From the viewpoint of achieving thinner semiconductor packaging substrates and providing a cured product with excellent insulation even when the cured resin composition layer is a thin film, the thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, and even more preferably 55 μm or less. The lower limit of the resin composition layer thickness is not particularly limited, and is typically 5 μm or more, 10 μm or more, etc.

[0323] The resin composition layer may further contain any components in combination with components (2A) to (C). Examples of such components include (D) a curing agent, (E) an inorganic filler, (2F) other maleimide compounds, (G) a free radical polymerizable resin, (H) an organic filler, (I) a curing accelerator, (J) an organic solvent, and (K) other additives. Hereinafter, the components contained in the resin composition layer of the resin sheet according to the second embodiment of the present invention will be described.

[0324] <(2A) Maleimide compounds with a second specific structure> The resin composition layer of the resin sheet according to the second embodiment of the present invention contains (2A) a maleimide compound having the structural unit shown in the following formula (2). Component (2A) may be used alone or in combination of two or more. [Chemical Formula 32] (In equation (2), R) a1 R a2 R a3 R a4 R a5 and R a6 Each can independently represent a hydrogen atom or a hydrocarbon group with 1 to 18 carbon atoms. R 11 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. R 12 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. R 13 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. R 16 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. 1Each represents an integer from 0 to 2 independently, m 6 Each element independently represents an integer from 0 to 2, satisfying m 1 +m 6 ≤2. m 2 Each represents an integer from 0 to 4 independently, m 4 Each represents an integer from 0 to 5 independently, n 1 Each element independently represents the number of repeating units.

[0325] In equation (2), R a1 R a2 R a3 R a4 R a5 and R a6 Each of the following independently represents a hydrocarbon group with 1 to 18 hydrogen atoms or carbon atoms, and is related to R in formula (1). a1 R a2 R a3 and R a4 and R in equation (4) a5 and R a6 They have the same meaning.

[0326] In equation (2), R 11 Each of the following groups independently represents a hydrocarbon group with 1 to 18 carbon atoms, and is related to R in formula (T-2). 11 They have the same meaning.

[0327] In equation (2), R 12 Each of the following groups independently represents a hydrocarbon group with 1 to 18 carbon atoms, and is related to R in formula (T-2). 12 They have the same meaning.

[0328] In equation (2), R 13 Each of the following groups independently represents a hydrocarbon group with 1 to 18 carbon atoms, and is related to R in formula (1). 13 They have the same meaning.

[0329] In equation (2), R 16 Each of the following groups independently represents a hydrocarbon group with 1 to 18 carbon atoms, and is related to R in formula (4). 16 They have the same meaning.

[0330] In equation (2), m 1 Each represents an integer from 0 to 2 independently, m 6 Each element independently represents an integer from 0 to 2, satisfying m 1 +m 6 ≤2. m 1 Preferably 0 or 1, more preferably 0. m 6 Preferably 0 or 1, more preferably 0.

[0331] In equation (2), m 2Each independently represents an integer from 0 to 4, and m in equation (1) 2 They have the same meaning.

[0332] In equation (2), m 4 Each independently represents an integer from 0 to 5, and m in equation (4) 4 They have the same meaning.

[0333] In equation (2), n 1 Each represents the number of repeating units independently, and is related to n in equation (1). 1 They have the same meaning.

[0334] In one embodiment, component (2A) is preferably a maleimide compound having the structure shown in formula (3). [Chemical Formula 33] [Chemical Formula 34] In equations (3), (4), and (5), R a1 R a2 R a3 R a4 R a5 and R a6 Each can independently represent a hydrogen atom or a hydrocarbon group with 1 to 18 carbon atoms. R 11 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. R 12 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. R 13 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. R 16 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. 1 Each represents an integer from 0 to 2 independently, m 6 Each represents an integer from 0 to 2 independently, m 5 Each element independently represents an integer from 0 to 3, satisfying m 1 +m 6 ≤2 and m 1 +m 5 ≤3. m 2 Each represents an integer from 0 to 4 independently, m 4 Each represents an integer from 0 to 5 independently, n 1 Each element independently represents the number of repeating units, and each of n independently represents an integer greater than 1. X M1 X represents a hydrogen atom or a monovalent group as shown in formula (4). M2 * Represents a hydrogen atom or a monovalent group as shown in formula (5). * Represents a linking bond.

[0335] In equations (3), (4), and (5), R a1 R a2 R a3 R a4 R a5 and R a6 Each of the following independently represents a hydrocarbon group with 1 to 18 hydrogen atoms or carbon atoms, and is related to R in formula (1). a1 R a2 R a3 and R a4 and R in equation (4) a5 and R a6 They have the same meaning.

[0336] In equations (3), (4), and (5), R 11 Each of the following groups independently represents a hydrocarbon group with 1 to 18 carbon atoms, and is related to R in formula (T-2). 11 They have the same meaning.

[0337] In equation (3), R 12 Each of the following groups independently represents a hydrocarbon group with 1 to 18 carbon atoms, and is related to R in formula (T-2). 12 They have the same meaning.

[0338] In equation (3), R 13 Each of the following groups independently represents a hydrocarbon group with 1 to 18 carbon atoms, and is related to R in formula (1). 13 They have the same meaning.

[0339] In equations (3), (4), and (5), R 16 Each of the following groups independently represents a hydrocarbon group with 1 to 18 carbon atoms, and is related to R in formula (4). 16 They have the same meaning.

[0340] In equations (3) and (5), m 1 Each represents an integer from 0 to 2 independently, m 6 Each represents an integer from 0 to 2 independently, m 5 Each element independently represents an integer from 0 to 3, satisfying m 1 +m 6 ≤2 and m 1 +m 5 ≤3. m in equations (3) and (5) 1 and m 6 With m in equation (2) 1 and m 6 They have the same meaning. 5 Preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0341] In equation (3), m 2 Each independently represents an integer from 0 to 4, and m in equation (1)2 They have the same meaning.

[0342] In equations (4) and (5), m 4 Each independently represents an integer from 0 to 5, and m in equation (4) of the first embodiment. 4 They have the same meaning.

[0343] In equation (3), n 1 Each represents the number of repeating units independently, and is related to n in equation (1). 1 They have the same meaning.

[0344] In equation (3), X M1 This represents a hydrogen atom or a monovalent group as shown in formula (4). In one embodiment, X M1 Hydrogen atoms are preferred.

[0345] In equation (3), X M2 This represents a hydrogen atom or a monovalent group as shown in formula (5). In one embodiment, X M2 Preferably, it is a monovalent group as shown in formula (5).

[0346] The specific examples, preferred methods for number-average molecular weight and weight-average molecular weight, and preferred methods for content of component (2A) are the same as those for component (1A).

[0347] <(2A) Method for manufacturing maleimide compounds having a second specific structure> (2A) There are no restrictions on the manufacturing method of the component. (2A) The component can be manufactured, for example, by the manufacturing method described in the column <(1A) First manufacturing method of maleimide compound having a first specific structure> or the manufacturing method described in the column <(1A) Second manufacturing method of maleimide compound having a first specific structure>.

[0348] <(B) Epoxy Resin> The resin composition layer of the resin sheet according to the second embodiment of the present invention contains (B) epoxy resin. The (B) epoxy resin according to the second embodiment has the same meaning as the (B) epoxy resin according to the first embodiment.

[0349] <(C) Polycarbodiimide compounds> The resin composition layer of the resin sheet according to the second embodiment of the present invention contains a (C) polycarbodiimide compound. The (C) polycarbodiimide compound according to the second embodiment has the same meaning as the (C) polycarbodiimide compound according to the first embodiment. That is, in one embodiment, the mass ratio of component (2A) to component (C) in the resin composition layer [(2A) component / (C) component] is preferably 0.1 to 50.

[0350] <(D) Curing Agent> In the resin composition layer of the resin sheet according to the second embodiment of the present invention, (D) curing agent may be included as an optional component, and it is preferred to include (D) curing agent. The (D) curing agent according to the second embodiment has the same meaning as the (D) curing agent according to the first embodiment.

[0351] <(E) Inorganic Filler Materials> In the resin composition layer of the resin sheet according to the second embodiment of the present invention, (E) inorganic filler material may be included as an optional component, and it is preferred to include (E) inorganic filler material. The (E) inorganic filler material according to the second embodiment has the same meaning as the (E) inorganic filler material according to the first embodiment.

[0352] <(2F) Other maleimide compounds> In the resin composition layer of the resin sheet according to the second embodiment of the present invention, maleimide compounds other than component (2A) may be included as an optional component (hereinafter referred to as "(2F) other maleimide compounds"). The preferred embodiments and preferred contents of the (2F) other maleimide compounds are the same as those of the (1F) other maleimide compounds.

[0353] <(G) Free Radical Polymerizing Resin> In the resin composition layer of the resin sheet according to the second embodiment of the present invention, (G) free radical polymerizable resin may be included as an optional component. Substances belonging to components (2A) or (2F) are excluded from the (G) component. The (G) free radical polymerizable resin according to the second embodiment has the same meaning as the (G) free radical polymerizable resin according to the first embodiment.

[0354] <(H) Organic filler materials> In the resin composition layer of the resin sheet according to the second embodiment of the present invention, (H) organic filler material may be included as an optional component, and (H) organic filler material is preferred. The (H) organic filler material according to the second embodiment has the same meaning as the (H) organic filler material according to the first embodiment.

[0355] <(I) Curing Accelerator> In the resin composition layer of the resin sheet according to the second embodiment of the present invention, (I) curing accelerator may be included as an optional component, and it is preferred to include (I) curing accelerator. The (I) curing accelerator according to the second embodiment has the same meaning as the (I) curing accelerator according to the first embodiment.

[0356] <(J) Organic Solvents> In the resin composition layer of the resin sheet according to the second embodiment of the present invention, (J) organic solvent may be included as an optional component. The (J) organic solvent according to the second embodiment has the same meaning as the (J) organic solvent according to the first embodiment.

[0357] <(K) Other Additives> In the resin composition layer of the resin sheet according to the second embodiment of the present invention, other additives (K) may be included as arbitrary components to the extent that they do not impede the purpose of the present invention. The other additives (K) according to the second embodiment have the same meaning as the other additives (K) according to the first embodiment.

[0358] <Protective Film> The resin sheet according to the second embodiment of the present invention may also include a protective film selected based on the support as other layers, as needed. The protective film according to the second embodiment is the same as the protective film according to the first embodiment.

[0359] [Method for manufacturing resin sheets for forming insulating layers of semiconductor packaging substrates] Resin sheets for forming the insulating layer of a semiconductor packaging substrate can be manufactured, for example, by preparing a resin varnish by dissolving the components contained in the resin composition layer in an organic solvent, applying the resin varnish to a support using a die coater or similar machine, and then further drying it to form a resin composition layer.

[0360] As an organic solvent, examples can be made of the same organic solvents described as components of the resin composition layer. One organic solvent may be used alone, or two or more may be used in combination.

[0361] As a component of the resin composition, if a commercially available product diluted with a solvent is used, a solid resin obtained by removing the solvent can be used, or a commercially available product diluted with a solvent can be used directly. The solvent portion can also be used as an organic solvent (J).

[0362] Drying can be carried out by methods such as heating or hot air blowing. Drying conditions are not particularly limited, but drying is generally carried out with the organic solvent content in the resin composition layer typically at 10% by mass or less, preferably 5% by mass or less. Drying conditions also vary depending on the boiling point of the organic solvent in the resin composition. For example, when using a resin composition containing 30% to 60% by mass of organic solvent, a resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0363] Resin sheets can be stored in rolls. When the resin sheet has a protective film, it can usually be used by peeling off the protective film.

[0364] [Physical Properties of Resin Sheets] In one embodiment, the cured resin composition layer of the resin sheet for forming the insulating layer of the semiconductor packaging substrate according to the present invention exhibits excellent contamination removal properties. For example, as described in the <Evaluation Test for Contamination Removability> section below, when a through-hole is formed in the cured material and a decontamination treatment is performed, the longest contaminant extending from the wall surface at the bottom of the through-hole is preferably less than 5 μm in length.

[0365] In one embodiment, the cured resin composition layer of the resin sheet used for forming the insulating layer of the semiconductor packaging substrate according to the present invention exhibits high copper peel strength (CZ). For example, as described in the section on "Determination of Adhesion Strength (CZ Copper Peel Strength) to Conductor Layer Before and After Exposure to High Temperature and Humidity Environment (HAST)" described later, the load used for measuring the copper foil peel strength of the cured product (before exposure to high temperature and humidity environment (HAST)) is preferably 0.30 kgf / cm or more, more preferably 0.40 kgf / cm or more, further preferably 0.50 kgf / cm or more or 0.60 kgf / cm or more, and particularly preferably 0.65 kgf / cm or more or 0.70 kgf / cm or more. The upper limit is not particularly limited and can be 10 kgf / cm or less, 1 kgf / cm or less, etc.

[0366] In one embodiment, the cured resin composition layer of the resin sheet used for forming the insulating layer of the semiconductor packaging substrate according to the present invention exhibits a high CZ copper peel strength even after exposure to a high temperature and humidity environment (HAST). For example, as described in the section on "Determination of Adhesion Strength (CZ Copper Peel Strength) to the Conductor Layer Before and After Exposure to a High Temperature and Humidity Environment (HAST)" described later, the load used to measure the copper foil peel strength of the cured product after exposure to a high temperature and humidity environment (HAST) is preferably 0.20 kgf / cm or more, more preferably 0.30 kgf / cm or more, even more preferably 0.40 kgf / cm or more, particularly preferably 0.45 kgf / cm or more or 0.50 kgf / cm or more. The upper limit is not particularly limited and can be 10 kgf / cm or less, 1 kgf / cm or less, etc.

[0367] In one embodiment, the cured resin composition layer of the resin sheet used for forming the insulating layer of the semiconductor packaging substrate according to the present invention exhibits a low dielectric constant (Dk) even at high temperatures. For example, as described in the section on <Measurement Test of Dielectric Constant and Dielectric Loss Tangent> described later, when measured at a measurement frequency of 10 GHz and a measurement temperature of 90°C, the dielectric constant (Dk) of the cured resin composition layer of the resin sheet according to the present invention is preferably 5 or less or 4.5 or less, more preferably 4 or less or 3.9 or less, further preferably 3.8 or less or 3.7 or less, and particularly preferably 3.6 or less or 3.5 or less. The lower limit is not particularly limited and can be 1.0 or more, etc.

[0368] In one embodiment, the cured resin composition layer of the resin sheet used for forming the insulating layer of the semiconductor packaging substrate of the present invention exhibits a low dielectric loss tangent (Df) even at high temperatures. For example, as described in the <Test for Determination of Dielectric Constant and Dielectric Loss Tangent> section below, when measured at a measurement frequency of 10 GHz and a measurement temperature of 90°C, the dielectric loss tangent (Df) of the cured resin composition layer of the resin sheet according to the present invention is preferably 0.0100 or less, more preferably 0.0080 or less or 0.0060 or less, even more preferably 0.0040 or less or 0.0035 or less, and particularly preferably 0.0030 or less or 0.0025 or less. The lower limit is not particularly limited and can be 0.0001 or more, 0.0010 or more, etc.

[0369] In one embodiment, the cured resin composition layer of the resin sheet used for forming the insulating layer of the semiconductor packaging substrate according to the present invention exhibits excellent heat resistance (high glass transition temperature). For example, as described in the section on <Determination Test of Glass Transition Temperature (Tg) and Coefficient of Linear Thermal Expansion (CTE)> described later, when measured using a thermomechanical analysis apparatus, the glass transition temperature (Tg) of the cured resin composition layer of the resin sheet according to the present invention is preferably 130°C or higher or 140°C or higher, more preferably 150°C or higher or 155°C or higher, further preferably 160°C or higher or 165°C or higher, and particularly preferably 170°C or higher, 175°C or higher, or 180°C or higher. There is no particular upper limit; it can be 400°C or lower, 300°C or lower, etc.

[0370] In one embodiment, the cured resin composition layer of the resin sheet used for forming the insulating layer of the semiconductor packaging substrate according to the present invention exhibits a low coefficient of linear thermal expansion (CTE). For example, as described in the section on <Test for Determination of Glass Transition Temperature (Tg) and Coefficient of Linear Thermal Expansion (CTE)> described later, when measured using a thermomechanical analysis apparatus, the CTE of the cured resin composition layer of the resin sheet according to the present invention is preferably 30 ppm / °C or less, more preferably 25 ppm / °C or less, further preferably 20 ppm / °C or less or 18 ppm / °C or less, and particularly preferably 16 ppm / °C or less or 15 ppm / °C or less. The lower limit is not particularly limited and can be 0.1 ppm / °C or more, 1 ppm / °C or more, 3 ppm / °C or more, etc.

[0371] In one embodiment, the cured resin composition layer of the resin sheet used for forming the insulating layer of the semiconductor packaging substrate according to the present invention exhibits a characteristic of suppressed warpage. For example, when measured as described in the <Warpage Measurement> section below, the warpage of the fully cured product on an inner layer substrate cut into 120mm × 160mm dimensions is preferably 40mm or less or 35mm or less, more preferably 30mm or less or 25mm or less, further preferably 22mm or less or 20mm or less, and particularly preferably 18mm or less or 16mm or less. The lower limit is not particularly limited and can be 0.1mm or more, 1mm or more, etc.

[0372] In one embodiment, the cured resin composition layer of the resin sheet for forming the insulating layer of the semiconductor packaging substrate according to the present invention exhibits high plating peel strength. For example, when the measurement is performed as described in the "Measurement of Plating Peel Strength" section below, the load for measuring the peel strength between the insulating layer (cured product) and the plating conductor layer is preferably 0.15 kgf / cm or more, more preferably 0.20 kgf / cm or more, even more preferably 0.25 kgf / cm or more or 0.30 kgf / cm or more, and particularly preferably 0.32 kgf / cm or more or 0.34 kgf / cm or more. The upper limit is not particularly limited and can be 10 kgf / cm or less, 1 kgf / cm or less, etc.

[0373] In one embodiment, the cured resin composition layer of the resin sheet for forming the insulating layer of the semiconductor packaging substrate of the present invention exhibits a small arithmetic mean roughness (Ra) after roughening treatment. For example, when the measurement is performed as described in the section on "Determination of the arithmetic mean roughness (Ra) of the surface of the insulating layer after roughening treatment" described later, the arithmetic mean roughness (Ra) of the surface of the insulating layer after roughening treatment is preferably 100 nm or less or 90 nm or less, more preferably 80 nm or less or 70 nm or less, further preferably 60 nm or less or 50 nm or less, and particularly preferably 40 nm or less or 35 nm or less. The lower limit is not particularly limited and can be 0.1 nm or more, 1 nm or more, 10 nm or more, etc.

[0374] In one embodiment, the cured resin composition layer of the resin sheet used for forming the insulating layer of the semiconductor packaging substrate according to the present invention exhibits excellent reflow soldering resistance. For example, as described in the <Reflow Soldering Test> section below, after absorbing moisture for 19 hours in a constant temperature and humidity bath at 85% RH and 55°C, and undergoing 20 reflow soldering cycles at a peak temperature of 260°C, expansion preferably does not occur.

[0375] Here, during the reflow soldering test, as described in the "Reflow Soldering Test" section below, an inner layer substrate with copper foil laminated on both sides of the resin substrate is used; however, sometimes an inner layer circuit is formed on this copper foil. In cases where the resin substrate is exposed by forming the inner layer circuit ( Figure 1 The inner layer circuits (2-4) easily absorb moisture from this exposed portion, thus easily expanding during reflow soldering tests. On the other hand, when the resin substrate is not exposed ( Figure 1 The inner layer circuit 1) is prone to expansion because the gas generated in the resin composition layer during reflow soldering has no escape path. That is, expansion during reflow soldering can be caused by the two reasons mentioned above, but it is preferable that expansion caused by any reason does not occur. That is, it is preferable that even when using... Figure 1 When any one of the inner layer circuits 1 to 4 is used, no expansion occurs during the reflow soldering test.

[0376] [Semiconductor packaging substrate and its manufacturing method] The semiconductor packaging substrate of the present invention includes a circuit substrate and a semiconductor chip mounted on the circuit substrate. The circuit substrate includes an insulating layer formed by curing a resin composition layer from the resin sheet of the present invention. This semiconductor packaging substrate can be manufactured by bonding the semiconductor chip onto the circuit substrate. The circuit substrate is described below.

[0377] As long as the terminal electrodes of the semiconductor chip are conductively connected to the circuit wiring of the circuit board, the bonding conditions are not particularly limited, and the known conditions used in flip-chip mounting of semiconductor chips can be used. Furthermore, bonding can be achieved between the semiconductor chip and the circuit board using an insulating adhesive.

[0378] A preferred embodiment involves pressing a semiconductor chip onto a circuit board. For example, the pressing conditions may include a pressing temperature in the range of 120°C to 240°C (preferably 130°C to 200°C, more preferably 140°C to 180°C), and a pressing time in the range of 1 second to 60 seconds (preferably 5 seconds to 30 seconds).

[0379] Another preferred embodiment is to bond the semiconductor chip to the circuit board via reflow soldering. The reflow soldering conditions can be set, for example, in the range of 120°C to 300°C.

[0380] After bonding the semiconductor chip to a circuit board, a semiconductor chip package can also be obtained, for example, by filling the semiconductor chip with a molding underfill material. The method of filling with molding underfill material can be implemented using known methods.

[0381] The circuit board includes an insulating layer formed from a cured resin composition layer utilizing the resin sheet of the present invention. This circuit board can be manufactured, for example, by a manufacturing method including the following steps (I) and (II): (I) A process of laminating a resin sheet onto an inner substrate in such a way that the resin composition layer of the resin sheet is bonded to the inner substrate; (II) A process of curing the resin composition layer to form an insulating layer.

[0382] The "inner layer substrate" used in process (I) refers to a component that becomes a circuit board, such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, or a thermosetting polyphenylene ether substrate. Furthermore, this substrate may have a conductive layer on one or both sides, which may be patterned. An inner layer substrate with a conductive layer (circuit) formed on one or both sides of the substrate is sometimes called an "inner layer circuit board." In addition, intermediate components that require further formation of insulating layers and / or conductive layers during the manufacturing of the circuit board are also included in the aforementioned "inner layer substrate." When the circuit board is a circuit board with components built-in, an inner layer substrate with built-in components can be used.

[0383] The lamination of the inner substrate and the resin sheet can be achieved, for example, by heating and pressing the resin sheet onto the inner substrate from the support side. Examples of components for heating and pressing the resin sheet onto the inner substrate (hereinafter also referred to as "heat-pressing components") include, for example, a heated metal plate (SUS end plate, etc.) or a metal roller (SUS roller, etc.). It should be noted that it is preferable not to directly press the resin sheet onto the heat-pressing component, but rather to press it using an elastic material such as heat-resistant rubber, so that the resin sheet fully conforms to the surface irregularities of the inner substrate.

[0384] The lamination of the inner substrate and the resin sheet can be performed using vacuum lamination. In vacuum lamination, the heating and pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C; the heating and pressing pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa; and the heating and pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination can preferably be performed under reduced pressure conditions below 26.7 hPa.

[0385] Lamination can be performed using commercially available vacuum laminators. Examples of commercially available vacuum laminators include the vacuum pressure laminator manufactured by Meiki Manufacturing Co., Ltd., the vacuum dressing machine manufactured by Nikko-Materials Co., Ltd., and batch vacuum pressure laminators.

[0386] After lamination, the laminated resin sheets can be smoothed under normal pressure (atmospheric pressure), for example, by pressing the heated pressing member from the support side. The pressing conditions for smoothing can be the same as the heating and pressing conditions for lamination described above. Smoothing can be performed using a commercially available laminator. It should be noted that lamination and smoothing can be performed continuously using the aforementioned commercially available vacuum laminator.

[0387] The support can be removed between process (I) and process (II), or it can be removed after process (II).

[0388] In step (II), the resin composition layer is cured to form an insulating layer containing the cured resin composition layer. The curing of the resin composition layer is typically performed by heat curing. Specific curing conditions for the resin composition layer can use those typically used when forming an insulating layer for a circuit board.

[0389] For example, the thermosetting conditions of the resin composition layer vary depending on the types of components contained in the resin composition layer. In one embodiment, the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and even more preferably 170°C to 210°C. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0390] The resin composition layer can be preheated at a temperature lower than the curing temperature before heat curing. For example, before heat curing the resin composition layer, it can be preheated at a temperature of 50°C to 150°C, preferably 60°C to 140°C, more preferably 70°C to 130°C, for at least 5 minutes, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes.

[0391] When manufacturing a circuit board, steps (III) of opening holes in the insulating layer, (IV) of roughening the insulating layer, and (V) of forming a conductor layer can be further performed. These steps (III) to (V) can be performed according to various methods known to those skilled in the art for manufacturing circuit boards. It should be noted that if the support is removed after step (II), the removal of the support can be performed between steps (II) and (III), between steps (III) and (IV), or between steps (IV) and (V). Furthermore, the formation of the insulating and conductor layers in steps (I) to (V) can be repeated as needed to form a multilayer wiring board.

[0392] Process (III) is the process of creating openings in the insulating layer, thereby forming through holes, vias, and other holes in the insulating layer. Process (III) can be performed using, for example, a drill bit, laser, plasma, etc., depending on the composition of the resin composition used to form the insulating layer. The size and shape of the holes can be appropriately determined according to the design of the printed circuit board.

[0393] Step (IV) is a process for roughening the insulating layer. Typically, contaminant removal is also performed in this step (IV). The steps and conditions for roughening are not particularly limited, and known steps and conditions commonly used in forming the insulating layer of a circuit board can be employed. For example, the insulating layer can be roughened sequentially by performing a swelling treatment using a swelling solution, a roughening treatment using an oxidizing agent, and a neutralization treatment using a neutralizing solution.

[0394] Examples of swelling solutions used for roughening treatment include alkaline solutions and surfactant solutions, with alkaline solutions being preferred. Sodium hydroxide solution and potassium hydroxide solution are more preferred. Commercially available swelling solutions include, for example, "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Ammet Japan Co., Ltd. Swelling treatment using a swelling solution can be performed, for example, by immersing the insulating layer in a swelling solution at 30°C to 90°C for 1 to 20 minutes. From the viewpoint of controlling the swelling of the resin in the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling solution at 40°C to 80°C for 5 to 15 minutes.

[0395] Examples of oxidants used in roughening treatments include alkaline permanganate solutions obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. Roughening treatment using alkaline permanganate solutions or similar oxidants preferably involves immersing the insulating layer in an oxidant solution heated to 60°C to 100°C for 10 to 30 minutes. Furthermore, the concentration of permanganate in the alkaline permanganate solution is preferably 5% to 10% by mass. Commercially available oxidants include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Ammet Japan Co., Ltd.

[0396] The neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and commercially available products include, for example, "Reduction Solution Securiganth P" manufactured by Ammet Japan Co., Ltd. The treatment using the neutralizing solution can be performed by immersing the roughened surface treated with an oxidant in a neutralizing solution at 30°C to 80°C for 5 to 30 minutes. From an operability perspective, it is preferable to immerse the roughened object treated with an oxidant in a neutralizing solution at 40°C to 70°C for 5 to 20 minutes.

[0397] Step (V) is the step of forming a conductor layer, which is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer comprises one or more metals selected from gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer can be a single metal layer or an alloy layer. Examples of alloy layers include layers formed from alloys of two or more metals selected from the above-mentioned metals (e.g., nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys). From the viewpoints of versatility, cost, and ease of pattern formation in conductor layer formation, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium, copper-nickel, or copper-titanium alloys, is preferred. More preferably, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloys, is even more preferred. A single metal layer of copper is even more preferred.

[0398] The conductor layer can be a single-layer structure, or a multi-layer structure consisting of two or more single-metal layers or alloy layers of different types of metals or alloys. When the conductor layer is a multi-layer structure, the layer in contact with the insulating layer is preferably a single-metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.

[0399] The thickness of the conductor layer depends on the desired design of the semiconductor packaging substrate, but is generally 3μm to 35μm, preferably 5μm to 30μm.

[0400] In one embodiment, the conductor layer can be formed by plating. For example, the surface of the insulating layer can be plated using conventionally known techniques such as semi-additive or fully additive methods to form a conductor layer with the desired wiring pattern. From the viewpoint of ease of manufacture, the semi-additive method is preferred. An example of forming a conductor layer using the semi-additive method is shown below.

[0401] First, a seed layer is formed on the surface of an insulating layer by electroless plating. Next, a mask pattern is formed on the formed seed layer, corresponding to a desired wiring pattern, exposing a portion of the seed layer. After forming a metal layer on the exposed seed layer by electrolytic plating, the mask pattern is removed. Then, the unwanted seed layer is removed by etching or the like, thereby forming a conductor layer with the desired wiring pattern.

[0402] In another embodiment, the conductor layer can be formed using metal foil. When using metal foil to form the conductor layer, step (V) is preferably performed between steps (I) and (II). For example, after step (I), the support is removed, and metal foil is laminated onto the surface of the exposed resin composition layer. The lamination of the resin composition layer and the metal foil can be performed by vacuum lamination. The lamination conditions can be the same as those described for step (I). Next, step (II) is performed to form an insulating layer. Then, using the metal foil on the insulating layer, a conductor layer with the desired wiring pattern can be formed using conventionally known techniques such as subtractive processing or modified semi-additive processing.

[0403] Metal foils can be manufactured using known methods such as electrolysis and rolling. Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Metals Corporation, and 3EC-III foil and TP-III foil manufactured by Mitsui Metals & Mining Corporation.

[0404] [Semiconductor Devices] Examples of semiconductor devices for mounting the semiconductor packaging substrate of the present invention include various semiconductor devices supplied to electrical products (e.g., computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical devices, and televisions) and vehicles (e.g., two-wheeled motor vehicles, automobiles, trams, ships, and aircraft). Example

[0405] The present invention will be specifically described below with reference to embodiments. However, the present invention is not limited to these embodiments. In the following description, unless otherwise specified, "parts" and "%" refer to "parts by mass" and "% by mass," respectively. In addition, the temperature and pressure conditions, unless otherwise specified, are room temperature (23°C) and atmospheric pressure (1 atm).

[0406] <Synthetic Example 1: Synthesis of maleimide compound (A-1)> (I) Synthesis of intermediate amine compound (c-1) In a flask equipped with a thermometer, cooling tubes, a Dean-Stark trap, and a stirrer, 400 g (3.3 mol) of 2-ethylaniline, 127 g of compound (b) with a benzyl ether skeleton (NIKANOL L, manufactured by Fudow), 193 g of toluene, and 53 g of activated clay were added. The mixture was heated to 120 °C while stirring and held for 30 minutes. Then, the temperature was increased to 150 °C and held for 3 hours. After this holding period, the temperature was increased to 200 °C over 30 minutes and held for 10 hours. After this holding period, the mixture was diluted with 193 g of toluene, and the activated clay was separated by filtration. The solvent and excess 2-ethylaniline were removed from the filtrate by distillation under reduced pressure to obtain the intermediate amine compound (c-1) (amine equivalent 209 g / eq.).

[0407] (II) Maleimide In a 2L flask equipped with a thermometer, cooling tube, Dean-Stark separator, and stirrer, 73.2 g (126 mol, 1.3 equivalents) of maleic anhydride and 461 g of toluene were added and stirred at room temperature. Next, a mixed solution of 209 g (1 equivalent) of intermediate amine compound (C-1) and 57.7 g of N,N-dimethylformamide (DMF) was added dropwise over 1 hour, and the reaction was allowed to proceed for 2 hours. Then, 9.72 g of p-toluenesulfonic acid monohydrate was added to the reaction solution, and the solution was heated to 115°C. After cooling and separating the azeotropic water and toluene under reflux, only the toluene was returned to the system for a 5-hour dehydration reaction. After air cooling to room temperature, the resulting brown solution obtained by vacuum concentration was dissolved in 600 g of ethyl acetate, washed three times with 200 g of deionized water, and then washed three times with 150 g of 2% sodium bicarbonate aqueous solution. After adding sodium sulfate and drying, the reactants obtained by vacuum concentration were dried at 80°C for 4 hours to obtain maleimide compound (A-1). [Chemical Formula 35] Maleimide compound (A-1)

[0408] <Synthetic Example 2: Synthesis of maleimide compound (A-2)> (I) Synthesis of intermediate amine compound (c-2) In a flask equipped with a thermometer, cooling tube, Dean-Stark water separator, and stirrer, 242.4 g (2.0 mol) of 2-ethylaniline, 242 g of xylene, and 80 g of activated clay were added. The mixture was heated to 130 °C while stirring and maintained for 30 minutes. Then, 272.0 g of DVB-810 (a mixture of divinylbenzene and ethylstyrene (divinylbenzene:ethylstyrene = 81:19 (mol%)), manufactured by Nippon Steel Chemical Materials Co., Ltd.), was added dropwise over 2 hours, reacting directly for 1 hour. The temperature was then raised to 190 °C over 6 hours and maintained for 10 hours. After the reaction, the mixture was air-cooled to 100 °C, diluted with 300 g of toluene, and the activated clay was removed by filtration. The solvent and unreacted low-molecular-weight compounds were removed by distillation under reduced pressure, yielding the intermediate amine compound (c-2). The amine equivalent of the intermediate amine compound (c-2) was 214 g / eq.

[0409] (II) Maleimide In a 2L flask equipped with a thermometer, cooling tube, Dean-Stark separator, and stirrer, 117.7 g (1.2 mol) of maleic anhydride and 700 g of toluene were added and stirred at room temperature. Then, a mixed solution of 214 g (1 equivalent) of intermediate amine compound (c-2) and 175 g of DMF was added dropwise over 1 hour, and the reaction was allowed to proceed for 2 hours. 37.1 g of p-toluenesulfonic acid monohydrate was added to the reaction solution, and the mixture was heated to 115°C. After cooling and separating the azeotropic water and toluene under reflux, only the toluene was returned to the system for a 5-hour dehydration reaction. After air cooling to room temperature, the mixture was neutralized with a 49% sodium hydroxide (NaOH) aqueous solution. Then, toluene and water were removed by vacuum distillation at 60°C. 600 g of MEK (methyl ethyl ketone) was added to the remaining DMF solution in the flask. The solution was then heated to 60°C and subjected to three separate treatments with 200 g of deionized water to remove salts from the solution. After adding sodium sulfate and drying, the reactants obtained by vacuum concentration were dried at 80°C to obtain maleimide compound (A-2). Maleimide compound (A-2) is a mixture with the following three maleimide compounds as the main components. [Chemical Formula 36] Maleimide compound (A-2)

[0410] <Synthesis Example 3: Synthesis of Active Ester Resin (D-1)> 320 g (2.0 mol) of 2,7-dihydroxynaphthalene, 184 g (1.7 mol) of benzyl alcohol, and 5.0 g of p-toluenesulfonic acid monohydrate were added to a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer. The mixture was stirred while being purged with nitrogen at room temperature. Then, the temperature was raised to 150 °C, and the generated water was distilled off while stirring for 4 hours. After the reaction was complete, 900 g of methyl isobutyl ketone and 5.4 g of 20% sodium hydroxide aqueous solution were added for neutralization. The aqueous layer was then removed by separation, followed by three washes with 280 g of water, and the removal of methyl isobutyl ketone under reduced pressure to obtain 460 g of benzyl-modified naphthalene compound (D'). The obtained benzyl-modified naphthalene compound (D') was a black solid with a hydroxyl equivalent of 180 g / eq.

[0411] In a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer, 203.0 g of isophthaloyl chloride (2.0 mol of acyl chloride group) and 1400 g of toluene were added. The system was then purged with nitrogen under reduced pressure and dissolved. Next, 113.9 g (0.67 mol) of o-phenylphenol and 240 g of benzyl-modified naphthalene compound (D') (1.33 mol of phenolic hydroxyl group) were added, and the system was purged with nitrogen under reduced pressure and dissolved. Then, 0.70 g of tetrabutylammonium bromide was dissolved, and while purging with nitrogen and maintaining the system temperature below 60°C, 400 g of 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. Under these conditions, the mixture was stirred for another 1 hour to allow the reaction to proceed.

[0412] After the reaction was completed, the mixture was allowed to stand and separate to remove the aqueous layer. Then, water was added to the toluene layer containing the reactants and stirred for 15 minutes. The mixture was allowed to stand and separate to remove the aqueous layer. This process was repeated until the pH of the aqueous layer reached 7. The water was then removed using a decanter to obtain an active ester resin (D-1) in a toluene solution containing 65% by mass of non-volatile components. The active ester equivalent of the obtained active ester resin (D-1) was 238 g / eq. [Chemical Formula 37] Reactive ester resin (D-1)

[0413] <Synthesis Example 4: Synthesis of Reactive Ester Resin (D-3)> In a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer, 165 g of a dicyclopentadiene and phenol addition polymerization resin (hydroxyl equivalent: 165 g / eq., softening point 85 °C), 134 g (1.0 mol) of o-allylphenol, and 1200 g of toluene were added, and the system was purged with nitrogen under reduced pressure. Next, 203 g (1.0 mol) of isophthaloyl chloride was added, and the system was purged with nitrogen under reduced pressure. Then, 0.6 g of tetrabutylammonium bromide was added, and while purging with nitrogen and maintaining the system temperature below 60 °C, 412 g of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. After the addition was complete, the mixture was stirred for 1 hour. After the reaction was complete, the aqueous layer was removed by sedimentation. Water was further added to the resulting toluene layer, and the mixture was stirred for 15 minutes. The aqueous layer was then removed by sedimentation. This process was repeated until the pH of the aqueous layer reached 7. Then, the non-volatile components are adjusted to 70% by mass by heating and drying to obtain an active ester resin (D-3) expressed by the following formula. s represents an integer greater than or equal to 1, and the average value of r calculated based on the feed ratio is 1. Additionally, the wavy line represents the structure obtained by reacting isophthaloyl chloride, phenol, and / or o-allylphenol in an addition polymerization reaction. [Chemical Formula 38]

[0414] <Synthetic Example 5: Synthesis of Other Maleimide Compounds (F-1)> According to Synthesis Example 1 published by the Japan Invention Association under Patent No. 2020-500211, a MEK solution (62% by mass of non-volatile component) of the maleimide compound (F-1) shown in the following formula was prepared. The Mw / Mn ratio of this maleimide compound (F-1) is 1.81, and t” in the formula is 1.47 (mainly 1, 2 or 3). [Chemical Formula 39] Other maleimide compounds (F-1)

[0415] <Synthesis Example 6: Synthesis of Vinyl Resin (G-1)> 3.0 mol (390.6 g) of divinylbenzene, 1.8 mol (229.4 g) of ethylvinylbenzene, 10.2 mol (1066.3 g) of styrene, and 15.0 mol (1532.0 g) of n-propyl acetate were added to a 5.0 L reactor. Then, 600 mmol of a boron trifluoride diethyl ether complex was added at 70 °C, and the reaction was carried out for 4 hours. The polymerization was stopped with an aqueous sodium bicarbonate solution. The oil layer was then washed three times with pure water, and the polymer was recovered by vacuum devolatilization at 60 °C. The obtained polymer was weighed, confirming that 896.7 g of vinyl resin (G-1) was obtained. The weight-average molecular weight (Mw) of vinyl resin (G-1) was 41300.

[0416] <Synthesis Example 7: Synthesis of Vinyl Resin (G-2)> In a four-necked separable flask equipped with a stirrer, 33.85 g of 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane, 16.66 g of 4,6-dichloro-2-phenylpyrimidine, and 18.66 g of potassium carbonate were weighed and added. 42.50 g of N-methyl-2-pyrrolidone was then added, and the mixture was reacted at 10°C for 6 hours under a nitrogen atmosphere. After the reaction, with the container cooled to 10°C, 8.68 g of m,p-(chloromethyl)styrene was added dropwise, and the mixture was reacted at 100°C for 4 hours.

[0417] N-methyl-2-pyrrolidone (55.0 g) was added to the resulting reaction solution. After removing the salt from the diluted liquid by filtration, the resulting solution was added to methanol (6900 g). The precipitated solid was separated by filtration, washed with a small amount of methanol, filtered again, and recovered. The solid was then dried under reduced pressure at 60°C for 12 hours using a vacuum dryer to obtain vinyl resin (G-2) (yield 46.55 g, 90%). The weight-average molecular weight (Mw) of vinyl resin (G-2) was 3400.

[0418] <Synthetic Example 8: Synthesis of Polycarbodiimide Compound (C-1)> 100 parts by mass of dicyclohexylmethane-4,4'-diisocyanate (HMDI) and 0.5 parts by mass of 3-methyl-1-phenyl-2-phospho-1-oxide as a carbodiimide catalyst were added to a reaction vessel equipped with a reflux tube and a stirrer. The mixture was stirred and mixed at 185°C for 24 hours under a nitrogen atmosphere to carry out the carbodiimide reaction, yielding isocyanate-terminated polycarbodiimide. The obtained isocyanate-terminated polycarbodiimide was confirmed by IR spectroscopy at a wavelength of 2150 cm⁻¹. -1 The absorption peaks are around 100° based on the carbodiimide group. Additionally, the terminal NCO content is 8.19% by mass, and the average degree of polymerization of the carbodiimide group determined by the above method is 3.5.

[0419] Next, 8.8 parts by weight of ethylene glycol monoacrylate and 4 parts by weight of dihydroxyl-terminated polybutadiene ("G-1000" manufactured by Nippon Soda Co., Ltd., with a number average molecular weight of 1400, 1,2-addition structural units of more than 85%, and trans-1,4-addition structural units of less than 15%) were added to the above-mentioned isocyanate-terminated polycarbodiimide. The mixture was heated to 180°C and stirred for 2 hours to allow the reaction to proceed. IR spectroscopy confirmed the reaction at wavelengths of 2200–2300 cm⁻¹. -1 After the absorption peak of the isocyanate group disappears, the reaction product is removed from the reaction vessel and cooled to room temperature to obtain a pale yellow, transparent solid polycarbodiimide compound (a compound with a carbodiimide structure containing free radical polymerizable groups; the main component is a compound of the following formula; b' refers to the average degree of polymerization of the carbodiimide group. d' refers to the average degree of polymerization of the combined unit of polybutadiene and polycarbodiimide. e' refers to the average degree of polymerization of the butadiene unit corresponding to the above number-average molecular weight. As the e' unit, only the 1,2-addition structural unit is represented, but it also includes the 1,4-addition structural unit (cis and trans)). [Chemical Formula 40] Carbodiimide compounds (C-1)

[0420] <Examples 1-17 and Comparative Examples 1-7> (1) Manufacturing of resin composition Weigh and mix the components according to the formulation described in Table 1 below, then mix 10 parts of MEK (methyl ethyl ketone) and 10 parts of cyclohexanone, and disperse evenly using a high-speed rotary mixer to obtain a resin composition (resin varnish). It should be noted that the formulation described in Table 1 represents the amount (parts by mass) of non-volatile components. [Table 1]

[0421] In addition, the details of each component listed in Table 1 are as follows. (A) Maleimide compounds with specific structures • Maleimide compound (A-1): The maleimide compound (A-1) synthesized in Synthesis Example 1. • Maleimide compound (A-2): The maleimide compound (A-2) synthesized in Synthesis Example 2.

[0422] (B) Epoxy resin HP-4032SS: Epoxy equivalent 144 g / eq., manufactured by DIC, naphthalene-type epoxy resin. YL9133: Epoxy equivalent 191 g / eq., manufactured by Mitsubishi Chemical Corporation, bisphenol C type epoxy resin. NC-3000L: Epoxy equivalent 270g / eq., manufactured by Nippon Kayaku Co., Ltd., biphenyl type epoxy resin.

[0423] (C) Polycarbodiimide compounds V-03: Active group equivalent approximately 216 g / eq., manufactured by Nisshinbo Chemical Co., Ltd. • Polycarbodiimide compound (C-1): The polycarbodiimide compound (C-1) synthesized in Synthesis Example 8.

[0424] (D) Curing agent LA-3018-50P: A phenolic hydroxyl equivalent of 151 g / eq., a 50% by mass solution of 1-methoxy-2-propanol containing non-volatile components, manufactured by DIC Corporation, containing phenolic resins. • Active ester resin (D-1): Active ester group equivalent 238 g / eq., the active ester resin (D-1) synthesized in Synthesis Example 3. • Active ester resin (D-2): 250 g / eq. of active ester group equivalent, active ester resin as shown in the following formula (where n≥0), and a toluene solution containing 60% by mass of non-volatile components. [Chemical Formula 41] Reactive ester resin (D-2) • Reactive ester resin (D-3): 214 g / eq. of active ester group equivalent, reactive ester resin (D-3) synthesized in Synthesis Example 4, and a toluene solution containing 70% by mass of non-volatile components. • Active ester resin (D-4): 248 g / eq. of active ester group equivalent, active ester resin as shown in the following formula (mainly composed of compounds with n being integers from 0 to 6 and m being integers from 0 to 6), and a toluene solution containing 70% by mass of non-volatile components. [Chemical Formula 42] Reactive ester resin (D-4) • Active ester resin (D-5): Active ester group equivalent 1002 g / eq., active ester resin as shown in the following formula [Chemical Formula 43] HPC-8000L-65MT: An active ester resin containing a dicyclopentadiene-type diphenol structure, with an active ester equivalent of 223 g / eq. and 65% by mass of non-volatile components in a toluene / MEK solution. Manufactured by DIC Corporation.

[0425] (E) Inorganic filler materials • SO-C2: Spherical silica particles surface-treated with an amino-based silane coupling agent (Shin-Etsu Chemical Industry Co., Ltd. "KBM573", N-phenyl-3-aminopropyltrimethoxysilane), with an average particle size of 0.5 μm and a specific surface area of ​​5.8 m². 2 / g, manufactured by Yaduma Company

[0426] (F) Other maleimide compounds Other maleimide compounds (F-1): Other maleimide compounds (F-1) synthesized in Synthetic Example 5. • MIR-3000-70MT: A toluene / MEK solution containing 70% by mass of non-volatile components, manufactured by Nippon Kayaku Co., Ltd., containing a maleimide compound having the structure shown in the following formula (where n represents 1 to 100). [Chemical Formula 44] SLK-6895: An aliphatic maleimide compound manufactured by Shin-Etsu Chemical Co., Ltd. SLK-1500: An aliphatic maleimide compound manufactured by Shin-Etsu Chemical Co., Ltd.

[0427] (G) Free radical polymerizable resin OPE-2St 1200: A 65% by weight toluene solution of non-volatile components, manufactured by Mitsubishi Gas Chemical Co., Ltd., a styrene-based free radical polymerizable resin with a polyphenylene ether backbone. • Vinyl resin (G-1): The vinyl resin (G-1) synthesized in Synthesis Example 6 • Vinyl resin (G-2): The vinyl resin (G-2) synthesized in Synthesis Example 7

[0428] (H) Organic filler materials EXL-2655: An organic filler material containing rubber components manufactured by Dow Chemical Company.

[0429] (I) Curing accelerator • 1B2PZ: Imidazole-based curing accelerator (1-benzyl-2-phenylimidazolium) manufactured by Shikoku Chemical Industry Co., Ltd.

[0430] (2) Manufacturing of resin sheets As a support, a polyethylene terephthalate film (38 μm thick) that had been released using an alkyd resin-based release agent (Lintec Corporation's "AL-5") was prepared. The obtained resin composition was uniformly coated onto the release layer of this support, resulting in a dried resin composition layer thickness of 40 μm. The resin composition was then dried at 80°C to 100°C (average 90°C) for 4 minutes to obtain resin sheet A with a resin composition layer / support layer structure. Furthermore, resin sheet B was manufactured using the same manufacturing method as resin sheet A, except that the coating thickness of the resin composition was varied to achieve a dried resin composition layer thickness of 27.5 μm.

[0431] <Experimental Determination of Dielectric Constant and Dielectric Loss Tangent> Resin sheet A was heated in an oven at 190°C for 90 minutes to cure the resin composition layer. Then, the support was peeled off to obtain the cured resin composition layer. This cured layer was cut into samples with a length of 30 mm and a width of 40 mm to obtain cured samples for measuring the dielectric constant and dielectric loss tangent.

[0432] For the solidified samples, the dielectric constant Dk and dielectric loss tangent Df were measured using a measuring apparatus (Agilent Technologies, "HP8362B") at a measurement frequency of 10 GHz and a measurement temperature of 90 °C via the split cylinder method. Measurements were performed on two samples, and their average values ​​were calculated.

[0433] <Test for Determination of Glass Transition Temperature (Tg) and Coefficient of Linear Thermal Expansion (CTE)> Resin sheet A was cured in an oven at 190°C for 90 minutes, and then the support was peeled off to obtain a cured film. The cured film was cut into 20 mm long and 6 mm wide sections to obtain cured samples for measuring the glass transition temperature (Tg) and coefficient of linear thermal expansion (CTE). For these cured samples, a TMA apparatus (Thermomechanical Analysis Apparatus, Rigaku Corporation) was used, heated from 25°C to 220°C at a heating rate of 5°C / min, and measurements were taken. Subsequently, the same sample was heated from 25°C to 250°C at a heating rate of 5°C / min and measurements were taken. The Tg and CTE were calculated based on the results of the second measurement.

[0434] <Determination of the adhesion strength (CZ copper peel strength) between the conductor layer and the conductor layer before and after exposure to high temperature and high humidity (HAST) environment> (1) Resin sheet A is laminated on the inner substrate. As the inner layer substrate, a glass cloth substrate epoxy resin double-sided copper-clad laminate with copper foil on the surface was prepared (copper foil thickness 18μm, substrate thickness 0.8mm, Panasonic "R1515A"). The copper foil on this surface was etched with a copper etching amount of 1μm using a micro-etching agent (MEC "CZ8101") to roughen the surface.

[0435] Using a batch vacuum pressure laminator (Nikko-Materials Co., Ltd., 2-stage stacking laminator "CVP1700"), the resin sheet A obtained above was laminated onto both sides of the inner layer substrate in such a manner that the resin composition layer of resin sheet A was in contact with the inner layer substrate. The lamination was performed by depressurizing for 30 seconds to bring the pressure down to below 13 hPa, and then pressing for 30 seconds at a temperature of 100°C and a pressure of 0.74 MPa.

[0436] Next, the laminated resin sheet A is hot-pressed at atmospheric pressure, 100°C, and 0.5 MPa for 60 seconds to smooth it. Then, the support is peeled off to obtain an "intermediate multilayer I" that sequentially comprises a resin composition layer / inner substrate / resin composition layer.

[0437] (2) Layering of copper foil A copper foil with a glossy surface (35 μm thick, manufactured by Mitsui Metals & Mining Co., Ltd., "3EC-III") was prepared. The glossy surface of the copper foil was roughened by etching with a micro-etching agent (manufactured by MEC, "CZ8401") at a copper etching depth of 0.1 μm. The copper foil obtained in this way is called "roughened copper foil".

[0438] The roughened copper foil is laminated on both sides of the intermediate multilayer body I by bonding the roughened surface of the copper foil to the resin composition layer of the intermediate multilayer body I. This lamination is performed under the same conditions as the lamination of resin sheet A on the inner substrate described above. Thus, an "intermediate multilayer body II" is obtained, which sequentially comprises roughened copper foil / resin composition layer / inner substrate / resin composition layer / roughened copper foil.

[0439] (3) Thermosetting of the resin composition layer The obtained intermediate multilayer II was heated in an oven at 130°C for 30 minutes, and then transferred to an oven at 170°C for another 30 minutes. Next, the intermediate multilayer II was removed from the oven and allowed to cool to room temperature, then placed in an oven at 190°C for an additional 90 minutes. This process thermally cured the resin composition layer, resulting in an "evaluation substrate" sequentially comprising a roughened copper foil, an insulating layer as a cured resin composition layer, an inner substrate, an insulating layer as a cured resin composition layer, and a roughened copper foil. In this evaluation substrate, the roughened copper foil serves as a conductor layer.

[0440] (4) Determination of adhesion strength with conductor layer (CZ copper peel strength) Using the obtained evaluation substrate, the peel strength between the roughened copper foil and the insulating layer was measured. This peel strength measurement was performed based on JIS C6481. Specifically, the peel strength was measured using the following procedures.

[0441] A rectangular section, 10 mm wide and 100 mm long, was cut into the roughened copper foil of the evaluation substrate. One end of this rectangular section was peeled off and clamped in a jig (TSE AUTOCOM type testing machine "AC-50C-SL"). A 35 mm long section of this rectangular section was peeled vertically, and the peel load (kgf / cm) was measured as the peel strength. The peeling was performed at a speed of 50 mm / min at room temperature. Furthermore, after a 100-hour high-temperature and high-humidity environmental test (HAST) at 130°C and 85% RH, the same procedure was performed to measure the peel strength.

[0442] <Evaluation Test of Stain Removal Performance> (1) Preparation of inner layer substrate The inner layer substrate is obtained by etching both sides of the glass cloth substrate epoxy resin double-sided copper-clad laminate (copper foil thickness 18μm, substrate thickness 0.8mm, Panasonic "R1515A") with a micro etchant (MEC "CZ8101") to a thickness of 1μm.

[0443] (2) Lamination of resin sheet B Using a batch vacuum pressure laminator (Nikko-Materials Co., Ltd., 2-stage stacking laminator "CVP1700"), resin sheet B is laminated onto both sides of the inner layer substrate in such a manner that the resin composition layer contacts the inner layer substrate. The lamination is performed as follows: after depressurization for 30 seconds to adjust the pressure to below 13 hPa, it is pressed for 30 seconds at 120°C and 0.74 MPa. Next, it is hot-pressed for 60 seconds at 100°C and 0.5 MPa to smooth the resin composition layer.

[0444] (3) Thermosetting of the resin composition layer Then, the inner substrate with the resin sheet B stacked on it is placed in an oven at 130°C and heated for 30 minutes, followed by heating in an oven at 170°C for 30 minutes to thermally cure the resin composition layer and form an insulating layer. Then, the support is peeled off to obtain a cured substrate X with an insulating layer / inner substrate / insulating layer structure.

[0445] (4) Formation of through holes For the insulating layer of the obtained cured substrate X, through-holes were formed using a CO2 laser processing machine (Via Mechanics "LK-2K212 / 2C") at a frequency of 2000 Hz, a pulse width of 3 microseconds, an output power of 0.95 W, and a firing rate of 3. The opening diameter (top diameter) of the insulating layer surface of the formed through-hole is 50 μm, and the diameter of the bottom surface of the insulating layer is 40 μm.

[0446] (5) Roughening treatment The insulating layer of the cured substrate with through-holes is subjected to a decontamination treatment as a roughening process. As a decontamination treatment, the following wet decontamination treatment is performed.

[0447] (Wet stain removal treatment) The cured substrate with through-holes was immersed in a swelling solution (an aqueous solution of Swelling DipSecuriganth P manufactured by Amtec Japan, diethylene glycol monobutyl ether, and sodium hydroxide) at 60°C for 10 minutes. Then, the cured substrate was immersed in an oxidizing agent solution (an aqueous solution of Concentrate Compact P manufactured by Amtec Japan, approximately 6% potassium permanganate, and approximately 4% sodium hydroxide) at 80°C for 25 minutes. Finally, the cured substrate was immersed in a neutralizing solution (an aqueous solution of Reduction solution Securiganth P manufactured by Amtec Japan, sulfuric acid) at 40°C for 5 minutes. Then, the cured substrate was dried at 80°C for 15 minutes. This decontamination-treated cured substrate is sometimes referred to below as "evaluation substrate A".

[0448] (6) Evaluation of stain removal performance For the evaluation substrate A, the area around the bottom of the via was observed using a scanning electron microscope (SEM). Based on the obtained images, the length of the longest contaminant (resin residue) extending from the wall surface at the bottom of the via (maximum contaminant length) was measured and evaluated according to the following criteria. "No contamination residue": Maximum contamination length is less than 5μm. "Contaminated residue": The maximum length of contaminated residue is 5μm or more.

[0449] <Determination of Coating Peel Strength> (1) Roughening treatment The cured substrate X was immersed in a swelling solution (an aqueous solution of Swelling Dip Securiganth P manufactured by Amtec Japan, diethylene glycol monobutyl ether, and sodium hydroxide) at 60°C for 10 minutes. Next, the cured substrate was immersed in a roughening solution (an aqueous solution of Concentrate Compact P manufactured by Amtec Japan (KMnO4: 60 g / L, NaOH: 40 g / L)) at 80°C for 20 minutes. Then, the cured substrate was immersed in a neutralization solution (an aqueous solution of Reduction Solution Securiganth P manufactured by Amtec Japan, sulfuric acid) at 40°C for 5 minutes. Finally, the cured substrate was dried at 80°C for 30 minutes to obtain "Evaluation Substrate A'".

[0450] (2) Plating using a semi-additive process Evaluation substrate A' was immersed in an electroless plating solution containing palladium chloride (PdCl2) at 40°C for 5 minutes, followed by immersion in an electroless copper plating solution at 25°C for 20 minutes. Then, it was annealed at 150°C for 30 minutes. A resist layer was then formed, and an etching-based pattern was created. Next, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 20 μm. Finally, it was annealed at 190°C for 90 minutes to obtain "evaluation substrate B'".

[0451] (3) Determination of coating peel strength A cut was made in the conductor layer of the evaluation substrate B' to enclose a rectangular portion with a width of 10 mm and a length of 100 mm. One end of the rectangular portion was peeled off and clamped in a jig (TSE Corporation, AUTO COM type testing machine "AC-50C-SL"). Using the jig, the rectangular portion was peeled off vertically at a speed of 50 mm / min at room temperature, and the load (kgf / cm) at which 35 mm was peeled off was used as the plating peel strength.

[0452] <Determination of the arithmetic mean roughness (Ra) of the surface of the insulation layer after roughening treatment> The arithmetic mean roughness (Ra) of the insulating layer surface of the roughened cured substrate (evaluation substrate A) prepared in the <Evaluation Test for Contamination Removability> was determined using a non-contact surface roughness meter (Bruker WYKO GT-X), with VSI mode, a 50x lens, and a measurement range set to 121 μm × 92 μm. The values ​​were obtained by calculating the average of 10 points.

[0453] <Determination of Warpage> (1) Preparation of inner layer substrate The copper on both sides of a glass cloth substrate epoxy resin double-sided copper-clad laminate (copper foil thickness 18μm, substrate thickness 0.2mm, manufactured by Lisennoco "E700G") is removed by etching to obtain the inner substrate.

[0454] (2) Lamination of resin sheet A Using a batch vacuum pressure laminator (Nikko-Materials Co., Ltd., 2-stage stacking laminator "CVP1700"), resin sheets A cut to 110mm × 150mm are laminated onto the center of one side of an inner layer substrate cut to 120mm × 160mm, with the resin composition layer in contact with the inner layer substrate. The lamination is performed as follows: after depressurization for 30 seconds to adjust the pressure to below 13hPa, it is pressed for 10 seconds at 140°C and 0.74MPa.

[0455] (3) Thermosetting of the resin composition layer Then, the inner substrate with the resin sheet A stacked on it is placed in an oven at 130°C and heated for 30 minutes, followed by heating in an oven at 170°C for 30 minutes to thermally cure the resin composition layer and form an insulating layer. Then, the support is peeled off to obtain a cured substrate Y with an insulating layer / inner substrate structure.

[0456] (4) Evaluation of warping after complete curing The cured substrate Y was placed in an oven at 200°C and heated for 90 minutes to obtain a cured substrate Y'. The cured substrate Y' was placed on a flat table, and the two adjacent sides were fixed to the table. The distance from the table to the cured substrate Y' was measured with a ruler, and the value was recorded as the warpage.

[0457] <Reflow Soldering Test> (1) Preparation of inner layer substrate Will as Figure 1 The glass cloth substrate epoxy resin double-sided copper-clad laminate (copper foil thickness 35μm, substrate thickness 0.2mm, manufactured by Lisennoco "E700G") with inner layer circuitry shown is etched to 1μm on both sides with a micro-etching agent (MEC "CZ8101") to roughen the copper surface, thus obtaining the inner layer substrate. Figure 1 As shown, four types of inner layer circuits are formed on the inner layer substrate. Figure 1 Point 10 refers to the copper foil with holes formed on the surface of the epoxy resin of the glass cloth substrate, exposing the epoxy resin of the glass cloth substrate. That is, no holes are formed in the copper foil in inner layer circuit 1, holes are formed in the copper foil at 1.5mm intervals in inner layer circuit 2, holes are formed in the copper foil at 1mm intervals in inner layer circuit 3, and holes are formed in the copper foil at 0.5mm intervals in inner layer circuit 4.

[0458] (2) Lamination of resin sheet A Using a batch vacuum pressure laminator (Nikko-Materials Co., Ltd., 2-stage stacking laminator "CVP1700"), resin sheet A is laminated onto both sides of the inner layer substrate in such a manner that the resin composition layer contacts the inner layer substrate. The lamination is performed as follows: after depressurization for 30 seconds to adjust the pressure to below 13 hPa, it is pressed for 10 seconds at 140°C and 0.74 MPa. Next, it is hot-pressed for 60 seconds at 110°C and 0.5 MPa to smooth the resin composition layer.

[0459] (3) Thermosetting of the resin composition layer Then, the inner substrate with the resin sheet A stacked on it is placed in an oven at 130°C and heated for 30 minutes, followed by heating in an oven at 170°C for 30 minutes to thermally cure the resin composition layer and form an insulating layer. Then, the support is peeled off to obtain a cured substrate P with an insulating layer / inner substrate / insulating layer structure.

[0460] (4) Roughening treatment The cured substrate P was immersed in a swelling solution (Swelling Dip Securiganth P manufactured by Amtec Japan, an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60°C for 10 minutes. Next, the cured substrate was immersed in a roughening solution (Concentrate Compact P manufactured by Amtec Japan (an aqueous solution of KMnO4: 60 g / L and NaOH: 40 g / L)) at 80°C for 20 minutes. Then, the cured substrate was immersed in a neutralization solution (Reduction Solution Securiganth P manufactured by Amtec Japan, an aqueous solution of sulfuric acid) at 40°C for 5 minutes. Finally, the cured substrate was dried at 80°C for 30 minutes to obtain the "evaluation substrate Q".

[0461] (5) Plating using a semi-additive process Evaluation substrate Q was immersed in an electroless plating solution containing palladium chloride (PdCl2) at 40°C for 5 minutes, followed by immersion in an electroless copper plating solution at 25°C for 20 minutes. Then, it was annealed at 150°C for 30 minutes. Next, a resist layer was formed, and an etching-based pattern was created. Then, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 20 μm. Finally, it was annealed at 190°C for 90 minutes to obtain "evaluation substrate R".

[0462] (6) Reflow soldering test The evaluation substrate R was cut according to the four inner layer circuit insertion methods described above and absorbed moisture for 19 hours in a constant temperature and humidity bath at 85% RH and 55°C. Then, it was reflow soldered at a peak temperature of 260°C using a reflow oven. The same test piece was reflowed 20 times, and any expansion was recorded. Evaluation was performed according to the following criteria. “○”: No expansion “×”: There is expansion

[0463] As shown in Table 1, Examples 1-17, which contain (A) a maleimide compound with a specific structure, (B) an epoxy resin, and (C) a polycarbodiimide compound, exhibit excellent stain removal properties and excellent heat resistance (glass transition temperature), and also show high adhesion strength (CZ copper peel strength) even when exposed to high temperature and high humidity environments, resulting in cured products that possess all three properties. On the other hand, Comparative Examples 1-7, which do not contain component (A) or component (C), show at least one deterioration in stain removal properties, heat resistance (glass transition temperature), and adhesion strength (CZ copper peel strength), failing to possess all three properties.

[0464] Symbol Explanation 1. Inner layer circuitry not exposed on the resin substrate 2. The exposed inner layer circuitry on the resin substrate is spaced 1.5mm apart. 3. The exposed inner layer circuitry on the resin substrate is spaced 1.0 mm apart. 4. The exposed inner layer circuitry on the resin substrate is spaced 0.5mm apart. 10. Exposed portion of the resin substrate (0.2 mm in diameter).

Claims

1. A resin sheet for forming an insulating layer of a semiconductor packaging substrate, the resin sheet having a support and a resin composition layer disposed on the support. The resin composition layer contains: (1A) A maleimide compound having a partial structure as shown in formula (1), a partial structure as shown in formula (T-1) chemically bonded to the partial structure as shown in formula (1), and a partial structure as shown in formula (T-2) chemically bonded to the partial structure as shown in formula (1). (B) Epoxy resin, and (C) Polycarbodiimide compounds, In equation (1), R a1 R a2 R a3 and R a4 Each can independently represent a hydrogen atom or a hydrocarbon group with 1 to 18 carbon atoms. R 13 Each can independently represent a hydrocarbon group with 1 to 18 carbon atoms. m 2 Each represents an integer from 0 to 4 independently, n 1 Indicates the number of repeating units. The two asterisks represent connecting keys, indicating that a connecting key is in the L of the following equation (T-1). 13 or L 14 The two bonds are chemically bonded at one position, and the other linking bond is in the L position of the following formula (T-2). 11 or L 12 Chemical bonding occurs at the position of [the location]. In the above equations (T-1) and (T-2), R 11 and R 15 Each can independently represent a hydrocarbon group with 1 to 18 carbon atoms. R 12 and R 14 Each can independently represent a hydrocarbon group with 1 to 18 carbon atoms. L 11 L 12 L 13 and L 14 Each represents a connector independently, where, In L 11 or L 12 The position is chemically bonded to part of the structure shown in equation (1), and in L 13 or L 14 The position is chemically bonded to part of the structure shown in equation (1). m 1 and m 3 Each can independently represent an integer from 0 to 2.

2. The resin sheet for forming the insulating layer of the semiconductor packaging substrate according to claim 1, wherein, In equations (T-1) and (T-2), L is not chemically bonded to the partial structure shown in equation (1). 11 L 12 L 13 and L 14 Bonded to a hydrogen atom or a monovalent group as shown in formula (4) below, In equation (4), R a5 and R a6 Each can independently represent a hydrogen atom or a hydrocarbon group with 1 to 18 carbon atoms. R 16 Each can independently represent a hydrocarbon group with 1 to 18 carbon atoms. m 4 Represents integers from 0 to 5. * indicates a connection key.

3. A resin sheet for forming an insulating layer of a semiconductor packaging substrate, the resin sheet having a support and a resin composition layer disposed on the support. The resin composition layer contains: (2A) Maleimide compounds having the structural unit shown in formula (2) below, (B) Epoxy resin, and (C) Polycarbodiimide compounds, In equation (2), R a1 R a2 R a3 R a4 R a5 and R a6 Each can independently represent a hydrogen atom or a hydrocarbon group with 1 to 18 carbon atoms. R 11 Each can independently represent a hydrocarbon group with 1 to 18 carbon atoms. R 12 Each can independently represent a hydrocarbon group with 1 to 18 carbon atoms. R 13 Each can independently represent a hydrocarbon group with 1 to 18 carbon atoms. R 16 Each can independently represent a hydrocarbon group with 1 to 18 carbon atoms. m 1 Each represents an integer from 0 to 2 independently, m 6 Each element independently represents an integer from 0 to 2, and satisfies m 1 +m 6 ≤2,m 2 Each represents an integer from 0 to 4 independently, m 4 Each can independently represent an integer from 0 to 5. n 1 Each element independently represents the number of repeating units.

4. The resin sheet for forming the insulating layer of the semiconductor packaging substrate according to claim 3, wherein, (2A) is a maleimide compound having the structure shown in formula (3) below. In equations (3), (4), and (5), R a1 R a2 R a3 R a4 R a5 and R a6 Each can independently represent a hydrogen atom or a hydrocarbon group with 1 to 18 carbon atoms, R 11 Each can independently represent a hydrocarbon group with 1 to 18 carbon atoms. R 12 Each can independently represent a hydrocarbon group with 1 to 18 carbon atoms. R 13 Each can independently represent a hydrocarbon group with 1 to 18 carbon atoms. R 16 Each can independently represent a hydrocarbon group with 1 to 18 carbon atoms. m 1 Each represents an integer from 0 to 2 independently, m 6 Each represents an integer from 0 to 2 independently, m 5 Each element independently represents an integer from 0 to 3, and satisfies m 1 +m 6 ≤2 and m 1 +m 5 ≤3, m 2 Each represents an integer from 0 to 4 independently, m 4 Each can independently represent an integer from 0 to 5. n 1 Each of these elements independently represents the number of repeating units, and each of these elements independently represents an integer greater than or equal to 1. X M1 This represents a hydrogen atom or a monovalent group as shown in formula (4). X M2 This represents a hydrogen atom or a monovalent group as shown in formula (5). * indicates a connection key.

5. The resin sheet for forming the insulating layer of the semiconductor packaging substrate according to any one of claims 1 to 4, wherein, R 13 Each is an alkyl group having 1 to 18 carbon atoms.

6. The resin sheet for forming the insulating layer of the semiconductor packaging substrate according to claim 1 or 2, wherein, The mass ratio of component (1A) to component (C) in the resin composition layer [(1A) component / (C) component] is 0.1 to 50.

7. The resin sheet for forming the insulating layer of the semiconductor packaging substrate according to claim 3 or 4, wherein, The mass ratio of component (2A) to component (C) in the resin composition layer [component (2A) / component (C)] is 0.1 to 50.

8. The resin sheet for forming the insulating layer of a semiconductor packaging substrate according to any one of claims 1 to 4, wherein, The resin composition layer further contains (D) a curing agent.

9. The resin sheet for forming the insulating layer of the semiconductor packaging substrate according to claim 8, wherein, The ratio of the number of moles of the active groups of the curing agent (D) to the number of moles of the epoxy groups of the epoxy resin in the resin composition layer, i.e., the ratio of the number of moles of the active groups of the curing agent to the number of moles of the epoxy groups of the epoxy resin, is 1 or more.

10. The resin sheet for forming the insulating layer of the semiconductor packaging substrate according to any one of claims 1 to 4, wherein, The resin composition layer further contains (E) inorganic filler material.

11. The resin sheet for forming the insulating layer of the semiconductor packaging substrate according to claim 10, wherein, When the non-volatile component in the resin composition layer is set to 100% by mass, the content of component (E) in the resin composition layer is 80% by mass or less.

12. The resin sheet for forming the insulating layer of the semiconductor packaging substrate according to claim 1 or 2, wherein, The resin composition layer further contains maleimide compounds other than component (1A), hereinafter referred to as "(1F) other maleimide compounds".

13. The resin sheet for forming the insulating layer of the semiconductor packaging substrate according to claim 3 or 4, wherein, The resin composition layer further contains maleimide compounds other than component (2A), hereinafter referred to as "(2F) other maleimide compounds".

14. The resin sheet for forming the insulating layer of the semiconductor packaging substrate according to any one of claims 1 to 4, wherein, The resin composition layer further contains (G) free radical polymerizable resin.

15. The resin sheet for forming the insulating layer of a semiconductor packaging substrate according to any one of claims 1 to 4, wherein, The resin composition layer further contains (H) organic filler material.

16. The resin sheet for forming the insulating layer of a semiconductor packaging substrate according to any one of claims 1 to 4, wherein, The resin composition layer further contains (I) a curing accelerator.

17. The resin sheet for forming the insulating layer of the semiconductor packaging substrate according to any one of claims 1 to 4, wherein, The support is a thermoplastic resin film or metal foil.

18. A semiconductor packaging substrate having an insulating layer comprising a cured resin composition layer of a resin sheet for forming an insulating layer of the semiconductor packaging substrate according to any one of claims 1 to 4.

19. A semiconductor device comprising the semiconductor packaging substrate of claim 18.

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